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Nanoscience and nanotechnology in Spain 2010-2011

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This second version of the report “Nanoscience & Nanotechnology in Spain” provides insights by identifying R&D directions and priorities in Spain. Moreover, it aims to be a valid source …

This second version of the report “Nanoscience & Nanotechnology in Spain” provides insights by identifying R&D directions and priorities in Spain. Moreover, it aims to be a valid source of guidance, not only for the scientific community but also for the industry.

This report covers a wide range of interdisciplinary areas of research and development, such as Graphene, Nanochemistry, Nanomedicine, Carbon
Nanotubes, Nanomaterials for Energy, Modelling, etc., and provides insights in these areas, currently very active worldwide and particularly in Spain. It
also provides an outlook of the entire Spanish nanotechnology system, including nearly 250 research institutions and over 50 companies.

Expected impact of initiative s suc h a s this document is to enhance visibility, ommunication and networking between specialists in several
fields, facilitate rapid information flow, look for
areas of common ground between different technologies and therefore shape and consolidate the Spanish and European research communities.

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  • 1. Nanoscience and Nanotechnology in SPAINFunded by In collaboration with Coordinated and edited by
  • 2. Coordinator Antonio Correia (Phantoms Foundation)Design and Layout Carmen Chacón (Phantoms Foundation) Viviana Estêvão (Phantoms Foundation) Maite Fernández (Phantoms Foundation) Concepción Narros (Phantoms Foundation) José Luis Roldán (Phantoms Foundation)Experts Adrian Bachtold - Carbon nanotubes and Graphene Fundació Privada Institut Català de Nanotecnologia (ICN), Barcelona Antonio Correia - Introduction - Preface Phantoms Foundation and NanoSpain Network Coordinator, Madrid Viviana Estêvão - Introduction Phantoms Foundation, Madrid Ricardo García - Scanning Probe Microscopy Instituto de Microelectrónica de Madrid (IMM-CNM, CSIC), Madrid Francisco Guinea - Carbon nanotubes and Graphene Instituto de Ciencia de Materiales de Madrid (ICMM, CSIC), Madrid Wolfgang Maser - Carbon nanotubes and Graphene Instituto de Carboquímica (ICB, CSIC), Zaragoza Rodolfo Miranda - Nanomaterials IMDEA: Madrid Institute for Advanced Studies in Nanosciences (Imdea Nanociencia) Xavier Obradors - Nanomaterials for Energy Materials Science Institute of Barcelona, Barcelona Roberto Otero - Nanomaterials IMDEA: Madrid Institute for Advanced Studies in Nanosciences (Imdea Nanociencia) Francesc Pérez-Murano - Nanoelectronics and Molecular Electronics Instituto de Microelectrónica de Barcelona (IMB-CNM, CSIC), Barcelona Emilio Prieto - Nanometrology, nano-eco-toxicology and standardization Spanish Centre of Metrology (CEM), Madrid Stephan Roche - Carbon nanotubes and Graphene Centre d’ Investigació en Nanociencia y Nanotecnología (CIN2, ICN-CSIC), Barcelona Juan José Sáenz - Theory and Simulation Universidad Autónoma de Madrid, Madrid Josep Samitier - Nanomedicine Institute for Bioengineering of Catalonia and Universitat of Barcelona, Barcelona Pedro A. Serena - Introduction Instituto de Ciencias de Materiales de Madrid (ICMM-CSIC), Madrid Niek van Hulst - Nanooptics and Nanophotonics The Institute of Photonic Sciences (ICFO), Barcelona Jaume Veciana - Nanochemistry Instituto de Ciencia Materiales de Barcelona (ICMAB-CSIC), BarcelonaDisclaimer The Phantoms Foundation has exercised due diligence in the preparation and reporting of information contained in this book, obtaining information from reliable sources. The contents/opinions expressed in this book are those of the authors and do not necessarily reflect views of the Phantoms Foundation.
  • 3. C O N T E N T S05 Preface07 Introduction19 Nanoscience & Nanotecnology in Spain: Research Topics 19 27 37 45 59 67 81 89 95105113 Emerging N&N Centers in Spain113114116117119120123124126129130 Annex I: Spanish Nanotechnology Network (NanoSpain) / Statistics144 Annex II: R&D funding148 Annex III: Publications / Statistics152 Annex IV: Spain Nanotechnology Companies (Catalogue)156 Annex V: NanoSpain Conferences160 Annex VI: Maps for relevant Spanish Initiatives
  • 4. 4
  • 5. PREFACEConsidering the fast and continuous technologies and therefore shape andevolvements in the interdisciplinary field of consolidate the Spanish and European researchNanotechnology, Institutions such as the communities.Phantoms Foundation and national initiativessuch as the Spanish Nanotechnology Network I hope you will enjoy reading this document, a“NanoSpain”, should help identifying and collection of ten chapters written by researchersmonitoring the new emerging fields of research, who are at the forefront of their field in N&N,drivers of interest for this Community, in and look forward to the next edition beginningparticular in Spain. of 2013 which will explore some new strategic research areas.Therefore, this second version of the report“Nanoscience & Nanotechnology in Spain” I would also like to thank all the authors andprovides insights by identifying R&D directions reviewers for turning this project into reality.and priorities in Spain. Moreover, it aims to be avalid source of guidance, not only for thescientific community but also for the industry. The EditorThis report covers a wide range of interdisciplinary Dr. Antonio Correiaareas of research and development, such as Phantoms FoundationGraphene, Nanochemistry, Nanomedicine, Carbon (Madrid, Spain)Nanotubes, Nanomaterials for Energy, Modelling,etc., and provides insights in these areas, currentlyvery active worldwide and particularly in Spain. Italso provides an outlook of the entire Spanishnanotechnology system, including nearly 250research institutions and over 50 companies.Expected impact of initiatives such as thisdocument is to enhance visibility, communicationand networking between specialists in severalfields, facilitate rapid information flow, look forareas of common ground between different 5
  • 6. > ANTONIO CORREIAPlace and date of birthParis (France), 1966EducationPhD in Materials Science, Universidad Paris 7, 1993ExperienceAntonio Correia has over 15 years’ experience with projects and initiatives related with Nanoscience and Nanotechnology networking. He isauthor or co-author of 60 scientific papers in international journals and guest Editor of several books. Antonio Correia is currently Presidentof the Phantoms Foundation (Spain) and Coordinator/Board member of several EU funded projects (nanoICT, AtMol, MULT-EU-SIM, nanoCODE,nanomagma, COST “BioInspired Nanotechnologies”) or initiatives (NanoSpain, M4nano, ICEX Spanish Nanotechnology plan, etc.). Chairmanof several conferences (TNT, Nanospain, Imaginenano or Graphene), he is also editor of the Enano newsletter published by the PhantomsFoundation.antonio@phantomsnet.net> VIVIANA ESTÊVÃOPlace and date of birthCaldas da Rainha (Portugal), 1982 Education • Degree in Public Relations & Advertising, INP, 2004. • Master Degree in Digital Marketing, EUDE. Experience Works at Phantoms Foundation since January 2010 after a long period working in United Kingdom and Portugal as Marketing Researcher & Communications Account within a broad range of sectors & clients. viviana@phantomsnet.net > PEDRO A. SERENA Place and date of birth Madrid (Spain), 1962 Education • Degree in Physical Sciences, Universidad Autónoma de Madrid, 1985 • PhD in Physics, Universidad Autónoma de Madrid, 1990 Experience Researcher at the Madrid Materials Science Institute (ICMM) of Spanish National Research Council (CSIC). His research interests include the theoretical study of mechanical and electrical properties of nanosized and low-dimensional systems (metallic surfaces, clusters and nanowires, viral capsids, etc). He is co- author of 125 articles published in international and national journals covering different topics: basic science, scientific dissemination, scientific policy, technologies convergence, prospective studies, sustainable development, etc. He has been editor of the book “Nanowires” (Kluwer,1997), and co-author of the “Unidad Didáctica sobre Nanotecnología” (FECyT, Spain, 2009) and author of the book “¿Qué sabemos de la nanotecnología?” (CSIC-La Catarata, 2010). He was coordinator (2000-2003) of the Nanoscience Network and co-founder and co-coordinator (2000-2005) of the NanoSpain Network. Since 2002 to 2005 he was Deputy Director of the ICMM . From 2007 he has been working as Advisor/Assistant of the Spanish Ministry for Science and Innovation to manage the Strategic Action in Nanoscience and Nanotechnology.From 2006 is secretary of the Scientific Advisory Board of the Madrid Science Park and from 2010 is member of the CSIC Scientific Advisory Committee. pedro.serena@icmm.csic.es 6
  • 7. INTRODUCTION1. Introduction existent to being object of extensive articles and reports in scientific and non-scientific journals,Nanoscience and Nanotechnology (N&N) have as well as to be a favorite discussion topic in webbecome a rapidly growing research and pages, forums and blogs in Internet.development (R&D) field that is cutting acrossmany traditional research topics. Nowadays the When we speak about social impact, we areability to construct nano-objects and nano- referring to the capacity of Nanotechnology todevices provides novel advanced materials and generate applications and devices that willastonishing devices and will lead to the future induce true changes in our daily life, our jobs, ourdevelopment of fully functional nano-machines homes, our health, etc. N&N will fundamentallyand nano-materials, virtually having an effect on restructure the technologies currently used forevery manufactured product, the production and manufacturing, medicine, security, defence,storage of energy, and providing a host of medical energy production and storage, environmentalapplications ranging from in situ and real time management, transportation, communication,diagnostics to tissue regeneration. N&N are more computation and education. Given thethan simply the next frontier in miniaturization, multidisciplinary character of N&N, the list ofsince the properties of materials and devices expected application areas is very long.dramatically change when their characteristicdimensions moves down the nanoscale, revealing The broad scope of N&N applications will affectan entirely new world of possibilities. different aspects of the activity of human beings. Nevertheless, we can highlight that many of2. Potential nanotechnology applications and these applications are focused on thetheir social impact improvement of human health, whereas others will facilitate a more sustainable economicThe evaluation of the expected impact of a development allowing the optimization oftechnology wave is always an uncertain business. resources and diminishing environmental impact.Yet there seems little doubt that the very natureof nanotechnology will precipitate important 3. Nanotechnology Research Fundingchanges, the only question is its timetable. In thecase of N&N, perhaps, the first measurable Nanoscience, transformed in Nanotechnology, isimpact has been its effect on the media. In a taking now its first steps outside the laboratoriesdecade everything nano has gone from non- and many small and large companies are 7
  • 8. N & N i n S p a i n launching a first wave of nanoproducts into the control of Nanotechnology know-how. According markets. However, the actual power of to Mihail Roco, Japan increased their budget Nanotechnology resides in an immense potential from US$ 245 million in 2000 to US$ 950 million for the manufacture of consumer goods that, in in 2009, proving a significant rising of the many cases, will not be commercialized before a investment from the Japanese Government. couple of decades, thus bringing tangible and Taiwanese, Japanese and South Korean promising results for the economy. Because this companies are leading the NanotechnologyINTRODUCTION huge expected economic impact, investments in their respective countries. In the nanotechnology has roused great interest among meantime, China has become a key player in the the relevant public and private R&D stakeholders Nanotechnology field, leading sectors as the of the world’s most developed countries: funding fabrication of nanoparticles and nanomaterials. agencies, scientific policymakers, organisations, Countries as Israel, Iran, India, Singapore, institutions and companies. Thailand, Malaysia and Indonesia have launched specific programmes to promote the use of N&N represent one of the fastest growing areas Nanotechnologies in many industrial sectors with of R&D. In the period of 1997-2005 worldwide local or regional impact (manufacture, textile, investment in Nanotechnology research and wood, agriculture, water remediation, etc). development has increased approximately nine times, from US$ 432 million to US$ 4200 million. Europe has intensively promoted This represents an average annual growth rate of Nanotechnology within the VI (FP6) and the VII 32%. A great example is the National (FP7) Framework Programme through thematic Nanotechnology Initiative (NNI) that was Areas denominated NMP1 and ICT2. During the established in 2000 and links 25 federal agencies period of 2003-2006 the budget for NMP was closely related to activities in N&N. NNI budget 1429 million Euros and a remarkable increase of allocated to the federal departments and agencies 3475 million Euros for funding N&N over the increased from US$ 464 million in 2001 to duration of FP7 (2007-2013). There’s a proven approximately US$ 1700 million in 2009. For 2011 commitment of the EU to strengthen research in the funding request for nanotechnology research Europe. Initiatives involving not only increased and development (R&D) in 15 federal investment, but also stronger coordination and departments and agencies is US$ 1760 million, collaboration between all stakeholders like the reflecting a continuous growth in strategic FET flagship (ICT) are being implemented. In collaboration to accelerate the discovery and order to improve the competitiveness of deployment of nanotechnology. In addition to the European industry, to generate and ensure federal initiative, an important effort has been transformation from a resource-intensive to a carried out by the different US state governments, knowledge-intensive industry were created the as well as companies (Motorola, Intel, Hewlett- FET Flagships Initiatives. FET-Proactive acts as a Packard, IBM, Amgen, Abbot Lab., Agilent, etc). pathfinder for the ICT program by fostering novel non-conventional approaches, Industrialized Asian countries have promoted foundational research and supporting initial the development of Nanotechnology from the developments on long-term research and industrial and governmental sectors, with technological innovation in selected themes. investments similar to those of USA. Countries Under the FP7 program were created AMOL-IT, as Taiwan and Korea have made a great effort to nanoICT and Towards Zero-Power ICT projects in keep their current privileged positions in the order to focus resources on visionary and 8
  • 9. N & N i n S p a i nchallenging long-term goals that are timely and coordinates NANO measures on the nationalhave strong potential for future impact. There and regional levels and is supported by severalhas been a boom of European initiatives Ministries, Federal provinces and Fundingdedicated to develop and popularize institutions, under the overall control of theNanotechnology and this area maintains its BMVIT Federal Ministry for Transport,outstanding role in the FP7 Program. Innovation and Technology. The orientation and the structure of the Austrian NANO Initiative INTRODUCTIONAmong the EU members, Germany stands right have been developed jointly with scientists,at the forefront of international Nanoscience entrepreneurs and intermediaries. The Austrianand is considered as a key location for nano NANO Initiative4 has funded nine RTD projectresearch. The Federal Government by clusters involving more than 200 Austrianexceptional funding programs is helping to turn companies and research institutions.Germany into the leading nano spot. In 2008about 430 million Euros were invested by public EU authorities have also taken into accountfunding in Nanotechnology. Nowadays, around serious concerns on Nanotechnology, appearing740 companies work on the development, in diverse social and economic forums during theapplication and distribution of nanotechnology last decade, in relation with its possibleproducts. Following similar long term strategies, environmental and health effects. These non-on December 2009, French Government desired drawbacks would provide a negativeunveiled a 35000 million Euros national bond to social perception on the development onprepare France for the challenges of the future. Nanotechnology and could lead to an unexpectedThe spending spree over the coming years cut of private and public investments, with thecontemplates higher education and research as subsequent delay in the arrival of the bunch ofthe main priorities, among others. Part of this promised goods, devices and materials. In orderamount will be applied to create new Campus of to allow a coherent (rational, sustainable, non-Excellence, develop research teams, boost aggressive, etc) development of Nanotechnology,competitiveness and increase efforts in the EU has promoted basic and applied researchbiotechnology and nanotechnology. The on nanoecotoxicology and different studies onNanoNextNL3 (2011-2016) consortium in social perception on N&N. Simultaneously,Netherlands which supports research in the field several EU Departments have launched initiativesof nano and microtechnology is another great to improve the communication andexample of the efforts made by the European dissemination among population on the futurecountries. This initiative embrace 114 partners advances and risks that Nanotechnology willand the total sum involved is 250 million Euros, bring. A good example is the European Projecthalf of which is contributed by the collaboration NanoCode5, funded under the Programof more than one hundred businesses, Capacities, in the area Science in Society, withinuniversities, knowledge institutes and university the 7th Framework Program (FP7) which startedmedical centres and the other half by the in January 2010 in order to implement theMinistry of Economic Affairs, Agriculture and European Code of Conduct for ResponsibleInnovation. NanoNextNL is the successor of Nanosciences & Nanotechnologies.NanoNed and MicroNed programmes whichwere also greatly supported. In the same line, In addition, EU has also promoted the generationwe must mention the Austrian NANO Initiative, of knowledge based on Nanotechnologya multi-annual funding programme for N&N that emphasizing the role of this techno-scientific area 9
  • 10. N & N i n S p a i n as foundation for future convergence with other enabled communication between scientific disciplines such as Biotechnology, Medicine, communities and different areas, improving the Cognitive Science, Communications and interaction between Spanish groups and Information Technologies, Social Sciences, etc. improving the visibility of this community. NanoSpain network6 is the clearest example of 4. Nanotechnology in Spain: a successful history self-organization of scientists that helped to promote to the authorities and the general publicINTRODUCTION At the end of 90´s, Spain had not any the existence of this new knowledge, in order to institutional framework nor initiative pointed generate and achieve competitive science, which towards the support and promotion of R&D in can result into high value added products in the Nanotechnology. This fact pushed the scientific near future. NanoSpain network comprises community to promote several initiatives to nearly 300 R&D groups (See Annex I) from strengthen research in Nanotechnology and, at universities, research centers and companies, the same time, to raise the awareness of Public distributed throughout the country. These groups Administration and industry about the need to respresent a research task force formed by more support this emergent field. than 2000 scientists working in N&N. Despite being the meeting point of the continuously Among the initiatives that emerged in Spain in increasing Spanish nanotechnology community, this last decade we can highlight the creation of NanoSpain network has received little support several thematic networks with a strong from Spanish Administration in contrast to those multidisciplinary character. These networks have networks established in other countries. Figure 1. Regional Distribution of research groups – NanoSpain Network. (As of March 31, 2010). 10
  • 11. N & N i n S p a i nAnother Spanish initiative, which emerged from scale initiatives as the building of new R&Dthe scientific community and has become an centers or public-private consortia and platforms.international benchmark, is the celebration ofeleven consecutive editions of the conference The International Campus of Excellence program"Trends in Nanotechnology"7. These meetings, was discussed in 2008, first staged competitivelya true showcase of Spanish nanoscience and in 2009 and in 2010 became firmly establishednanotechnology, attracted the most prestigious and aims to put major Spanish universities among INTRODUCTIONinternational researchers, improving the the best in Europe, promoting internationalvisibility of Spanish scientists. The international recognition and supporting the strengths of theevent, ImagineNano8, is also a step further, a Spanish university system. The program ismeeting that gather nearly 1500 participants managed by the Ministry of Education infrom all over the world, combining within the collaboration with other ministries and supportedsame initiative a set of high impact conferences by the Autonomous Communities. In many cases,and an industry exhibition with more than 160 as the Excellence Campus of Universidadinstitutions/companies. Autónoma de Madrid or the Universidad Autónoma de Barcelona include remarkableIn early 2003 the initiatives launched by the activities related to the promotion of N&N.scientific community (networks, workshops,conferences) related to nanotechnology led to the Under the policies of the General Stateincorporation of the Strategic Action in Administration (GSA), the Ingenio 2010 programNanoscience and Nanotechnology in the National through programs such as CENIT, CONSOLIDERPlan R+D+I for the 2004-2007 period. This and AVANZA, allowed many economic resourcesStrategic Action has had its continuity in the in strategic areas such as nanotechnology.current National Plan (2008-2011), also including Currently, 8 CONSOLIDER and 9 CENIT projectstopics related to new materials and production are related to nanotechnology, with a total GSAtechnologies. Both strategic actions maintained an funding of 37.9 and 127.8 million Euros,increasing rate of investment in nanotechnology respectively. In the case of CENIT projects,in the period of 2004-2009. For example, the participating companies provided an additionaleffort made by the General State Administration amount of 127.8 M €. Over the next few years(GSA) in the implementation of N&N has been we expect to see the results of these initiativesover 82 million Euros in 2008. During the 2004- through several indicators. Another important2007 period the Strategic Action focused on small initiative is the Biomedical Research Networkingscale projects whereas during the 2008-2011 center in Bioengineering, Biomaterials andperiod the funding was mainly allocated to large Nanomedicine9 (CIBER-BBN), a consortia, created under the leadership of the “Carlos III Health Institute” (ISCIII) to promote research excellence in bioengineering and biomedical imaging, biomaterials and tissue engineering and nanomedicine, diagnosis and monitoring and related technologies for specific treatments such as regenerative medicine and nanotherapies.Table 1. Fiscal effort made by Spanish government in the field of In addition to GSA strategies, the regionalNanoscience and Nanotechnology in the year 2008 (Source: Ministry governments expressed with more or lessof Science and Innovation of Spain). 11
  • 12. N & N i n S p a i nINTRODUCTION Figure 2. Emerging N&N Centers in Spain. emphasis their interest in nanotechnology, membership of other countries of Europe and including this topic in its regional plans of R&D other regions of the world. and encouraging the creation of new regional networks. However, most palpable manifestation Some of the centers indicated in Fig. 2 are under of the widespread interest in nanotechnology is construction and are expected to be fully the establishment of new research centers as operational during the decade 2010-2020. This joint projects of the Ministry of Science and set of centers, along with those already existing Innovation, Autonomous Communities and in the public research organizations, the network Universities. (See Annex VI and Fig. 2). of Singular Scientific and Technological Infrastructures forms a system of huge potential The International Iberian Nanotechnology forms research in nanoscience and Laboratory10 (INL) is the result of a joint decision nanotechnology. The task of knowledge of the Governments of Portugal and Spain, taken generation must be completed by the technology in November 2005 whereby both countries transfer offices of universities and public research made clear their commitment to a strong organizations, the Technology Centers, and the cooperation in ambitious science and many Science and Technology Parks that have technology joint ventures for the future. The been successfully implemented in Spain11. Also new laboratory is established by Portugal and emerge thematic "nano-networks" and “nano- Spain, but in the future will be open to the platforms” oriented to productive sectors as 12
  • 13. N & N i n S p a i nRENAC12 (Network for the application of designed to spread among teachers in secondarynanotechnologies in construction and habitat and high school education along with booksmaterials and products), SUSCHEM13 (Spanish devoted to N&N dissemination that have beenTechnology Platform on Sustainable Chemistry), recently issued. On the other hand, events asGÉNESIS14 (Spanish Technology Platform on “Atom by Atom” or “Passion for Knowledge”Nanotechnology and Smart Systems Integration), disclose the progresses, challenges andNANOMED15 (Spanish Nanomedicine Platform), implications of various “nano-areas” to a broad INTRODUCTIONMATERPLAT16 (Spanish Technological Platform on and general audience. Furthermore, initiatives asAdvanced Materials and Nanomaterials) or the SPMAGE international contest19 of SPMFotonica2117 (The Spanish Technology Platform of (Scanning Probe Microscopy) images or thePhotonics), among many others. exhibition “A walk around the nanoworld” are succesful initiatives to disseminate N&N. Recently,These strategies for generation and transfer of an Iberoamerican Network for Dissemination andknowledge are reinforced by other Training in N&N (NANODYF)20 has been funded bycomplementary activities aimed at both the the Iberoamerican Programme for Science andinternationalization of our scientific-technological Technology (CYTED) in order to promote formalresults and the dissemination of science. As an and non-formal education of N&N inexample of the internationalization, the Spanish Iberoamerican countries where more than 460Institute of Foreign Trade (ICEX), through its million people communicate in Spanish."Technology Plan" in Nanotechnology(coordinated by Phantoms Foundation) One could say that in this last decade we haveencourages external promotion activities of seen an explosion of initiatives in the field ofresearch centers and companies, enabling the nanotechnology. All initiatives represent a clearparticipation of Spain with pavilions and commitment that Spain is situated in theinformative points in several international medium term between the group of countriesexhibitions as Nanotech Japan (2008-2011), one that can lead the change towards a knowledge-of the most important events in nanotechnology, based society. However, it is necessary toNSTI fair (2009) in U.S. and Taiwan Nano (2010)18. maintain a constant tension to strengthen the settlement of all initiatives. The short-termMore recently, a catalogue of N&N companies in challenge is to continue the investement,Spain was compiled by Phantoms Foundation and despite being in an economic crisis, and improvefunded by ICEX and gives a general overview of coordination of all players involved in the R+D+I.the enterprises working in this field. Since the The next decade will confirm whether effortsyear of 2000 until 2010, were created 36 have been sufficient to be amongst the mostcompanies mainly in nanomaterials, advanced economies, fulfilling the expectationsnanocomposites, nanobio and nanoparticles. So for nanotechnology as an engine of Spanishfar 60 companies performing R&D in nanoscience industry in 2020. Everything achieved so far hasand nanotechnology are listed and is predicted a required a great effort, but still we have a R&Dsignificant increase in the upcoming years. system relatively weak compared with those countries which we want to look like. Any changeIn terms of outreach efforts we can mention in the sustained investment policies in our R&Dseveral initiatives. On one hand the edition of the system can take us back several years, as budgetfirst book in N&N issued by the Spanish cuts are announced to overcome this period ofFoundation for Science and Technology (FECYT), crisis they can also be very harmful in an 13
  • 14. N & N i n S p a i n emerging issue as nanotechnology. We hope automation, and therefore contributing to global these cuts are punctual and that soon will regain sustainable development. On the other hand, the road of support R&D&I. the nanotechnological revolution will speed up the seemingly unstoppable expansion of the In the meantime, before recovering the previous information technologies, and causing the momentum, we need to implement new globalization of the economy, the spreading of strategies intended to keep the path we started ideas, the access to the different sources ofINTRODUCTION ten years ago under a more restrictive economic knowledge, the improvement of the educative scenario. These strategies must be based in few systems, etc, to increase vertiginously. Finally, the ingredients, including among others: (i) the irruption of the Nanotechnologies will directly stimulus of the dialogue between Spain affect human beings by substantially improving Ministries and Regional Goverments, on one diagnosis and treatment of diseases, and also our side, and scientific community using existing capacities to interact with our surroundings. networks that must be suitably funded on the other; (ii) the increasing coordination of research Right now we are facing a powerful scientific centres and large scale infrastrutures in order to paradigm with a multidisciplinary character, optimize the access to scientific services of where Chemistry, Engineering, Biology, Physics, public and private groups; (iii) to enhace public- Medicine, Materials Science, and Modelling- private cooperation through Technology Computation converge. Establishing links Platforms, Industry Networks and Science and between the scientific communities, looking for Technology Parks; (iv) an actual support to small contact points and promoting the existence of N&N spin-offs emerging from research centres, multidisciplinary groups, where imaginative (v) the formation of a new generation of PhD solutions to nanoscale problems are forged, students and technicians highly skilled for becomes now essential. multidisciplinary research through specific training programs (Master and PhD courses); Further reading and (vi) the involvement of society through well designed dissemination activities using Introduction emerging communication technologies. • C. P. Poole and F. J. Owens, “Introduction to 5. Conclusions the Nanotechnology”, Wiley-VCH, Weinheim (2003). Nanoscience and Nanotechnology represent • R. Waser (Ed.) “Nanoelectronics and scientific-technical areas that in less than two Information Technology“, Wiley-VCH, decades have gone from being in the hands of a Weinheim (2003). reduced group of researchers who glimpsed • M. Ventra, S. Evoy, J.R. Heflin (Eds.), their great potential, to constitute one of the “Introduction to Nanoscale Science and recognized pillars of the scientific advance for Technology”, Series: Nanostructure Science the next decades. The ability to manipulate the and Technology, Springer (2004). matter on atomic scale opens the possibility of • A. Nouaihat, “An Introduction to Nanosciences designing and manufacturing new materials and and Nanotechnology” , Wiley-ISTE (2008). devices of nanometric size. This possibility will • G. L. Hornyak, J. Dutta, H.F. Tibbals and A. Rao, alter the methods of manufacturing in factories, “Introduction to Nanoscience”, CRC Press allowing for greater process optimization and (2008). 14
  • 15. N & N i n S p a i n• S. Lindsay, “Introduction to Nanoscience”, • Research in Germany: Oxford University Press (2009). www.research-in-germany.de/dach• M- Pagliaro, “Nano-Age: How Nanotechnology portal/en/downloads/download-files/ Changes our Future”, Wiley-VCH (2010). 9434/welcome-to-nanotech-germany.pdf• S.H. Priest, “Nanotechnology and the Public: www.research-in-germany.de/research- Risk Perception and Risk Communication areas/68296/nanotechnology.html (Perspectives in Nanotechnology)”, CRC Press • “Paris plans science in the suburbs”: INTRODUCTION (2011). www.nature.com/news/2010/101020/full/ 467897a.htmlFunding • “French research wins huge cash boost”: www.nature.com/news/2009/091215/• Marks & Clerk, Nanotechnology, Report full/462838a.html (2006). • http://ec.europa.eu/health/ph_risk/• www.nano.gov/about-nni/what/funding documents/ev_20040301_en.pdf• “The long view of Nanotechnology develop- • A. Nordmann, “Converging Technologies – ment: The national Nanotechnology Initia- Shaping the Future of European Societies”: tive at ten years”, Mihail Roco (2011) www.ntnu.no/2020/final_report_en.pdf www.nsf.gov/crssprgm/nano/reports/nano2 /chapter00-2.pdf Nanotechnology in Spain• “Some Figures about Nanotechnology R&D in Europe and Beyond”, European Commis- • I+D+I National Plan 2008-2011 sion, Research DG http://publicacionesopi.micinn.es/docs/ ftp://ftp.cordis.europa.eu/pub/ PLAN_NACIONAL_CONSEJO_DE_ nanotechnology/docs/nano_funding_data_ MINISTROS.pdf 08122005.pdf • P.A. Serena, “Report on the implementation• UE FP7 (NMP theme): of the Action Plan for Nanosciences and http://cordis.europa.eu/fp7/cooperation/ Nanotechnologies in Spain (2005-2007)", nanotechnology_en.html Oficina Europea Micinn:• EU FP7 Nanotechnology funding opportuni- www.oemicinn.es/programa-marco/ ties: http://cordis.europa.eu/ cooperacion/nanociencias-nanotecnologias- nanotechnology/src/eu_funding.htm materiales-y-nuevas-tecnologias-de-la-• EU FP7 Technological Platforms: produccion/documentos-de-interes/in- http://cordis.europa.eu/technology- forme-de-la-implementacion-del-plan-de-ac- platforms/ home_en.html cion-de-nanociencias-y-nanotecnologias-par• FET Flagships a-el-periodo-2005-2007-en-espana http://cordis.europa.eu/fp7/ict/ • P. A. Serena, “A survey of public funding of programme/fet/flagship/ nanotechnology in Spain over 2008”. Mi-• EU-FP7 (ICT-FET) proactive initiative (nano nistry of Science and Innovation report to ICT - NANO-SCALE ICT DEVICES AND SYSTEMS): the European Commission. http://cordis.europa.eu/fp7/ict/fet- www.oemicinn.es/content/ proactive/nanoict_en.html download/1122/7623/file/• http://cordis.europa.eu/search/ REPORT2008-First-Implementation-Plan- index.cfm?fuseaction=prog.document& FINAL-INL.pdf PG_RCN=8737574 15
  • 16. N & N i n S p a i n 14 • www.educacion.gob.es/campus- www.genesisred.net/index.php 15 excelencia.html www.nanomedspain.net 16 • www.micinn.es/portal/site/MICINN/ menui- www.materplat.es 17 tem.7eeac5cd345b4f34f09dfd1001432ea0/? www.fotonica21.org 18 vgnextoid=b0b841f658431210VgnVCM1000 www.phantomsnet.net/nanotech2008/; 001034e20aRCRD (Technological Platforms) www.phantomsnet.net/nanotech2009/; • J.A. Martín-Gago et al. “Teaching Unit www.phantomsnet.net/nanotech2010/;INTRODUCTION Nanoscience and Nanotechnology. Among www.phantomsnet.net/NSTI2009/; the science fiction of the present and the www.phantomsnet.net/Taiwan2010/ 19 future technology”, Foundation for Science www.icmm.csic.es/spmage/ 20 and Technology (FECYT), Madrid 2008 www.nanodyf.org • Event Atom by Atom (San Sebastian, Spain): http://atombyatom.nanogune.eu/ • Event Passion for knowledge (San Sebastian, Spain): www.dipc10.eu/es/passion-for- knowledge • “Industrial Applications of Nanotechnology in Spain in 2020 Horizon, Fundación OPTI and Fundación INASMET-TECNALIA, Madrid. (2008). The book can be downloaded free from: www.opti.org References 1 FP6 Thematic Area denominated “Nanotechnologies and nano-sciences, knowledge-based multifunctional materials and new production processes and devices” and FP7 denominated “Nanosciences, Nanotechnologies, Materials and new Production Technologies” 2 ICT: Information and Communication Technologies 3 www.nanonextnl.nl 4 www.nanoinitiative.at 5 www.nanocode.eu 6 www.nanospain.org 7 www.tntconf.org 8 www.imaginenano.com 9 www.ciber-bbn.es 10 www.inl.int 11 www.apte.org 12 www.nano-renac.com 13 www.suschem-es.org 16
  • 17. N & N i n S p a i n 17
  • 18. > JAUME VECIANA Place and date of birth San Salvador (Rep. El Salvador), 1950 Education Degree in Chemical Science, Univ. Barcelona, June 1973. Doctor in Chemistry, Univ. Barcelona, November 1977. Experience Main research activities are focused on functional molecular materials with metallic- transport and magnetism-properties, supramolecular materials and to the development of molecular nanoscience and nanotechnology. Research is also aimed towards the development of new processing methods for structuring functional molecular materials as nanoparticles and their patterning on surfaces. Also activities in Nanomedicine are currently developed.vecianaj@icmab.es 18
  • 19. NANOCHEMISTRY1. Introduction in this area will contribute to solving multiple societal issues and will have an enormousNanochemistry is the term generally used to impact in many aspects and activities of ourgather all activities of Nanoscience and lives; especially those related with:Nanotechnology (N&N) having in common theuse of the traditional concepts, objectives and a) Energytools of Chemistry. Accordingly, Nanochemistry b) Information and Communication Technologiesdeals with the design, study, production, and c) Healthcaretransformation of basic materials into other d) Quality of Lifeoften more complex products and materials that e) Citizen Protectionshow useful properties due to their nanoscopic f) Transportdimensions. This area of research has thepotential to make a significant impact on our Indeed, activities in this discipline will enable ourworld since it has an enabling character European society to become more sustainable,underpinning technology clusters such as due to new and improved products andmaterials and manufacturing. processes that supply new and existing products more efficiently.Application areas include construction,cosmetics, pharmaceutical, automotive, and Moreover, it is anticipated that the economicalaerospace industry, as well as polymer additives, and social impacts of Nanochemistry in our societyfunctional surfaces, sensors and biosensors, will be very high both in terms of generatingmolecular electronics, and targeted drug greater wealth and larger economical revenues,release. It is just in this area of research where improving our trade balances, as well as in theone of the most important and commonly used generation and maintaining employmentsapproaches of N&N, the “bottom-up-approach”, because it will push and renew traditionalcomes from, whose objectives are to organize activities of chemical industry in Europe.the matter at the nanoscale from atoms ormolecules with the purpose of obtaining new This aspect is important because the chemicalproperties or applications. industry is one of the pillars of the European economy. It is ubiquitous and is a significantDue to the transversal character of factor in the improved quality of life enjoyed byNanochemistry, it is expected that the research European citizens today. 19
  • 20. N & N i n S p a i n 2. State of the Art (recent advances, etc.) In order to analyse the state of the art of this area and describe the recent advances, over the 2007-2009 period, a search was made in the ISI Web of Knowledge (Web of Science) crossing the terms chem* and nano*. This search gaveNANOCHEMISTRY 36.400 results corresponding to papers that appeared in journals devoted to general science, chemistry, nanoscience, materials science, and physics. A careful analysis of the most cited articles of this search permitted to localize those topics inside Nanochemistry that have received more attention among the scientific community. A list of those topics, randomly ordered, is as follows: Figure 1. SEM image of a drug processed as a particulate material for • Self-assembled organizations in 0-, 1-, 2-, and controlling its delivery. Courtesy of NANOMOL, ICMAB (CSIC)-CIBER- BBN. 3-Dimensions. • Hierarchical functional supramolecular According with the vision paper of the European organizations. Technology Platform for Sustainable Chemistry (SUSCHEM), “The vision for 2025 and beyond”, • Studies on molecular dynamics on surface the EU is a leading global chemicals producing reactions. area, with 32% of world chemicals production. • Basic studies on interfacial structural aspects of small molecules. This sector contributes 2.4% to European Union GDP and comprises some 25,000 enterprises in • Synthesis and studies of molecular Europe, 98% of these are SMEs, which account motors/machines/valves. for 45% of the sectors added value. The • Design, preparation and study on chemical industry of the 25 State Members of nanoreactors. EU currently employs 2.7 million people directly, of which 46% are in SMEs, with many times this • Design and preparation of metal-organic number employed indirectly. frameworks with new properties. • Chemically modified surfaces for microfluidics. Consequently, N&N could help to boost European research, development and innovation in • Nanogels obtained by polymerization chemical technologies becoming a major techniques. determining factor to secure the sectors • Catalytic activity studies of metallic clusters. competitiveness and consequently the overall competitiveness. Thus, the future activities in • Chirality enhancement of surfaces or nanotubes. Nanochemistry will be of the utmost importance • New methods for preparation of nanocrystals for our lives and economy. /nanowires/nanotubes/nanovesicles. 20
  • 21. N & N i n S p a i n• Chemically modified surfaces / nanofibres / • Molecule-based techniques for printing. nanotubes and their applications. • Plasmon resonance studies of functionalized• Nanofabrication based on “layer-by-layer” surfaces/particles. assembly techniques. • Electron transport in molecular junctions and• Polymers with responsive properties to in nanotubes and graphenes. external stimuli. NANOCHEMISTRY • Nanoparticles and nanostructrued materials• Nanoparticles for being used as sensors, for sensing Hg2+ ions in water. medical imaging and therapy. • Preparation and functionalization of• Nanostructured materials for gas storage polymeric dendrons and dendrimers. applications. • Synthesis and characterizaton of monodisperse• Nanostructured materials for photovoltaics structured (hollow, core-shell, capsules, etc.) and photonics. nanoparticles.• Nanostructured materials for energy 3. Most relevant international papers in the area applications. appearing during 2007-2009• Nanostructured materials for drug delivery and targeting purposes. The most cited papers found in the above men- tioned searching using the terms nano* and• Self-assembled nanoprobes for NMR imaging. chem* are the following:• Synthesis, functionalization, and application of magnetic nanoparticles. •“Synthetic molecular motors and mechanical machines”.• Mesoporous materials for drug delivery. Kay, ER; Leigh, DA; Zerbetto, F., Angew. Chem.• Drug encapsulation in nanostructured objects Int. Ed., 46, 72-191 (2007). for biomedical applications. •“Titanium dioxide nanomaterials: Synthesis,• DNA hybridized materials for use in medical properties, modifications, and applications”. and sensing applications. Chen, X; Mao, SS, Chem. Rev., 107, 2891-2959 (2007).• Basic studies on cell internalization of nanostructured organizations. •“Chemically derived, ultrasmooth graphene nanoribbon semiconductors”.• Functionalization of quantum dots for cellular Li, XL; Wang, XR; Zhang, L; Lee, SW; Dai, HJ, imaging. Science, 319, 1229-1232 (2008).• Positioning and manipulating enzymes, •“Detection of individual gas molecules nucleic acids, and protein-based objects in adsorbed on graphene”. nanoreactors. Schedin, F; Geim, AK; Morozov, SV; Hill, EW;• Synthesis and studies of graphene and Blake, P; Katsnelson, MI; Novoselov, KS, derivatives. Nature Mater, 6, 652-655 (2007).• “Click” chemistry and its applications. •“Click chemistry in polymer and materials science”.• Modification of surface wetting properties. Binder, WH; Sachsenhofer, R, Macromol. Rapid Comm., 28, 15-54 (2007). 21
  • 22. N & N i n S p a i n •“Polyoxometalate clusters, nanostructures from Saccharomyces cerevisiae by electron and materials: From self assembly to designer transfer dissociation (ETD) mass materials and devices”. spectrometry”. Long, DL; Burkholder, E; Cronin, L, Chem. Soc. Chi, A; Huttenhower, C; Geer, LY; Coon, JJ; Rev., 36, 105-121 (2007). Syka, JEP; Bai, DL; Shabanowitz, J; Burke, DJ; Troyanskaya, OG; Hunt, DF, Proc. Nat. Acad. •“Synthesis of tetrahexahedral platinum Sci. USA, 104, 2193-2198 (2007).NANOCHEMISTRY nanocrystals with high-index facets and high electro-oxidation activity”. Tian, N; Zhou, ZY; Sun, SG; Ding, Y; Wang, ZL, 4. Actuations to undertake in Spain during Science, 316, 732-735 (2007). 2010-2013 •“Localized surface plasmon resonance It would be convenient that actions to promote spectroscopy and sensing”. and boost Nanochemistry in Spain in the next Willets, KA; Van Duyne, RP, Ann. Rev. Phys. years follow the general directions undertaken by Chem., 58, (2007). the most important European initiatives. There •“Synthesis of graphene-based nanosheets via is a prospective roadmap, performed at the chemical reduction of exfoliated graphite European level by the “European Technology oxide”. Platform (ETP) for Sustainable Chemistry” Stankovich, S; Dikin, DA; Piner, RD; Kohlhaas, (SusChem) that appeared in its “Strategic KA; Kleinhammes, A; Jia, Y; Wu, Y; Nguyen, ST; Research Agenda” (SRA), where products and Ruoff, RS, Carbon, 45, 1558-1565 (2007). technologies are given, together with their short-, mid- and long-term priorities and the •“Processable aqueous dispersions of graphene expected market volume. Most of such products nanosheets”. and technologies can be benefited from advances Li, D; Muller, MB; Gilje, S; Kaner, RB; Wallace, in Nanochemistry and, therefore, grouped by GG, Nature Nanotechnology, 3, 101-105 (2008). socio-economical sectors are detailed below: •“New directions for low-dimensional thermoelectric materials”. Energy Dresselhaus, MS; Chen, G; Tang, MY; Yang, RG; Lee, H; Wang, DZ; Ren, ZF; Fleurial, JP; Gogna, Products: Materials for hydrogen storage and P, Adv. Mater., 19, 1043-1053 (2007). transport, fuel cells and batteries, conducting •“Nanoelectronics from the bottom up”. polymers, superconductors and semiconductors, Lu, W; Lieber, CM, Nature Mater, 6, 841-850 light emitting diodes, solar cells, and thermal (2007). insulating materials. •“Molecular architectonic on metal surfaces” Technologies: Scale-up processes for the Barth, JV, Ann. Rev. Phys. Chem., 58, 375-407 production of advanced materials, analytical (2007). technologies for the quality control of advanced •“Colorimetric detection of mercuric ion materials, and process development and control (Hg2+) in aqueous media using DNA- technology. functionalized gold nanoparticles”. Lee, JS; Han, MS; Mirkin, CA, Angew. Chem. Information and Communication Technologies Int. Ed., 46, 4093-4096 (2007). •“Analysis of phosphorylation sites on proteins Products: Supercapacitors, luminescent materials 22
  • 23. N & N i n S p a i nfor displays, OLEDs, E-paper, molecular Healthcareelectronics, molecule-based for spintronics,semiconducting materials, conducting polymers, Products: Tumor therapy, targeted drug-delivery,materials with enhanced mobility, materials for bone reconstruction, tissue engineering. Newstorage and transport of information and for antibiotics by novel microorganisms, preparationholography, batteries, eco-efficient electronic of antibodies, peptides, and proteins bydevices, optical materials, pico-second molecular bioprocesses, medical devices, Smart delivery NANOCHEMISTRYswitches, and portable devices for hydrogen systems, tissular engineering, instant diagnosis,transport. functional textiles, and “lab-on-a-chip” devices.Technologies: Scale-up processes for the Technologies: Formulation engineering of micro,production of advanced materials, process nanostructured emulsions/ dispersions anddevelopment and control technology, technologies particulate products for controlled release, genericwhich take advantage of structure-property methods for introduction of chiral centers, in-silicorelationships and interface effects, high-power prediction of drug pharmacokinetics, high-technologies, miniaturization, and biotechnological throughput screening technologies, new MRI,production processes of molecular components. NMR and spectroscopy techniques, scale-up processes for the production of advanced materials, innovative fermentation processes for novel antibiotics production, biocatalytic production of pharma building blocks. Quality of Life Products: Devices for efficient lightening, environment sensors, membranes for treatment of drinkable water, materials for acoustic and thermal insulation, smart electro- chromic devices, interactive functional textile devices, intelligent materials for packaging, and food quality sensors, enzymes for new detergents and for removal of carcinogenic compounds in food, food tracking systems. Technologies: SensingFigure 2. Weaved textile with metallic conducting properties based on a nanocomposite poly-meric material. Courtesy of NANOMOL, ICMAB (CSIC)-CIBER-BBN. materials and techniques, 23
  • 24. N & N i n S p a i n formulation of products with defined particulate technology-platforms/ individual_en.html where structure, adapting intensified process it is also possible downloading their strategic equipment, scale-up processes for the research agendas and implementation action production of advanced materials, process plans. development and control technology. Many of such ETPs have created mirror Citizen Protection platforms in Spain which are currentlyNANOCHEMISTRY developing intense activities to boost their Products: Devices for biometric identification, respective areas in our country. Probably those smart cards, protecting tissues, ETPs whose interests are closer to superhydrophobic fibers, conducting and optical Nanochemistry activities and will benefit from fibers, alarm devices, thermo-chromic windows, new advances in this area are the following: functionalized polymers and surfaces as recognition layers, electrostrictive materials, and • Advanced Engineering Materials and pressure sensitive carpets. Technologies (EuMaT); www.eumat.org Technologies: Scale-up processes for the production of advanced materials, sensing • European Construction Technology Platform materials and techniques, and process (ECTP); development and control technology. www.ectp.org • European Nanoelectronics Initiative Advisory Transport Council (ENIAC); www.eniac.eu Products: Devices for instantaneous diagnosis and attending car drivers, traffic management • European Space Technology Platform (ESTP); sensors, improved safety devices, materials for http://estp.esa.int/exp/E10430.php recyclable and biodegradable vehicles, materials • Food for Life (Food); for constant repair, silent car & road, instant http://etp.ciaa.be/asp/ home/welcome.asp diagnosis/sensors, enhanced safety for transportation systems, functional coatings, eco- • Future Manufacturing Technologies (MANU- efficient car, plane & ships, improved tyres, FUTURE); recyclable materials. www.manufuture.org • Future Textiles and Clothing (FTC); Technologies: Scale-up processes for the http://textile-platform.eu/textile-platform/ production of advanced materials, and process • Nanotechnologies for Medical Applications development and control technology. (NanoMedicine); http://cordis.europa.eu/nanotechnology/ 5. Relevant initiatives nanomedicine.htm During the last years several European • Photonics21 (Photonics); Technology Platforms (ETPs) have been created www.photonics21.org and boosted by industrial and academic • Photovoltaics (Photovoltaics); partners. A complete list of ETPs can be found at www.eupvplatform.org the website http://cordis.europa.eu/ 24
  • 25. N & N i n S p a i n• Sustainable Chemistry (SusChem); In order to achieve such a level important www.suschem.org financial efforts must be made from the different national and local research agencies to provide• Water Supply and Sanitation Technology with considerable amounts of funds to the most Platform (WSSTP); competitive Spanish laboratories and groups, www.wsstp.eu/site/online/home judging their past activity based only in terms of excellence and productivity. The traditional NANOCHEMISTRYFor training and formation activities it is worth attitude of such agencies to distribute smallto mention the European School on Molecular amounts of funds to all groups must beNanoscience that has been organized two completely disregarded. Such agencies must alsoeditions in Spain with a successful attendance of consider those small groups with promisingyoung researchers from all Europe with the backgrounds to boost their activities.participation of worldwide recognizedresearchers and professors.This initiative was organized by the EuropeanNetwork of Excellence MAGMANet becoming animportant international event whereNanochemistry plays a key role. There are alsofew Master Degrees that are given by someSpanish Universities where the training onchemistry and nanoscience is provided.6. Infrastructure needed (2010-2013)Because of the special characteristics ofNanochemistry, there is no need to performlarge investments in huge research facilities. Thefunds provided by the local and nationalgovernments must be addressed mostly toincrease the manpower of the groups and toachieve efficient and rapid ways to acquiresmall-medium equipments without long waitingtimes since this decrease the efficiency andcompetitiveness of the groups.7. ConclusionAs a general conclusion it is worth to mention theneed to promote in Spain the research addressed toall the topics reported before. Nowadays there is agood level of research in our country in comparisonwith Europe although we are still far from theoptimal rank of excellence and productivity existingin the most developed countries. 25
  • 26. > FRANCESC PÉREZ-MURANO Place and date of birth Barcelona (Spain), 1966 Education PhD on Physics. Universitat Autonoma de Barcelona Experience Prof. Francesc Pérez-Murano is research professor at IMB-CNM. His research activities are dedicated to developing novel methods of nanofabrication for micro and nano electronics, and to applications of MEMS and NEMS in the areas of Sensing. He made his PhD at the Universitat Autonoma de Barcelona, and he has made post-doctoral and visiting stays at MIC in Denmark, NIST in USA, AIST in Japan and EPFL in Switzerland. In 2001, he set-up the CSIC nanofabrication facilities and nanotechnology-oriented research at CNM-Barcelona. He has been strongly involved in EU collaborative research projects in FP5 and FP6 covering several aspects of Nanotechnology and Nanofabrication, including the coordination of an STREP project in FP6. He is co-author of more than 100 articles in peer reviewed International Journals and co-inventor of four patents. He is member of the Steering Committee of the MNE (Micro and Nano Engineering) conference series. francesc.perez@imb-cnm.csic.es 26
  • 27. NANOELECTRONICS AND MOLECULAR ELECTRONICS1. IntroductionIt is widely accepted that electronics based onnano-scale integration and nanostructuredmolecular materials provides new types ofdevices and intelligent systems. Nanoelectronicstechnology development is following severalapproaches to improve performance of systemsthrough miniaturization. On one side, electronicsindustry (traditionally called Microelectronics)relies on the classical top-down approach, wherereliability and throughput is guaranteed tomanufacture millions of chips with integrated Figure 1. Different areas of Nanoelectronics according to the charac-nanoscale transistors. As stated by the well teristic length of the devices.known Moore’s law, continuous reduction of thetransistor size allows improving circuit Within the “More than Moore” area,performance. Microprocessors with 2 billion microelectronics-based technology is used andtransistors (32 nm node) are now close to the extended to the fabrication of sensors andmarket. transducers, amongst other devices. A paradigmatic example of this is the growing areaThe extremely complexity and cost of this of nanoelectromechanical systems (NEMS).technology, together with the envisioned limits “Beyond CMOS” focuses on the introduction offor further miniaturization triggers the disruptive, emerging materials and technologiesdevelopment of other concepts, materials and aiming to continue the integrated circuitsmanufacturing technologies, encompassed in growing up device density race. Lot ofwhich are known as “More than Moore” and development is being achieved in the so-called“Beyond CMOS” areas of nanoelectronics, carbon-based electronics, where carbonaccording to ENIAC1 initiative. nanotubes and graphene can be used to provide more-powerful devices. Along with this,In this sense, the research area of polymers, single molecules and nanocrystals arenanoelectronics covers a large range of aspects, also being introduced to developed new kind ofsome of which will be revised in this report. concepts. 27
  • 28. N & N i n S p a i n The area of nanoelectronics and molecular further generations, however, 20 nm seems toNANOELECTRONICS AND MOLECULAR ELECTRONICS electronics extends also towards materials be challenging. High volume, high throughput science and chemistry on one side, and towards lithography is predicted to reach the sub 20 nm many aspects of sensing (including biosensing). feature scale in 20173 . The technologies at hand These aspects are almost not treated in this to provide such a resolution at sufficient feature report, which is mainly focused to information quality are rare. Also, for the time being, it is not processing. clear, if its potential successor, extreme ultraviolet (EUV) lithography is arriving at the At the end of the first decade of the 21st century, market. Other technologies like nanoimprint we are in the situation where researchers and lithography (NIL)4 or electron beam (EBL) mask- engineers are starting to take benefit of the new less lithography5 provide sufficient resolution. “nano-based” materials and technologies While EBL is too slow (and parallelization is originated in previous decades. We anticipate the difficult) to provide enough throughput for high outcome of a new area for nanoelectronics, volume production, NIL gathers increasing where a real merge between top-down attention and it is proposed to be used in FLASH (microelectronics) and bottom-up (molecular memory production in the near future6. electronics) will give place to extremely powerful systems to satisfy the increasing demands for However this solution still requires a mask efficient information processing and technology with the added difficulty to fabricate communications, including quantum computing. a 1X mask. In addition, because it is a contact lithography, mask defects is a main issue. 2. State of the art Scanning Probe lithography for mask fabrication and technology development are being 2.1 Miniaturization in Microelectronics considered as well7. In any case, Microelectronics industry is seriously considering incorporating Progress in nanotechnology and microelectronics nanotechnology tools and concepts, like block- is intimately linked to the existence of high copolymers self-assembly8. quality methods for producing nanoscale patterns and objects at surfaces. The explosive 2.2 Carbon based nanoelectronics (CNTs and growth in the capability of semiconductor Graphene) devices has to a large extent been due to advances in lithography. Miniaturization has The approaching limits of the top-down enabled both the number of transistors on a chip miniaturization have triggered a global effort to and the speed of the transistor to be increased generate alternative device technologies. By by orders of magnitude. Optical lithography has replacing the conducting channel of a MOS kept pace with this evolution for several decades transistor by structured carbon nanomaterials and has always been the workhorse for such as carbon nanotubes or graphene layers, patterning the critical layers in semiconductor devices with enhanced properties for electronic manufacturing. transport are encountered9. Emerging of graphene as a high performance semiconductor At present, technological solutions for the 32 nm material has been a major hit during 2007-2009. node exist. Today’s predominantly used technology, optical deep UV (DUV) lithography2 Key results on this aspects have been the will be extended by computational methods to achievement of ultrahigh electron mobility in 28
  • 29. N & N i n S p a i nsuspended graphene layers10 and the NEMS is a clear example of multidisciplinary NANOELECTRONICS AND MOLECULAR ELECTRONICSobservation of room - temperature quantum effort, where the progress is achieved byhall effect. Technology for CNT-based simultaneous efforts on advancednanoelectronic devices is arriving to a mature nanofabrication processing, use of nanoscalestage. Improvements on the control of CNT characterization methods and tools, andorientation and their combination with CMOS introduction of concepts from photonicstechnology are especially relevant for future biochemistry physics, etc. NEMS technologyapplications13. Also important are the new include aspects of top-down fabrication usingapplications of CNT based devices for charge nanolithography and advanced opticaldetection14 and for nanomechanical mass lithography, but also combination with bottom-sensing (see below, NEMS subsection). up fabrication for the development of NEMS based on carbon nanotubes17 and silicon2.3 Spintronics nanowires18. Most relevant results include the demonstration of single atom sensitivity for massSpin based electronics deals with the sensors using carbon nanotubes and siliconmanipulation of spin of charge carriers in solid nanowires , the joint effort of CEA-LETI and UCLAstate devices. It can be distinguished between to develop a robust/wafer scale technology forinorganic spintronics (devices based on metals NEMS integration19, and the initial detection ofor semiconductors) and molecular spintronics, the quantum limits of NEMS20 .(either the design of molecular analogs of theinorganic spintronic structures and the evolution 2.5 Molecular electronicstowards single molecule spintronics). Understanding the electronic properties ofA recent review about molecular spintronics can single molecules and developing methods forbe found in15. Besides the well known impact of making reliable and optimal contacts to them are major challenges in Nanotechnology. Evenspintronics in storage technology (giant though a single molecule electronic device ismagneto-resistance effect used in the operationof magnetic hard-drives heads), inorganicspintronics has a potential to provide low-powerdevices for memories (MRAM). On the otherhand, molecules and single-molecule magnetsoffer possibilities for future applications inquantum computing.2.4 Nanoelectromechanical systems (NEMS)The area of nanomechanical systems hasexperienced a tremendous advance during the2007-2009 period. Roughly, three maindirections are being pursued: development ofextremely sensitive nanomechanical sensors16,large scale integration of nanomechanicalstructures and quantum limits of Figure 2. Example of massive fabrication of nanoelectronics devices. A four inch-wafer containing 138,240 CNT-FET structures. I. Martin etnanomechanical resonators search. The area of al12. 29
  • 30. N & N i n S p a i n conceptually simple (a molecule and two or Carbon based nanoelectronics (CNTs andNANOELECTRONICS AND MOLECULAR ELECTRONICS three electrodes), it is not fully understood21. Graphene) Some progress has been made to know the influence of metal electrodes on the energy •A. Barreiro, M. Lazzeri, J. Moser, F. Mauri, A. spectrum of the molecule, and how the electron Bachtold. transport of the molecules depend on the Transport properties of graphene in the high- strengths of the electronic coupling between the current limit. Phys. Rev. Lett., 103, 076601 molecule and the electrodes. A major drawback (2009). is the lack of reproducible results from single molecule devices due to the lack of control of •A. Gruneis, M. J. Esplandiu, D. García-Sanchez, the electrode/molecule contact, since most and A. Bachtold. results are based on mechanical methods. Detecting Individual Electrons Using a Carbon Alternatives to develop functional integrated Nanotube Field-Effect Transistor. Nano Lett., systems based on organic molecules are the 7, 3766 (2007). ones related with the cross-bar structure22, a periodic array of crossed nanowires with a •Per Sundqvist, Francisco J. García-Vidal, monolayer of an organic material (for example, Fernando Flores, Miriam Moreno-Moreno, bi-stable [2] rotaxane molecules) in between. It Cristina Gómez-Navarro, Joseph Scott Bunch, is proved that these systems can be miniaturized and Julio Gómez-Herrero. further than CMOS technology and that it is Voltage and Length-Dependent Phase highly tolerant to manufacturing defects23. Diagram of the Electronic Transport in Carbon Nanotubes. Nano Letters 2007 7 (9), 2568- 3. Survey of relevant publications by Spanish 2573. and International groups in the area •H. Santos, L. Chico, L. Brey. (2007-2009) Carbon Nanoelectronics: Unzipping Tubes into Graphene Ribbons. Physical Review Letters, 3.1 Spanish groups 103, 086801 (2009). Spanish research community is very active in the Spintronics area and some groups are in the cutting edge of the research arena. The present survey is not •M. Reyes Calvo, Joaquín Fernández-Rossier, exhaustive and it is just intended to show the Juan José Palacios, David Jacob, Douglas high-quality research performed by Spanish Natelson & Carlos Untiedt. groups. The Kondo effect in ferromagnetic atomic Miniaturization in Microelectronics contacts. Nature 458, 1150-1153 (2009). • Eugenio Coronado, Arthur J. Epsetin, Editors. •J. Martínez, R. V. Martínez, R. García. Molecular Spintronics and Quantum Silicon Nanowire Transistors with a Channel Computing. Width of 4 nm fabricated by Atomic Force Special Issue of Journal of Materials Microscope Nanolithography. Nano Letters Chemistry, vol 19, 1661-1760 (2009). 2008 8 (11), 3636-3639. •J. Fernández-Rossier and J. J. Palacios. •I. Martín. Sansa, M.J. Esplandiu, E. Lora- Tamayo, F. Pérez-Murano, P. Godignon. Magnetism in Graphene Nanoislands. Phys. Massive manufacture and characterization of Rev. Lett. 99, 177204 (2007). single-walled carbon nanotube field effect •V. A. Dediu, L. E. Hueso, I. Bergenti and C. transistors. Microelectronics Engineering, in Taliani. Spin Routes in Organic Semiconductors. press. (2010). Nature Materials 8, 707 (2009). 30
  • 31. N & N i n S p a i n•H. López, X. Oriols, J. Suñé, X. Cartoixa. Tuning the conductance of a molecular switch NANOELECTRONICS AND MOLECULAR ELECTRONICS High-frequency behaviour of the Datta-Das Nature Nanotechnology 2, 176 (2007). spin transistor. Applied Physics Letters 83, •J Puigmartí, V. Laukhin, A.P. del Pino et al. 193592 (2008). Supramolecular conducting nanowires from•L.E. Hueso, J.M. Pruneda et al. organogels. Angewandte Chemie International Transformation of spin information into large Edition 46238-241 (2007). electrical signals using carbon nanotubes. Nature 445, 410 (2007). 3.2 International groupsNEMS Miniaturization in Microelectronics•B. Lassagne, D. Garcia-Sanchez, A. Aguasca, •A. Pantazi et al. and A. Bachtold. Probe-based ultrahigh-density storage Ultrasensitive Mass Sensing with a Nanotube technology. Electromechanical Resonator. Nano Lett. 8, IBM J. Res. Dev. 52, 493–511 (2008). 3735 (2008). •C.T. Black et al.•J. Mertens. C. Rogero, M. Calleja, D. Ramos, J.A. Martín-Gago, C. Briones, & J. Tamayo. Polymer self-assembly in semiconductor Label-free detection of DNA hybridization microelectronics. based on hydration-induced tension in nucleic IBM J. Res. & Dev. 51, 605 (2007). acid films. Nature Nanotechnology 3 (5) (2008). Carbon based nanoelectronics (CNTs and•J. Arcamone, M. Sansa, J. Verd, A. Uranga, G. Graphene) Abadal, N. Barniol, M. van den Boogaart, J. Brugger, F. Pérez-Murano. •KI Bolotin, KJ Sikes, Z Jiang, M Klima et al. Nanomechanical mass sensor for spatially- Ultrahigh electron mobility in suspended resolved ultra-sensitive monitoring of graphene. deposition rates in stencil lithography. Small, Solid State Communication 146, 351 (2008). 5, 176-180 (2009). •KS. Novoselov, Z Jiang, Y Zhang, SV Morozov,•Álvaro San Paulo, Noel Arellano, Jose A. Plaza, et al. Rongrui He, Carlo Carraro, Roya Maboudian, Roger T. Howe, Jeff Boko, and, Peidong Yang. Room-temperature quantum Hall effect in Suspended Mechanical Structures Based on graphene. Elastic Silicon Nanowire Arrays. Nano Letters Science 315, 652 (2007). 2007 7 (4), 1100-1104. Nanoelectromechanical systems (NEMS)Molecular Electronics •A. K. Naik, M. S. Hanay, W. K. Hiebert, X. L.•J. Hihath, C. R. Arroyo, G. Rubio-Bollinger, N. Feng, M. L. Roukes. J. Tao, N. Agraït. Towards single-molecule nanomechanical Study of Electron-Phonon Interactions in a mass spectrometry. Single Molecule Covalently Connected to Two Nature Nanotechnology 4, 445 (2009). Electrodes. Nanoletters 8, 1673-1678 (2008). •K. Jensen, K Kim, A Zettl.•M del Valle, R. Gutiérrez, C. Tejedor and G. An atomic-resolution nanomechanical mass Cuniberti. sensor. 31
  • 32. N & N i n S p a i n Nat. Nanotech. 3, 533, 2008. molecular electronics. Large joint projects inNANOELECTRONICS AND MOLECULAR ELECTRONICS •J. D. Teufel, T. Donner, M. A. Castellanos- the area, creation of networks, workshops, Beltran, J. W. Harlow and K. W. Lehnert, etc., should be proposed. Nanomechanical motion measured with an • Increase the critical mass of research groups imprecision below that at the standard active in the area. quantum limit. Nature Nanotechnology 4, 820 (2009). • Analyze/unify the undergraduate and post- graduate education in the area, enhancing the Molecular Electronics programs content. •K. Moth-Poulsen and T. Bjornholm. 5. Research infrastructure required Molecular electronics with single molecules in solid-state devices. Technological development for nanoelectronics Nature Nanotechnology 4, 551 (2009). and molecular electronics requires the use of clean •J. E. Green, J. W. Choi, A. Boukai, Y Bunimovich room facilities and equipment. There is an et al. increasing number of small size clean rooms in A 160-kilobit molecular electronic memory Spain that could provide an adequate environment patterned at 1011 bits per square centimetre for activities focused to basic/fundamental science. In addition, granted access to medium-size clean Nature 445, 414 (2007). rooms (CNM clean room, ISOM clean room) is •W. Lu and C. Lieber. available to Spanish researchers through dedicated Nanoelectronics from the bottom up. programs financed by the Ministry of science and Nature Materials 6, 841 (2007). Innovation (MICINN). However, more ambitious technological 4. Actions to develop in Spain for the period developments that would provide integrated (2010- 2013) solutions based on nano-electronics and molecular electronics requires updating and Future impact in the society of nanoelectronics and extending present capabilities, since, as molecular electronics will be dictated by the previously stated, multidisciplinary approach is envisioned end of the miniaturization of CMOS required for future developments of microelectronics technology, which will open nanoelectronics. Additionally well trained staff enormous opportunities to the new building blocks enhancing the managing and operating from Nanotechnology. It is now time to position in capabilities of the above mentioned free access this aspect. Nanoelectronics and molecular facilities need to be boosted. electronics community in Spain, although demonstrating a high quality research activity, it In this sense, actuations related with infrastructure looks quite fragmentized in small groups dealing should be focused to consolidate small-size clean with partial aspects of the field. As the future of room focused to basic research application and the area relies on a multidisciplinary approach, enforce medium-to-large size clean rooms that some actions that could be undertaken to assure a would allow them to adequately address competitive position of Spain in this area are: challenges for technological developments in nanoelectronics. Adequate programs for funding • Enhance the relation between the different and training dedicated technical staff related with groups active on nano-electronics and the clean rooms are clearly required. 32
  • 33. N & N i n S p a i n6. Relevant initiatives Nanoselect, Nanobiomed and Nanociencia NANOELECTRONICS AND MOLECULAR ELECTRONICS Molecular). Relevant networks financedENIAC is the well known European technological including topics of interest for nanoelectronicsplatform in the area of nanoelectronics are Nanospain and Nanolito.(www.eniac.eu). Its main goal was to definecommon research and innovation priorities to Courses at post-graduate level including subjectsensure a truly competitive nanoelectronics related with nanoelectronics and molecularindustry in Europe. Recently, the first research electronics are available at most of Science andprojects funded by ENIAC have started. The Technical Universities around Spain.research is largely focused to industrialapplication, with emphasis in More Moore and 7. ConclusionsMore than Moore areas. The expected end in few years of theICT program of FP7 (http://cordis.europa.eu/ miniaturization trend in microelectronics as wefp7/ict/) funds more exploratory projects related know it today, places nanoelectronics andwith nanoelectronics, including aspects of More molecular electronics as critical actors to providethan Moore and Beyond CMOS areas. Within ICT, future advances for the areas of informationThe Future and Emerging Technologies Open processing and storage. In Spain there is anScheme - FET-Open - is a roots-up approach for ongoing important and high quality researchexploring promising visionary ideas that can activity in this area, with already good expertise.contribute to challenges of long term importance However the area looks fragmentized in thefor Europe. The scheme stimulates non- sense that there is no coordination between theconventional targeted exploratory researchcutting across all disciplines, and acts as a groups and activities, which would allow toharbour for exploring and nurturing new better use resources and expertise, and thenresearch trends, helping them mature in position Spain in a compettive place in theemerging research communities. international arena.Nano-ICT (www.phantomsnet.net/nanoICT) is a AcknowledgmentsVII FP coordination action whose main objectiveis the consolidation and visibility of the research The author acknowledge helpful discussionscommunity in ICT nanoscale devices. Nano-ICT is with Adrian Bachtold, Nuria Barniol, Carles Cané,structured in several working groups including Xavier Cartoixa, Jordi Fraxedas, Ricardo Garcia,Alternative Electronics, NEMS, Carbon nanotubes, and Emilio Lora-Tamayo.spintronics and mono-molecular electronics. ReferencesWithin the Marie Curie training networks, forexample FUNMOLS (fundamentals of molecular 1 www.eniac.euelectronic assemblies) has Spanish participation.At the national level, several projects within 2 M. Rothschild, Materials Today, 8, 18 (2005).nanoelectronics are funded within the “PlanNacional” at different programs: TEC (Electronics 3 International Technology Roadmap forand Communication Technologies), MAT Semiconductors (ITRS), Semiconductor Industry(Materials) and FIS (Physics), and also within the Association, (2008).Consolider-Ingenio initiative (as for exemple 33
  • 34. N & N i n S p a i n 4 17 H. Schift, J. Vac. Sci. Technol. B, 26, 458 (2008). K. Jensen et al, Nat. Nanotech. 3, p533 (2008).NANOELECTRONICS AND MOLECULAR ELECTRONICS 5 18 R. Menon, A. Patel, D. Gil, H. I. Smith, Material R. He et al, Nano. Lett. 8, p1756 (2008). Today, 8, 26 (2005). 19 P. Andreucci, Very Large Scale Integration 6 M. LaPedus, "Toshiba claims to validate (VLSI) of NEMS based on top down approaches. nanoimprint litho," EETimes, October 16, 2007. Minatec Cross Road Workshop Nanomechanics for NEMS : scientific and technological issues. 7 A. Pantazi et al. Probe-based ultrahigh-density Minatec Grenoble (2008). storage technology. IBM J. Res. Dev. 52, 493–511 20 (2008). J. D. Teufel, T. Donner, M. A. Castellanos- Beltran, J. W. Harlow and K. W. Lehnert, 8 C.T. Black et al. Polymer self-assembly in Nanomechanical motion measured with an semiconductor microelectronics. IBM J. Res. & imprecision below that at the standard quantum Dev. 51, 605 (2007). limit. Nature Nanotechnology 4, 820 (2009). 9 21 Ph. Avouris, Z. Chen and V. Perebeinos. Nature K. Moth-Poulsen and T. Bjornholm. Nature nanotechnology, 2, 605 (2007). Nanotechnology 4, 551 (2009). 10 22 KI Bolotin et al. Solid State Communication Jonathan E. Green et al. Nature 445, 414 146, 351 (2008). (2007); W. Lu and C. Lieber. Nature Nanotechnology 6, 841 (2007). 11 KS. Novoselov et al. Science 315, 652 (2007). 23 J. Heath et al. Science 280, 1716 (1998). 12 I. Martín, M. Sansa, M.J. Esplandiu, E. Lora- Tamayo, F. Perez-Murano, P. Godignon. Massive manufacture and characterization of single- walled carbon nanotube field effect transistors. Microelectronics Engineering (2010). 13 SJ Kang et al, Nature Nanotechnology 2, 230 (2007). 14 A. Gruneis, M. J. Esplandiu, D. García-Sánchez, and A. Bachtold Nano Lett., 7, 3766 (2007). 15 Eugenio Coronado, Arthur J. Epsetin, Editors. Special issue of Journal of Materials Chemistry, vol 19, 1661-1760 (2007). 16 A. K. Naik, M. S. Hanay, W. K. Hiebert, X. L. Feng, M. L. Roukes Towards single-molecule nanomechanical mass spectrometry.Nature Nanotechnology 4, 445-450 (2009). 34
  • 35. N & N i n S p a i n 35
  • 36. > RODOLFO MIRANDAPlace and date of birthAlmería (Spain), 1953Education1975 BS in Physics, Universidad Autónoma de Madrid (UAM). Madrid, Spain; 1981 PhD with Prof.Juan M. Rojo, UAM, Madrid, Spain; 1882–1984 Postdoc with Prof. G. Ertl, Physikalische ChemieInstitut de la Universidad de Munich, Munich, Germany.ExperienceFull Professor of Condensed Matter Physics of the Faculty of Sciences at the UAM, Madrid, Spain &Director of the Madrid Institute for Advanced Studies in Nanoscience (IMDEA-Nanociencia). Prof.Miranda has been Vice-chancellor of Research and Scientific Policy (1998-2002) at the UniversidadAutónoma de Madrid, Executive Secretary of the R&D Commission for the Conference of Rectors of Spanish Universities (CRUE) (2000-2002) and Director of the Materials Science Institute “Nicolás Cabrera” at the Universidad Autónoma de Madrid. Prof. Miranda is Fellow of the American Physical Society (2008) and Member of the following societies: American Vacuum Society, American Physical Society, and Materials Research Society. Other honours include Membership of the Surface Science Division Committee IUVSTA (October 1989- October 1992), of the Advisory Board at the Max Planck Institute für Mikrostrur Physik, Halle (1993-2003), and the Spanish representative in the Scientific Advisory Committee of the European Synchrotron Radiation Facility (ESRF) at Grenoble (July 1988-January 1991). He is also a member of the Editorial Board of the journal Probe Microscopy. Prof. Miranda has published more than 200 scientific articles. rodolfo.miranda@imdea.org > ROBERTO OTERO Place and date of birth Córdoba (Spain), 1974 Education Degree in Physics at UAM (1997) and PhD in Science at UAM (2002) Experience Three years as Assistant Research Professor at the University of Aarhus and four years as Ramón & Cajal at UAM. roberto.otero@imdea.org 36
  • 37. N A N O M AT E R I A L S1. Introduction down the physical properties of macroscopic pieces of the same material. The lack ofA great deal of the expectations raised in the last scalability in the physical properties ofdecade in the fields of Science and Technology nanometer-sized structures opens newat the atomic scale arise from the lack of opportunities and methods for the fabrication ofscalability in the physical properties of matter nanoscopic structures with custom-desginedwhen its size falls in the nanometer range (the physical properties and, therefore, for themillionth part of a millimeter). Nanoscopic Science of Materials hosting nanometer-scalepieces of material can be made out of hundreds structural motifs.of atoms (at least in the dimension in which thesize of the material is in the nanometer range) In the following we will focus on recentlyinstead of the mind-boggling amount of 1023, developed methods to provide macroscopiccharacteristic of macroscopic materials. It is thus materials with nanometer-scale structural motifsnot surprising that many of the commonly used able to modify their physical and chemicalapproximations to understand the physical properties and endorse them with newproperties of large-scale materials cannot be functionalities. We will however not discuss theapplied to nanometer-scale structures. synthesis and properties of individual nanostructures, which also a burgeoning field withAmong these properties we find for example great potential for applications, but which will mostelectrical conductivity, that becomes quantized likely be covered in other sections of this report.in the limit of nanometer-thick wires; thechemical reactivity of nanoparticles, which is We will however make an exception for thedramatically affected by the larger number of explosive development of the research insurface atoms in these nanostructures as graphene, i.e. an atom-thick graphite layer. Thecompared to macroscopic materials; the discovery of methods to isolate and handlemagnetization of nanoscale magnets, that can individual graphene sheets has raised manybe severely reduced by the non-negligible effect expectations in the field of Nanoelectronics, dueof thermal fluctuations, etc. to its promising transport properties, which ultimately arise from a peculiar electronic bandThese effects exemplify that fact that the structure leading to very high Fermi velocity (ofphysical properties of nanostructures can the order of 106 m/s), giant electronic mobilitytherefore not be obtained simply by scaling- (in excess of 104 cm2/V⋅s) and zero effective 37
  • 38. N & N i n S p a i n mass. From the point of view of Materials applications. A very intense research effort is Science, the most important challenges to meet currently being developed to solve are the chemical functionalization of graphene (to nanostructures in the bulk of liquids. control its solubility, open a semiconducting gap Solubilization and biocompatibilization of light and control the sign and concentration of charge emitting and magnetic nanoparticles are carriers by doping) and the epitaxial growth of currently a hot topic for nanomedicine studies. graphene sheets with reduced defectN A N O M AT E R I A L S concentration. An analysis of the scientific papers New experimental non-invasive imaging published in the field of graphene research in the techniques and therapies for a number of last few years (2007-2009), shows that Spain has diseases, which are currently being developed, played a major role in this scientific enterprise, relay on the capability of these nanostructures occupying the 7th position in the ranking of to get incorporated into the blood stream countries, according to Web of Science. without triggering immune responses, and get into target cells and organs. 2. State of the Art For this purpose a major challenge that must be As described above, we will limit ourselves to tackled in the next few years is finding the the Materials Science aspects of current proper chemical functionalizations that would Nanoscience and Nanotechnology, i.e. to enable the nanostructures to bind selectively to materials that contain distributions of nanoscale the targeted organs. motifs that control or affect their macroscopic properties. Since their preparation methods and One possible alternative to incorporate the final properties are very different, we will classify nanostructures into a bulk material without the nanostructured materials depending on whether need of a matrix could be the direct the nanoscale motifs are distributed all over the crystallization of nanoparticles. The interactions bulk of the material or at its surface. between the nanoparticles that steer the self- assembly processes are dictated, and thus can 2.1 Embedding nanostructures at the bulk of a be controlled, by the proper choice of the material ligands that cover their surfaces. Nanostructures can be embedded in typically It was already described in the literature that amorphous matrices, very often polymeric nanoparticles can be embedded into larger matrices, resulting usually in random spatial colloidal particles, for which crystallization distribution and the nanoscale structural motifs. methods have been long known. The resulting Typical examples are polymeric matrices with photonic crystals have very interesting optical incorporated carbon nanotubes, which have very properties. Nanoporous materials, such as interesting effects in their elastic and thermal zeolites or organometallic coordination conduction properties, or semiconducting networks, can act as molecular sieves with very nanoparticles (quantum dots) dispersed in promising applications in the fields of catalysis polymeric matrices with very interesting and water purification. photovoltaic properties. The directionality of the bonds that hold the 3D Recently, hybrid CNT-QD systems have been structure of these materials, leads to the synthesized, holding promise for photovoltaic formation of ordered arrays of holes with well 38
  • 39. N & N i n S p a i ndefined size, shape and chemical composition. The methods to imprint patterns on surfaces areThese pores can selectively bond molecules with collectively termed lithographies. The simplestparticular shapes, enabling their function as of them is the microcontact printing technique,catalysts and molecular sieves. in which a stamp is dipped into an “ink” (a solution of molecules or nanostructures) and2.2 Surface Nanostructuration of Materials then brought into contact with a surface, so that the ink wets the surface preferentially following N A N O M AT E R I A L SThe surfaces of materials can be modified at the the pattern at the stamp.nanometer scale either by imprinting nanoscalepatterns on the otherwise homogenous surface, However, the time-honored, most commonsor adsorbing nanostructures on them, which could lithographic techniques are based on irradiatingbe either preformed and then deposited or can be the surface of the material (previously covered byself-assembled from their constituent building a radiation-sensitive layer) with energetic particlesblocks previously adsorbed on the surface. (photons, electrons, ions) through some masks with orifices of well defined shape and size.Both approaches can be combined by adsorbingnanostructures selectively on particular areas of The smallest nanostructures achieved hithertoa imprinted nanoscale pattern. In this way, for by electron beam lithography are some in excessexample, linear nanopatterns can be used to of 10 nm large. In order to achieve even smallerdirect the growth of 1D arrays of nanoparticles, nanostructures, the possibility of performingsomething that would be very challenging to do lithography with the tip of a Scanning Probeonly by exploiting self-assembly processes. Microscope is currently under investigation. Such method, though, still has to face the problem of scaling up the modified area, since today only relatively small patches of the surface can be modified within a reasonable time-span. There are also non-lithographic methods to imprint nanoscale patterns on solid surfaces. They are usually based on obtaining an ordered array of nanostructures in the surface by epitaxy or self-assembly. This array will act as a nanoscale pattern for the subsequent adsorption of other kind of nanostructures. For example, epitaxial growth of graphene on transition metal surfaces leads to nanoscale Moiré patterns originating from the lattice mismatch between the underlying metallic surface and the graphene layer. This Moiré pattern has been shown to direct the growth of metallic nanoparticles or organic material deposited on the rippled graphene.Figure 1. Hybrid carbon nanotube – Quantum Dot system. From Nano Nanoscale patterns can also be obtained fromLett. 7, 3564 (2007). Courtesy of B. H. Juárez 39
  • 40. N & N i n S p a i n the self-assembly or organic molecules by properties of individual chemically reduced hydrogen bonds or coordination bonds, and the graphene oxide sheets”, Nano Lett. 7, 3499 pores of the molecular network act as (2007). nucleation sites for the subsequent deposition •Elías D. C. et al. “Control of Graphenes of organic material. Properties by Reversible Hydrogenation: Evidence for Graphane”, Science 323, 610 Finally, nanoparticles or nanowires can also be (2009).N A N O M AT E R I A L S directly deposited on solid surfaces. Hitherto •Vázquez de Parga A. L. et al., “Periodically most of these works have performed the rippled graphene: Growth and spatially deposition directly from a solution of the resolved electronic structure”. Phys. Rev. Lett. nanostructures, by drop-casting, spin-coating or 100, 056807 (2008). Langmuir-Blodgetts techniques. In the last few •Brown, P. & Kamat, P. V, “Quantum Dot Solar years several groups have pursued new methods Cells. Electrophoretic Deposition of CdSe−C60 to deposit these nanoparticles under vacuum Composite Films and Capture of conditions, with methods based on electrospray Photogenerated Electrons with nC60 Cluster evaporation, laser irradiation sublimation Shell”, J. Am. Chem. Soc. 130, 8890 (2008). (MALDI) or pulsed-valve methods. •Zheng, D. et al. “Aptamer Nano-flares for Molecular Detection in Living Cells”, Nano Functionalizing solid surfaces with nanoparticles Lett. 9, 3258 (2009). is known to have some very interesting effects •Striemer, C. C. et al. “Charge- and size-based on the material reactivity or photovoltaic separation of macromolecules using ultrathin properties. Controlling the self-assembly of silicon membranes” Nature 445, 749 (2007). nanoparticles on solid surfaces remains however •Kang, H. et al. “Hierarchical Assembly of a challenge in which more work needs to be Nanoparticle Superstructures from Block developed in forthcoming years. The adsorption Copolymer-Nanoparticle Composites” Phys. of molecular wires such as DNA and carbon Rev. Lett. 100, 148303 (2008). nanotubes faces similar problems nowadays. In •Green, J. E. et al. “A 160-kilobit molecular this respect, however some interesting progress electronic memory patterned at 1011 bits per has been made by deposition of the catalytic square centimeter” Nature 445, 414 (2007). promoters on nanopatterned surfaces, which direct the growth of the CNT is specific •Guo, L. J. “Nanoimprint Lithography: Methods and Material Requirements” Adv. Mater. 19, directions. 495 (2007). 3. Relevant publications 2007–2009 •Park, S. Y. et al. “DNA-programmable nanoparticle crystallization”, Nature 451, 553 •Novoselov K. S. et al. “Room-temperature (2008). quantum hall effect in graphene”, Science •Juárez, B. H. et al. “Quantum Dot Attachment 315, 1379 (2007). and Morphology Control by Carbon •Sutter P. W., Flege J. I. & Sutter E.A. “Epitaxial Nanotubes”, Nano Lett. 7, 3564 (2007). graphene on ruthenium”, Nat. Mater.7, 406 •Écija, D. et al. “Crossover Site-Selectivity in the (2008). Adsorption of the Fullerene Derivative PCBM •Wehling T. O. et al. “Molecular doping of on Au(111)” Angew. Chem. Intl. Ed. 46, 7874 graphene”, Nano Lett. 8, 173 (2008). (2007). •Gómez-Navarro C. et al. “Electronic transport 40
  • 41. N & N i n S p a i n4. Actions to develop in Spain 2010–2013 field in its very essence. Promoting interdisciplinarity is thus an importantIt was mentioned above that the state of requirement for leadership in nanosciencescientific research in some areas of nanomaterials research. Some actions that would helpscience is quite competitive worldwide. However, promoting interdisciplinarity are theif we expand our publication research (based on following: positive evaluation ofWeb of Science data) to the larger field of interdisciplinary curricula in calls for public N A N O M AT E R I A L Snanomaterials in general, we find the Spain is funding; promotion of interdisciplinaryonly the 14th in rank of publishing countries. This research centers, such as the new nanoscience centers; promotion offact shows that Spain has nowadays the postgraduate master courses, perhaps bymanpower required to take the lead in the merging some of the very specific coursespursuit of some of the hottest topics in nowadays available in Spanish universitiesnanomaterials science research, but it into larger ones with broader scopes.nonetheless lacks enough scientificinfrastructures, evaluation mechanisms and • Strategic research objectives should be clearlyeducational opportunities to exploit at full its defined, and sufficient funding should behuman potential. delivered as Strategic Actions into particular fields both to keep the leadership in successfulThe actions to be undertaken in the near future areas and promote new topics in the Spanishmust aim at the double objective of keeping and scientific landscape.reinforcing our leadership in those successful • In general a closer contact between scientificareas, such as graphene research, Scanning research and industry must be pursued.Probe Microcopies of Nanobiotechnology, whilepromoting high-quality scientific research in 5. Required infrastructurethose areas in which it is missing and yet theyare recognized as strategically relevant for our The founding over the last few years of a number ofcountry. In the following we enumerate a research centers with a focus on nanosciencenumber of suggested actions that could help us research can in principle provide the Spanish scientificgetting closer to our objectives: community with a strong structural basis to pursue scientific excellence and leadership worldwide.• In the last few years, a number of research centers with specific focus on nanoscience In the next few years they should be equipped with and nanotechnology have appeared in the scientific infrastructure and technology that will different regions of Spain. These centers enable them to develop high-quality scientific should keep a sufficient funding to become research. The required investment must be attractive to foreign researchers or Spanish evaluated by external scientific committees to researchers working abroad. ensure that the funds are really helping capable• In order to keep the level of scientific funding researchers to carry out relevant investigations. high in the midst of an economic crisis, it is Constant and fluid communication channels must important that serious evaluations of be open among research groups and among research outcomes are routinely done, and nanoscience centers. Thus, the creation of new that the results of such evaluations is taken scientific and technological networks and the into account to obtain further funding. promotion of the already existing ones, such as the• Nanoscience is an interdisciplinary research successful NanoSpain network must be one of the axes of scientific policy. 41
  • 42. N & N i n S p a i n Spanish scientific community will profit Several aspects of nanostructured materials extraordinarily from the availability of large seem particularly relevant today, such as for infrastructures, such as synchrotron radiation example carbon-based electronics, specially sources, in Spain. based on graphene and carbon nanotubes; the use of nanoparticles in biomedicine; the The existence and use of these facilities must be magnetic properties of nanostructured materials promoted by sufficient funding and quality staff, or the use of self-assembly processes to directN A N O M AT E R I A L S so that they can become competitive with the growth of nanostructures. similar European facilities, with which Spanish researchers are already familiar and, in many Spain is performing well in some of these fields, cases experienced users. although works still remains to be done in other fields to achieve the level of scientific excellence 6. Relevant initiatives in the international arena. Spanish scientists in the Nanostructured An adequate level of funding, evaluation of Materials research field can profit from several scientific results and the promotion of the new Spanish and European initiatives aimed at Nanoscience centers seem to be the several ends of networking, educational cornerstones of any scientific policy aimed at opportunities, fundraising, etc. Some of these helping the progress of Materials Nanoscience opportunities are listed below: in our country. • NanoSpain network (www.nanospain.org): This network brings together almost every research group in the areas of Nanoscience and Nanotechnology in Spain promoting communication and networking in different ways such as an annual conference. • Master in Molecular Nanoscience (www.icmol.es/master/nnm/index.php): Postgraduate courses in Nanoscience in which different Universities are involved. It provides students with a general interdisciplinary view of the different fields contributing to Nanoscience. • Many Universities in Spain offer postgraduate courses in particular aspects of Nanoscience and Nanotechnology. 7. Conclusions The discovery of new and promising properties of nanostructures are revolutionizing the field of Materials Science. It is impossible today to imagine a future for Materials Science without including concepts, methods and materials taken from the field of Nanoscience. 42
  • 43. N & N i n S p a i n 43
  • 44. N A N O M E T R O L O G Y, N A N O - E C O - T O X I C O L O G YA N D S TA N D A R D I Z AT I O N> XAVIER OBRADORSPlace and date of birthManresa (Spain), 1956Education• Degree in Physics, Universitat de Barcelona , June 1978.• DEA in Physique des Solides, Université de Toulouse, June 1980.• Ph.D. in Physics, Universitat de Barcelona , October 1982. • Doctorat Materials Science , Université Scientifique et Médicale de Grenoble , January 1983. Research and teaching positions • Assistant Professor, Universitat de Barcelona, June 1978-79. • Doctoral fellow, CNRS Toulouse and Grenoble, 1979-82. • Postdoctoral fellow and Assistant Professor, Universitat de Barcelona, 1982-85. • Professor, Universitat de Barcelona, 1985-89. • Research scientist (1989-92) and Research Professor (1992-), National High Research Council. • Head of the Dpt. of Magnetic and Superconducting Materials, 1991-2002. • Vice-Director (2002-2008) and Director (2008-) Materials Science Institute of Barcelona, CSIC. Research interests and strategy The research activity promoted within the Magnetic and Superconducting Materials Department at ICMAB-CSIC has always been marked by a very broad approach, including materials preparation with controlled microstructures and the search for the comprehension of the physical mechanisms underlaying the magnetic and superconducting properties of the materials. The generation of industrially significant knowledge, both in materials processing and in electrotechnical device development, has been strongly stimulated. Several initiatives of technological transfer within an European scenario have been carried out. xavier.obradors@icmab.es 44
  • 45. N A N O M AT E R I A L S F O R E N E R G Y1. Introduction worldwide can only be successful through a decisive increase of the R&D on energyThe energy challenge of Humankind has become technologies where many breakthroughs areone of the greatest social, environmental, needed to fulfill the performances and costseconomical and technological (and hence required for a really successful low-carbonscientific) priorities since the recognition that economy. It is undoubtful that there is ampleglobal warming can’t be ignored any more. room for efficiency improvement onAchieving a reliable and sustainable energy conventional fossil-related energy technologiessupply and use is an issue of the highest or nuclear energy and certainly new scientificrelevance in order to avoid an undesirable developments are capable of improvingclimate change with potential devastating power. incrementally its efficiency. This type of activities will not be covered by the present report.At present the worldwide use of energy of fossil Instead, advanced technologies having a strongorigin is around 80 % while it is estimated that potential to reduce GHG emissions and with ato stabilize the CO2 content in the atmosphere long way to go in terms of technologicalat about 450-500 ppm (to limit the mean development will be the main choice.temperature increase of the earth to less than2-3OC) would require at least achieving 50 % of Nanoscience and nanotechnology, and theclean energy (carbon-free), even including the corresponding materials technologies derivedexpected population rise (from ~6x109 to from them, are crucial to achieve the ambitious~10x109 inhabitants by 2050) and the goals established to create a myriad of newcorresponding consumption increase per capita sustainable technologies. Actually, sustainable(mainly of the developing countries). technologies are still on its infancy and they are very far from their fundamental limits.This vision is extremely challenging andtherefore intermediate objectives in terms of At the same time, we must be aware that thereduction of green house gas (GHG) emissions energy industry is essentially driven by cost andare being established. Europe, for instance so no significant change in the energy mix willintends to achieve by 2020 the target of cutting occur unless low cost is achieved in parallel to the20 % GHG emissions, increase the share of enhanced performances based on variedrenewable generation to 20 % and reducing 20 % functionalities. It is a big priority to break thisthe use of primary energy through enhanced bottleneck to achieve a wide spread of renewableefficiency. The energy policies being considered energy sources and an efficient use of energy. 45
  • 46. N & N i n S p a i n Many different areas have a huge potential to electricity and hydrogen: chemical energy, contribute to the energy challenge of 21st century, electronic energy and electric energy. as it will be described later. However, it is clearN A N O M AT E R I A L S F O R E N E R G Y that the requirements of the new nanomaterials 2.1 Chemical energy to be used for energy purposes is that they can The most promising alternative to fossil fuels, be produced at large scale and at low cost. particularly for transport purposes, is hydrogen, an energy carrier which is abundant in chemical Therefore the bottom-up approach to compounds such as water and biomass. When nanofabrication will be the preferred choice in used as vector of the hydrogen-water cycle it the long term, even if this may induce some becomes a sustainable choice if it uses renewable reduction of performances. Top-down resources for generation. The whole cycle approaches to nanomaterials fabrication can be involves therefore generation, storage and final however considered as very appealing for “proof use, for instance with fuel cells. In all the three -of-principle” new technology demonstration or stages nanotechnology is required to achieve a also as elements for devices of intermediate cost mature and efficient hydrogen energy chain. but with very high performances. Hydrogen production with low CO2 generation While the nanofabrication issues considered for can arise from biomass or by photocatalytic energy uses are quite unique and require a splitting of water. Both strategies require specific widespread development of new methodologies, nanostructured materials, either for catalytic the demands in terms of nanoscale purposes or as semiconductors harvesting light characterization are also very demanding to split water. Noble metals supported on oxide because the advanced functionalities are nanoparticles continue to be the preferred associated in most of the cases to interfaces of choice in these catalytic processes and much materials with varied shapes and forms. It is more knowledge is being generated about the particularly outstanding the need of chemical active sites and mechanisms through the composition and structural characterization tools structural and spectroscopic analysis of surfaces at the nanoscale such as electron nanoscopy. oxides under real working conditions. 2. Worldwide state of the art Oxide, oxynitride and sulfide nanoparticles and nanorods, together with semiconducting Energy harvesting, transport, storage and use nanowires, are being very actively investigated can be performed in many ways and under many as photocathodes for electrochemical cells circumstances or for different purposes performing water splitting from the visible light (transport, domestic, industry) therefore it is a spectra. The tuning capability of the quantum difficult task to shortly summarize the R&D yield has shown a steady progress based on advances and the bottlenecks. further understanding of the physical and chemical processes involved. Even though, a classification of the worldwide activities following the general energy “forms” The practical application of this technology has the advantage of some thematic similarity, requires an important increase of efficiency even if an intermixing of all them can actually which must be linked to new materials discovery, not be avoided. Three wide conceptual groups as well as a tight control of nanostructure of the have therefore been selected which cover the photocatalysts and the semiconductors. two more promising sustainable vectors, i.e. 46
  • 47. N & N i n S p a i nHydrogen storage is one of the main concerns applications, and its practical complementaritiesfor any transport use of this fuel, the progress in and synergy with electricity as energy carrier,nanoscience and simulation to unveil the strongly rely on the advances in preparing N A N O M AT E R I A L S F O R E N E R G Ycapabilities of many types of materials to nanostructured materials because all thesurpass the many encountered challenges: mentioned processes require interfacial gas-nanoscale materials to minimize diffusion length solid ionic and electronic exchanges amongand time, catalytic efficiency of molecular dissimilar materials.hydrogen splitting, chemical bonding, structuraland microstructural effects on hosts (light alloys 2.2 Electronic energyor molecular compounds). A broad horizon hasbeen opened with such a demanding challenge Electronic materials are mainly semiconductorswhich now faces a new era for achieving the which can easily convert light or heat onrequired performances. electrons and viceversa and are therefore essential for energy purposes. It is particularlyFuel cells using hydrogen to generate efficiently worthwhile to stress the most promisingelectricity with water as exhaust are an opportunities in photovoltaic generationenvironmentally friendly alternative with a high converting visible and UV photons (58 % of solarefficiency and versatility. Polymer electrode spectrum) on electrons and thermoelectricmembranes and solid oxide fuel cells (SOFC) are materials for electron generation from infraredtwo alternative technologies working at radiation (42 % of the solar energy spectrum).different temperatures which are continuously Within this same classification we can includedisplaying a progress in performance, life time lightening materials such as LEDS.and cost reduction. One particular concern is tosubstitute expensive catalysts such as Pt. Photovoltaic cells are usually classified as 1st generation (Si based), 2nd generation (thin filmsUnderstanding the interplay between such as chalchogenides – CIGS and organic ornanostructure, composition and the hybrid cells) and 3rd generation (multijunctionperformances of electrolyte and electrodes and nanodot assisted semiconductor cells). The(ionic conduction, electronic conduction, three categories are characterized in terms ofcatalytic activity) and the quality of interfaces is achievable efficiency and cost per useful power.a very challenging objective which registers a While 1G cells can be fabricated with 20-25%continuous progress. Also the development of efficiency (very near the thermodynamic limit ofnanostructured oxides electrolytes have 31%) but in limited surfaces, 2G cellsdemonstrated a strongly enhanced interfacial concentrate on potentially large area materialsionic conductivity which appears very promising with reduced cost (organic and hybrid cells andfor further reduction of the working thin films), at cost of reducing efficiency (8-10%temperature in SOFC. Advanced at most at present). 3G cells are based oncharacterization techniques, such as 3D multilayered semiconductors includingtomography, greatly contribute to this purpose. nanodots where efficiency can be very highAn emerging application of such a devices is to (near 60%), even if they are fabricated at ause them in the reverse mode for chemical higher cost. The organic cells might to be usedenergy storage purposes. on very wide areas, for instance as indirect light recycling devices, while the 3G cells are at theThe emerging hydrogen economy and its core of solar concentration systems.competitiveness in transportation or static 47
  • 48. N & N i n S p a i n Light harvesting efficiency and several nanoscale mention dye-sensitized solar cells (DSC), first processes dominate the efficiency of such cells, introduced by Grätzell. These cells use mainly in those classified in the 2G and 3G nanocrystalline oxide semiconductorsN A N O M AT E R I A L S F O R E N E R G Y groups. Charge generation (exciton formation, (nanoporous, nanorods) in contact with organic electron – hole pair separation) and charge dyes which generate electrons through a transport to the corresponding electrodes photochemical reaction. These DSC cells have avoiding recombination are the key issues. Many the advantage of a low cost while they have different types of fully molecular organic already achieved efficiencies beyond 10%. They materials or hybrid organic – inorganic are being are very well adapted to the needs of large area investigated as nanocomposite blends; p-type applications, such as in buildings. conjugated polymers and n-type fullerene blends display the highest performance up to About 40% of the solar spectrum belongs to be IR now (~8%). Hybrid cells with p-type range while about 50% of the primary energy nanostructured inorganic semiconductors and p- ends up as heat. Therefore, there is an extremely type organic semiconductors are now being large room for direct recycling of such energy into deeply investigated. All these cells can be electric generation through thermoelectric processed through low cost techniques such as devices. This old phenomenon has recently seen solution spin coating or ink jet printing. an outstanding revival due to the discovery of either new materials or the development of The main issue here is to improve the quantum nanostructured materials where the conflicting efficiency of light transformation, avoiding functionalities can be combined. charge recombination at defects and long term degradation of the polymers. A very extensive Thermoelectrical power, electrical and thermal worldwide effort is being undertaken in this area conductivity can be controlled through quantum with emphasis on new molecular blends and size effects and hence semiconducting nanowire device processability with the purpose of engineering has turned out an emerging reaching an enhanced efficiency and the cost research field demanding deep consideration. threshold of 0.3 €/W. 3G multijunction cells consists mainly on III-V semiconductor stacks As a final technology with a large potential to grown by MBE or MOCVD, they absorb a wide reduce energy consumption and CO2 emissions spectrum of visible light and hence overcome through enhanced efficiency we should mention the thermodynamic limit of 1G cells. lightening materials (~20% electricity consumption worldwide). Inorganic semiconductor LEDs and New concepts such as multiphoton absorption OLEDs are being widely investigated as solid through quantum nanodots and hot carrier state systems which promise a deep worldwide generation have fostered new nanotechnology revolution because of its enhanced efficiency. based devices and so this area is very active at Increase of efficiency and lifetime, as well as the present in relationship to the interest of development of white light generation, all at low developing MW-class photovoltaic solar cost, are the more challenging objectives in this generators with power concentration ratios near field. The use of phosphors to convert UV light 1000. The idea of using self-assembled colloidal into visible light is also a very promising route. semiconductor nanodots as solar energy generators has been also recently raised and its Overall the present roadmaps indicate that in enormous potential has been widely stressed. 10-20 years LED’S will be the dominant As a last route to low cost cells we should technology and hence many materials 48
  • 49. N & N i n S p a i ndevelopments with nanostructure control will very often overcome through the development ofbe required. Particularly, novel wide band gap nanocomposite materials which can combine highsemiconductors such a ZnO or some nitrides are electronic conductivity with a fast and safe Li ion N A N O M AT E R I A L S F O R E N E R G Ybeing widely investigated. insertion capability, thus becoming a very promising route to new advanced battery2.3 Electrical energy systems. Nanoscale interfacial and strain characterization together with in-situ structuralElectrical energy has been continuously modification analysis of materials bearing a highincreasing its share as energy vector since its degree of disorder are key problems requiringimplementation, achieving at present values convenient tools such as HRTEM and scatteringnear 40%. It is expected that this process will techniques (neutrons, synchrotron radiation).continue in the future. Particularly the cleannessof this vector greatly facilitates its use in Supercapacitors are based on high surface areatransport systems (at present associated to 30% nanomaterials where the idea of a double layerof the total fossil fuel consumption). charge accumulation is implemented veryAdditionally, the increasing demand of efficiently. These systems can be assimilated toenhanced reliability and power quality, even a set of series capacitor system where thewith a strong increase of the intermittency of electrical charge is accumulated at the electroderenewable generation, has raised the concept of interfaces.smart grids where new semiconducting powerelectronics and superconducting power systems The main advantage of these storage systems isare needed. Even though, the issue of achieving their fast charge – discharge times (onlyefficient electricity storage systems continues to electronic charge transport is involved, nobe a key issue for any future development of this chemical reaction) and hence they are usefulenergy vector. We will therefore review as well complements to conventional batterieselectrochemical energy storage systems such as (accumulation of car breaking energy forbatteries and supercapacitors. instance). Conversely, only a low energy density has been achieved up to now, although newElectrical batteries and supercapacitors cover a ideas are promising to enhance it. The mostwide spectrum of the Ragone diagram (power widely investigated materials for such systemsdensity – energy density) and the improvement are Carbon based porous materials (nanotubes,rely on a full understanding of the electrical and fibres, etc.) although other alternatives such aselectrochemical processes in relationship with anodized alumina membranes coated withthe structural and chemical transformations at metals (ALD) or mesoporous transition metalthe nanoscale. Li ion batteries are the most oxides have recently appeared as very efficientpromising systems for hybrid and electrical cars materials with potential for increasing also theand so the major developments are associated energy density. A particular concern in suchto electrodes for Li insertion. A major concern is nanoporous materials is to achieve a tightto avoid material aging during the charge - control of the pore size.discharge processes and to reduce the requiredtime. These issues have been found to be much Superconducting materials have generated areduced in oxide or phosphate electrodes with boost of new efficient and reliable powernanometric dimensions (nanowires, nanoparticles) systems having a huge potential for smartwhere lattice expansion do not degrade the electrical energy distribution, energy storageperformances. Conflicting functionalities can be and generation and final use (motors). 49
  • 50. N & N i n S p a i n The key development for a fast market systems. In spite of the remarkable progress penetration is to fabricate long-length already achieved, there is still a large margin for nanostructured conductors at low cost, mainly improvement because the theoretical limits ofN A N O M AT E R I A L S F O R E N E R G Y through chemical deposition methodologies. these materials are still well above the achieved The most promising materials are at present the critical currents. It’s particularly essential to so called 2nd generation (2G) coated understand properly the relationship between conductors, based on YBa2Cu3O7 (YBCO). nanostructure and vortex pinning properties. The first goal has been to avoid the detrimental These conductors have demonstrated current effect of grain boundaries on critical current densities 10 times higher than Cu and so the density and this has already been achieved development of high power underground cables through clever methodologies to develop oxide (5-7 times conventional wire power) is one of epitaxial layers on metallic substrates while the closest priorities, together with Fault current keeping structural control at the nanoscale. limiters to reach a smarter grid allowing to Industrial production of 2G conductors over km integrate the renewable energies The worldwide lengths has been already demonstrated although roadmaps defined up to now suggests a much more effort is still required to simplify their progressive penetration of this new technology architecture and hence reduce the cost. in the market of power systems in the next 10-20 years. A second boost on performance of 2G superconductors has been recently 3. International publications (2007-2009) demonstrated through the development of nanocomposite films and conductors. The goal A selection of publications spanning all the fields here is to create a network of nanometric non- mentioned before is reported here. superconducting phases (nanodots, nanorods) within the superconducting matrix which pin •J. Gutiérrez, A. Llordés, J. Gázquez, M. Gibert, vortices and hence increase the critical current N. Romà, S. Ricart, A. Pomar, F. Sandiumenge, at high temperatures and under high magnetic N. Mestres, T. Puig and X. Obradors. fields. Strong isotropic flux pinning in solution- derived YBa2Cu3O7-x nanocomposite Understanding the growth mechanisms of superconductor films. complex oxide nanocomposites and the Nature Materials, 6 (2007), pp. 367-373. influence of induced strain on the •B. E. Hardin, E.T. Hoke, P.B. Armstrong, J.H. superconducting properties is one of the present Yum, P. Comte, T. Torres, J.M.J. Frechet, M.K. bottlenecks for further development of Nazeeruddin, M. Gratzel and M.D. McGehee materials with enhanced performance. Increased light harvesting in dye-sensitized solar cells with energy relay dyes. For the first time, the performance of these Nature Photonics, 3 (2009), pp. 406-411. nanostructured superconductors has surpassed at 77OK those of low Tc superconductors at liquid •H. Gommans, T. Aernouts, B. Verreet, P. He temperature. Heremans, A. Medina, C.G. Claessens, G Christian and T. Torres. Very high magnetic fields are expected to be Perfluorinated Subphthalocyanine as a New created for magnets (fusion), generation (wind Acceptor Material in a Small-Molecule Bilayer energy), motors (ships) and energy storage Organic Solar Cell. 50
  • 51. N & N i n S p a i n Advanced Functional Materials, 19 (2009), pp. Pennycook and J. Santamaría. 3435-3439. Colossal ionic conductivity at the interfaces of epitaxial ZrO2:Y2O3/ SrTiO3 heterostructures.•M. R. Palacín. N A N O M AT E R I A L S F O R E N E R G Y Science 321 (2008), pp. 676-680. Recent advances in rechargeable battery materials: a chemists perspective. •S.A. Haque, S. Koops, N. Tokmoldin, J. R. Chemical Society Reviews, 38 (9), (2009), pp. Durrant, J. S. Huang, D.D.C. Bradley and E. 2565-2575. Palomares.•G. F. Ortíz, I. Hanzu, T. Djenizian, P. Lavela, J. L. A multilayered polymer light-emitting diode Tirado and P. Knauth. using a nanocrystalline metal-oxide film as a Alternative Li-Ion Battery Electrode Based on charge-injection electrode. Self-Organized Titania Nanotubes. Advanced Materials, 19 (2007), pp. 683-687. Chemistry of Materials, 21 (2009), pp. 63-67. •R. Otero, D. Ecija, G. Fernández, J. M. Gallego,•M. Gibert, T. Puig, X. Obradors, A. Benedetti, L. Sánchez, N. Martin and R. Miranda. F. Sandiumenge and R. Hühne. An organic donor/acceptor lateral Self-organization of heteroepitaxial CeO2 superlattice at the nanoscale. nanodots grown from chemical solutions. Nano Letters, 7 (2007), pp. 2602-2607. Advanced Materials, 19 (2007), pp. 3937- •R. M. Navarro, M. C. Sánchez-Sánchez, M. C. 3942. Alvarez-Galván, F. del Valle and J. L. G. Fierro.•J. Gutiérrez, T. Puig, M. Gibert, C. Moreno, N. Hydrogen production from renewable Roma, A. Pomar and X. Obradors. sources: biomass and photocatalytic Anisotropic c-axis pinning in interfacial self- opportunities. assembled nanostructured trifluoracetate- Energy & Environmental Science, 2 (2009), pp. YBa2Cu3O7-x films. 35-54. Applied Physics Letters, 94 (2009), art. •S. Colodrero, A. Mihi , L. Haggman , M. Ocana, 172513. G. Boschloo, A. Hagfeldt and H. Miguez.•F. Fabregat-Santiago, J. Bisquert, L. Cevey, P. Porous One-Dimensional Photonic Crystals Chen, M.K. Wang, S.M. Zakeeruddin, M. Shaik Improve the Power-Conversion Efficiency of and M. Gratzel. Dye-Sensitized Solar Cells. Electron Transport and Recombination in Advanced Materials, 21 (2009), pp. 764-770. Solid-State Dye Solar Cell with Spiro-OMeTAD •I. González-Valls and M. Lira-Cantu. as Hole Conductor. Vertically-aligned nanostructures of ZnO for Journal of the American Chemical Society, 131 excitonic solar cells: a review. (2009), pp. 558-562. Energy & Environmental Science, 2 (2009), pp.•J. Álvarez-Quintana, X. Álvarez, J. Rodríguez- 19-34. Viejo, D. Jou, P.D. Lacharmoise, A. Bernardi, A.R. Goni and M.I. Alonso. 4. Initiatives to be undertaken in Spain within Cross-plane thermal conductivity reduction of the period 2010-2013 vertically uncorrelated Ge/Si quantum dot superlattices. The R&D activities related to the energy sector Applied Physics Letters, 93 (2008), art. 03112. have remained much dispersed up to now while•J. García-Barriocanal, A. Rivera-Calzada, M. it has become critical nowadays to achieve a Varela, Z. Sefrioui, E. Iborra, C. León, S. J. critical mass in those domains where there is 51
  • 52. N & N i n S p a i n clear technological demand. The chain value for should be limited. Additionally, the link between energy related issues is very wide, spanning from these research-based programs and the existing nanoscience and advanced materials, to development and valorization programs is veryN A N O M AT E R I A L S F O R E N E R G Y materials engineering, systems development weak and it should be strengthened. and integration and final use, including market pull views and regulations. Properly addressed roadmaps integrating the multiple initiatives would certainly help to It is clear that Spain has a large offer of maximize the overall efficiency of the R+D+i companies related to the final use of energy system. which can play a catalytic role for the whole chain value mentioned above. Also specific regulation The research activities on Nanomaterials for and governmental actions can decisively foster energy require quite specific equipments and the industrial dynamism of this sector. facilities and very often the implementation of research centers on Nanoscience and Unless decisive actions are taken to promote the nanotechnology do not cope adequately with transformation of more traditional industries into these specific needs. this new sector and to create new high-tech companies it is very likely that the final user The “bottom-up” approach characterizing these companies will base their business fully on activities require specific laboratories, materials, components and devices produced equipments and advanced characterization abroad. facilities which are not being properly attended up to now. It is also worth to stress the need of It is also worth to stress, however, that this is a significant efforts on multiscale nanomaterials global business and so in most of the cases the simulation to cope with the complexity of the Spanish industry will need to be integrated into many phenomena involved. European initiatives in order to have a global size. Hence it becomes very important to establish It is important to point out as well the need, in strategic actions and alliances much before than the very early stage of development, of scaling- any product becomes a commercial reality. up the production of nanomaterials in order to integrate them in demonstrators of systems or In most of the cases the research groups being devices for further engineering development active in Spain in the areas mentioned within the needs to be properly considered. “State of the art” section have not achieved enough critical mass to become leaders in the The demonstration stage is essential in this area; international scene, even if in many cases the otherwise the new technology penetration is research activities carried out have a very delayed and the capability of innovation through significant impact. technology transfer is lost. The establishment of larger research projects, On the other hand, the field of Nanomaterials such as the Consolider programs, has helped to for energy requires an accelerated action to a certain degree to overcome this limitation. prepare highly skilled personnel; otherwise there will a very important shortage of trained Still, however, these programs have not been scientists and technologists in a wide span of accompanied by the necessary investments on new technologies being developed. It is infrastructures and so the expected outputs therefore very important to define priorities for 52
  • 53. N & N i n S p a i nPhD fellowships, postgraduate courses and address the energy challenge should betechnical staff recruitment. strongly promoted. N A N O M AT E R I A L S F O R E N E R G YIn conclusion, the proposed priority actions to 5. Required infrastructure to reach thebe considered to foster a successful R&D&i in objectives (2010-2013)the area of Nanomaterials for energy are thefollowing: • Nanofabrication units adapted to the requirements of the materials for energy,• To define a few specific areas and laboratories mainly based on bottom-up approaches. (or networks) where research actions Specifically, clean room areas with tools including nanoscience-based materials are adapted to the chemical processes and in-situ taken with the purpose of integrating the full characterization methodologies should be chain of value. The definition of mid and long made available. These facilities should allow term roadmaps should be a specific individual researchers and small research requirement of this initiative. The goal will be groups to explore new ideas fast and using to achieve a scientific and technological the most advanced methodologies. leadership position. • Advanced characterization facilities with• The initiatives should involve scientific groups capabilities adapted to the specific with the required know-how and industries characteristics of the nanomaterials for from the whole chain of value, from the energy. Electron nanoscopic research is a manufacturing sector to the final users, particularly useful area because including the corresponding system compositional and structural analysis may be development companies. performed altogether. Very significant advances have been made recently in this The initiative should have also as an objective area (aberration correction microscopes in to promote the creation of spin-off transmission and scanning modes) which companies to develop the scientific advances requires a decisive action to keep the pace in worth of being commercialized and to handle the international scene. Three dimensional an aggressive IPR policy. microstructure imaging analysis by electron• To establish advanced research facilities in tomography is also becoming a useful tool for nanoscience with open access and adapted to the complex arrangement of components the required bottom-up nanofabrication needs. including nanomaterials for energy. Also to generalize the implementation of • Advanced tools for sample preparation are also advanced characterization facilities such as needed to make a full use of these “Nanoscopy spectroscopy centers” with the methodologies. The use of the new necessary equipment and technical skills to synchrotron radiation center ALBA will also cope with the demand of research having very help to carry out advanced structural and specific features relevant to this field. spectroscopic analysis of energy-related nanomaterials. Finally, specific physical and• To engage specific actions to attract highly chemical characterization tools with nanoscale motivated students to the field of analysis adapted to the complex nanomaterials for energy and energy functionalities of energy-related materials technologies in general. Outreach activities should be more widely implemented and/or stressing the potential of nanoscience to developed. 53
  • 54. N & N i n S p a i n • Mid-size materials fabrication laboratories • Molecular nanoscience (NANOMOL). integrating the developments on CSD 2007-00010, Coordinator: Eugenio nanomaterials. These laboratories are veryN A N O M AT E R I A L S F O R E N E R G Y Coronado Miralles, Center: Instituto de Ciencia specific but they are a key requirement to Molecular de la Universidad de Valencia. achieve a mature development for any new emerging technology. • Advanced materials and Nanotechnologies for innovative Electrical, Electronic and • Materials engineering skills are required and magnetoelectronic devices (NANOSELECT). their implementation should help to gain the required vertical integration of the whole CSD 2007-00041, Coordinator: Xavier chain of value. Obradors Berenguer, Center: CSIC Instituto de Ciencia de Materiales de Barcelona. 6. Relevant initiatives and projects • Advanced Wide Band Gap Semiconductor Devices for Rational Use of Energy. • Several materials research projects of the National Research Plan (Materials and CSD 2009-00046, Coordinator: José Millán Nanoscience strategic action) are related to the Gómez, Center: CSIC Centro Nacional de area of nanoscience in energy-related topics. Microelectrónica. • Also many master courses devoted to energy • Developments of more efficient catalysts for research are already offered by several the design of sustainable chemical processes Universities in Spain. A significant part of and clean energy production. these masters include materials related CSD 2009-00050, Coordinator: Avelino Corma, issues. Center: CSIC Instituto de Tecnología Química. Only a few examples of large research projects Additionally, it is worth to mention that related to nanomaterials for energy are several new research centers have been mentioned here. implemented in Spain related to the topics mentioned in this report. 6.1 Spain New research centers in Spain CONSOLIDER Projects • L’Institut de Recerca de l’Energia de Catalunya • Research on a New Generation of Materials, (IREC). New energy research center, Catalonia. Cells and Systems for the Photovoltaic • Centro de Investigación Cooperativa CIC Conversion (GENESIS-FV). energiGUNE. New energy research center, CSD 2006-00004, Coordinator: Luque López, Basque Country. Antonio, Center: Instituto de Energía Solar de • IMDEA Energía. New research center, Madrid. la Universidad Politécnica de Madrid. • Hybrid Optoelectronic and Photovoltaic for 6.2 Europe Renewable Energy (HOPE). A selection of EU based projects in the fields CSD 2007-00007, Coordinator: Juan Bisquert with Spanish participation: Mascarell, Center: Escuela Técnica Superior de • High performance nanostructured coated Ingeniería de la Universidad Jaume I, conductors by chemical processing (HIPERCHEM). Castellón. NMP3-CT-2005-516858, 2005-2008, 54
  • 55. N & N i n S p a i n Coordinator: ICMAB-CSIC. NASA-OTM-228701, 2009-2012, Instalaciones INABENSA, S.A., CSIC.• Efficient environmental-friendly electro- N A N O M AT E R I A L S F O R E N E R G Y ceramics coating technology and synthesis • Nanostructured Electrolyte Membranes Based (EFECTS). on Polymer-Ionic Liquids-Zeolite Composites for High Temperature PEM Fuel Cell EFECTS-205854-1, 2008-2011, ICMAB-CSIC. (ZEOCELL).• Development and field test of an efficient ZEOCELL-209481, 2008-2010, Universidad de YBCO Coated Conductor based Fault Current Zaragoza, Celaya Emparanza y Galdos SA, Limiter for Operation in Electricity Networks CIDETEC. (ECCOFLOW). • Nanotechnology for advanced rechargeable ECCOFLOW-241285, 2010-2013, ICMAB-CSIC, polymer lithium batteries (NANOPOLIBAT). Endesa, Labein. FP6-NMP-2004-33195, 2006-2009, Institut de• Modelling of interfaces for high performance Ciència de Materials de Barcelona (ICMAB- solar cell materials (HIPERSOL). CSIC). HIPERSOL-228513, 2009-2012, ISOFOTON, S.A. • Large-Area CIS Based Thin-Film Solar Modules• Development of photovoltaic textiles based on for Highly Productive Manufacturing (LARCIS). novel fibres (DEPHOTEX). FP6-SUSTDEV-19757, 2005-2009, Universitat DEPHOTEX-214459, 2008-2011, CETEMMSA, de Barcelona. CENER-CIEMAT, Asociación de la Industria • Advanced Thin-Film Technologies for Cost Navarra. Effective Photovoltaics (ATHLET).• Intermediate band materials and solar cells FP6-SUSTDEV-19670, 2006-2009, Centro de for photovoltaics with high efficiency and Investigaciones Energéticas, reduced cost (IBPOWER). Medioambientales y Tecnológicas. IBPOWER-211640, 2008-2012, Universidad • Ionic liquid based Lithium batteries (ILLIBATT). Politécnica de Madrid. FP6-NMP-2004-33181, 2007-2010, Celaya• Efficient and robust dye sensitzed solar cells Emparanza y Galdos SA, CIDETEC. and modules (ROBUST DSC). • Advanced lithium energy storage systems ROBUST DSC-212792, 2008-2011, Institut based on the use of nano-powders and nano- Català d’Investigació Química, Universidad composite electrodes/electrolytes (ALISTORE). Autónoma de Madrid.• Smart light collecting system for the efficiency FP6-SUSTDEV-503532, 2004-2008, Institut de enhancement of solar cells (EPHOCELL). Ciència de Materials de Barcelona (ICMAB- CSIC), Universidad de Córdoba. EPHOCELL-227127, 2009-2013, Acondicionamiento Tarrasense Asociación, 7. Conclusions MP Bata Consultoria Medioambiental S.L. CIDETE Ingenieros S.L., Universitat Politecnica Spain is particularly well positioned in the de Catalunya. international scene in the field of energy• NAnostructured Surface Activated ultra-thin technologies, with several companies and Oxygen Transport Membrane (NASA-OTM). industrial sectors being widely recognized for its 55
  • 56. N & N i n S p a i n 4 innovative profile. Research in energy N.S.Lewis, “Powering the planet”, MRS Bulletin technologies and materials related issues, 32, 808 (2007). particularly nanoscience and nanotechnology, isN A N O M AT E R I A L S F O R E N E R G Y now very stringently promoted worldwide, linked 5 “Climate change 2007”, Intergovernmental with the urgent need of addressing the energy Panel on Climate Change report, Cambridge challenge of the 21st century. Therefore, it is clear Univ. Press (2007) (www.ipcc.ch). that it’s strategically very important to position the R&D&i in nanomaterials for energy as a priority. 6 R. E. Smalley, MRS Bulletin 30, 412 (2005); D. J. Nelson, M. Strano, Nature Nanotechnology 1, 96 A certain number of initiatives have been (2006). already engaged to develop the above mentioned potential, however, there are still 7 “Alternative energy technologies”, Nature 441, many drawbacks in the coordination of 332 - 377 (2001). initiatives and in the definition of priorities which have been described here in a certain 8 “Harnessing Materials for energy”, MRS Bulle- detail. For sure, nanomaterials for energy brings tin 38, 261 - 477 (2008). a timely and unique opportunity for innovation which Spain can not miss, mainly taking into 9 “Novel materials for energy applications”, Eu- account the present need for a turning point in ropean Comission, I. Vouldis, P. Millet and J.L. our economic model. Vallés eds. (2008). (http://ec.europa.eu/research/industrial_ References technologies/). 1 US Department of Energy reports 10 Toward a Hydrogen economy”, Science 305, (www.sc.doe.gov/bes/reports) 957 – 1126 (2004). • “Basic research needs to assure a secure 11 energy future” A. P. Malozemoff, Nature Materials 6, 617 • “Workshop on solar energy utilization” (2007). • “Basic research needs for the Hydrogen eco- nomy” • “Basic research needs for superconductivity” • “Basic research needs for Solid state lighting” • “Basic research needs for electrical energy storage” • “Grid 2030: a national vision for electricity’s second 100 years” • “Transforming electricity delivery – Strategic plan” (2007). 2 “Climate change“, Science 302, 1719 - 1926 (2003). 3 “Climate change”, Nature 445, 578 - 582 (2007). 56
  • 57. N & N i n S p a i n 57
  • 58. > JOSEP SAMITIER Place and date of birth Barcelona (Spain), 1960 Education • M.S. Degree; Physics; Barcelona University. • Ph.D Degree; Physics; Barcelona University. Thesis Title: GaAs MESFET Devices and electro- optical characterization of III-V semiconductors. Profesional Experience • Full Professor of Electronics, Barcelona University. • Chair of Department of Electronics, Barcelona University. • Director of the Nanobioengineering Laboratory (IBEC). Director of Bioengineering Section. • Barcelona Science Park. Deputy head Electronic Engineering School. • Visiting Professor LAAS (Toulouse). • Assistant professor of Electronics. • Visiting research fellow at the Philips Electronic Laboratory (LEP) Paris (France). Honors and Awards Barcelona city Prize in the area of technology. jsamitier@ibecbarcelona.eu 58
  • 59. NANOMEDICINE1. Introduction 2. State of the Art nanomedicine (from the nanomedicine roadmap 2020)Nanomedicine has emerged as a novel fieldwhich involves the application of 2.1 Regenerative Medicinenanotechnology to human health. Varioustherapeutic and diagnostic modalities have been A really broad definition of Regenerative Medicinedeveloped which can potentially revolutionize includes the repair, replacement, or regenerationdisease diagnostic and treatment. The know- of damaged tissues or organs with a combinationhow in nanotechnology offers new ways to of several technological approaches, which can becreate better laboratory diagnostic tools for roughly devided into two subareas: smartnon-invasive screening. biomaterials and advanced cell therapy.Accurate and early diagnosis, will facilitate Smart Biomaterialstimely clinical intervention and can mitigate pa-tient risk and disease progression. The Since 2006, research on biomaterials has fosteredconventional oral and parental routes of drug many steps forward and significant changes onadministration have several disadvantages owing the tissue regeneration approach. Majorto altered pharmacokinetic parameters and wide attention has been given to the importance ofspread distribution. Targeted delivery of drugs, biomaterial mode of action. Research efforts havenucleic acids and other molecules using moved from the development of inert polymersnanoparticles are the focus of current research which mimic the biomechanical properties ofand development. The goal of tissue engineer- native tissue to bioactive materials whiching or regenerative medicine is the improvement, promote the tissue self healing.repair, or replacement of tissue and organfunction. The ultimate goal is to enable the body The development of smart biomaterial can be dividedto heal itself by introducing and engineered into two phases: discovery and process optimization. Inscaffold that the body recognizes as own. The the discovery phase, the main issue is productchallenges are not minor. If nanotechnology is to characterization. 3D functional assays and devices tobe translated into meaningful benefits for measure intracellular signals are useful tools in thispatients, innovation in the laboratory must be phase. The process optimization phase involves thesupported by the pillars of evidence based translation of prototype into product assuring scalability,medicine and predictable regulatory pathways. quality, and safety of the proposed treatment. 59
  • 60. N & N i n S p a i n Cell therapies particles should be biocompatible and acceptable to regulatory agencies e.g. not retained in the From May 2005 the European Commission body, even if inert. Therapeutic particles should prepared several draft regulation intended to be relatively inexpensive, manufacturable, harmonize in EU the legislation on human tissue acceptable to regulators, and stable to storage. engineered products. The finalization of a common European regulatory framework Another topic will be that of transporters orNANOMEDICINE required slow and complex public consultation, technologies capable of moving therapeutic which ended in September 2008 with the nanoparticles across biological membranes, publication of the final guidelines. tissues or organs at a transport rate such that therapy can be effective. For proteins for example The development of an effective cell therapy this lies in the range of 10 mgs per day orally. includes different phases: the identification of best materials for cell transplantation and the Besides that, the choice of the delivery route or optimization of the production process. The first the barriers to be crossed will be important, e.g. phase takes into account the development and Intracellular, Dermal, Oral, Pulmonary, Blood characterization of different devices for cell Brain Barrier. This choice will determine the transplantation. The process optimization phase technologies applicable. Another factor to be involves quantifying the relationship between addressed will be the bioavailability of culture parameters and cell output, as well as macromolecule which has to be larger than 10%. research on scale-up. The third phase consists of toxicology assessment and quality control for The choice of the therapeutic modality will be therapeutic delivery of the cell product. essential. This could include proteins, antibod- ies, nucleic acids, peptide mimetics, PNAs, Cell-materials compounds or engineered tissues foldamers, “non-Lipinski” molecules and can be considered as a “delivery system” where materials that require some external activation the cells are immobilised within polymeric and such as ultrasound. Small molecules could also biocompatible devices and secrete therapeutic be included but they normally already have a products. In this light, drug delivery control is a good bioavailability and expensive delivery key parameter for the development of a new technologies may not be reimbursed making medicine. Research on biomaterials has been them probably a lower priority. focused on the design of safe and manufacturable technologies for the local and To bring to the market new therapeutic systemic delivery of therapeutic molecules from modalities or to expand the current clinical uses the enclosed cells. of biologicals therapeutic entities such as nucleic acids are required. Such new therapeutic classes 2.2 Drug Delivery (Nanopharmaceutical and should offer radical improvements in the Nanodevices) treatment of difficult diseases. One area identified of being crucial for future 2.3 Diagnostics breakthroughs is the area of Nano-encapsulation or nanodelivery systems that have a significant The area of diagnostics can be divided into in therapeutic payload and are capable of being vivo and in vitro technologies. In both areas the transported through biological barriers. Such goal is to detect an evolving disease as early as 60
  • 61. N & N i n S p a i npossible up to the point of detecting single cells development. The trend here is clearly onor biomarkers indicating the onset of a disease. implementing these imaging modalities alone orMajor objectives are the development of: in combination.• Devices for combined structural and Miniaturization of imaging devices and functional imaging, improvement of technical specifications of existing imaging systems can be achieved thanks• Portable point of care devices, NANOMEDICINE to nanotechnology. In the perspective of• Devices for multi parameter measurement developing a lightweight, small footprint CT6 (multiplexing), system, a proposed disruptive technology uses carbon nanotube based X-Ray sources in CT to• Devices for monitoring therapy and shrink the size of the complete systems. This personalized medicine. would allow to bring CT to the doctor’s officesIn the In vivo imaging area some substantial or even to ambulances. On the opposite, “babychallenges have been identified. One of the cyclotrons” seem to be out of reach.foremost obstacles is the difficulty in obtaining anapproval of new and innovative contrast agents. In vivo imaging can also be used for guiding therapy with MR, PET, Optical and X-ray/CT,This includes obviously also the necessity to MRgFUS for biopsy and drug release. Targetedconfirm the benefits for the patients. therapy is expected to lead to improved quality ofChallenging is as well the task to further improve healthcare, in reducing treatments withthe imaging equipment as such and not to forget unsatisfactory patient outcome or with adversethe training of endusers. Nanotechnology can effects.contribute to the development of the in vivoimaging area by two means: Reducing the concentration of contrast agents is one means to reduce costs. The characteristics• Improving the existing and/or discovering of contrast agents (size, composition, coating, new quantitative imaging systems. and physical properties) can be adjusted to respond efficiently to design requirements, for• Developing new contrast agents for instance for a better sensitivity and specificity. enhancing contrast.The benefits expected from nanotechnology are Another option is to design or develop amainly based on the physical and chemical contrast medium capable of serving severalproperties of novel materials at the nanoscale. modalities. This could consequently also reduceHowever, the development of nanotech based in the volumes and reinjection rates. In fact, thesevivo imaging also depends on several non- contrast agents which can be used in differenttechnical parameters like, regulatory approval of modalities separately or combined in acontrast agents, education and training of multimodality approach are highly desirable.healthcare operators and healthcarereimbursement policy. New types of carriers for contrast agents are envisaged such as magnetic nanoparticles orWhile some conventional imaging modalities like even empty viruses or magnetic bacteria.PET1, MRI2, SPECT3, US4, are revisited by Magnetic particles would offer higher efficiencynanotech, some new imaging modalities like the due to narrower magnetic characteristicMPI5 method (by Philips) are currently under distribution, precise control of magnetic 61
  • 62. N & N i n S p a i n properties, and an inherent potential for lower •Seven Challenges for nanomedicine, Nature costs. The production of magnetic nanoparticles nanotechnology Vol 3 May 2008. could also be envisaged by biomimetic •Emerging trends of nanomedicine an templating. Another category of nanoscale overview, Fundamental & Clinical particles are crystalline nanoparticles used for Pharmacology 23 (2009) 263-269. therapeutic purposes or for diagnostic applications in combination with external devices •Translational nanomedicine: status asessementNANOMEDICINE such as MRI, Laser, Radiotherapy, CT Scan, and opportunities, Nanomedicine Vol 5 (2009) Ultrasound, HF, etc. In particular the up-scaling 251-273. of the production methods for contrast agents is •Designer Biomaterials for nanomedicine, Adv. thought to provide a great economic potential Funct. Mater 2009 19 3843-3854. that could create substantial economic returns. •Detecting rae cancer cells, Nature 3. International publications nanotechnology, Vol 4 Dec 2009 798-799. •Nanomedicine – challenge and perspectives, If you introduce the world nanomedicine in the Angew. Chem. Int. 2009 48, 972-897. web (www.gopubmed.com/web/gopubmed) we •Nanomedicine: perspective and promises with obtain 1,388 documents distributed. ligand-directed molecular imaging, European J. of radiology 70 (2009) 274-285. We observe that Spain is in the second position after USA, and Barcelona is the second city after 4. Initiatives Boston. Nanomedicine European Technology Platform Its difficult to remark the most important paper (ETP) published, so we prefer to summire the best results and challenges of nanomedicine The Nanomedicine ETP is important initiative led published in some review and opinion papers as: by industry set up together with the European Commission. A group of 53 European stakeholders composed of industrial and academic experts established the European Technology Platform on nanomedicine in 2005. The first task of this high level group was to write a vision document for this highly future-oriented area of nanotechnology-based health-care in which experts describe an extrapolation of needs and possibilities until 2020. At the beginning of 2006 the Platform was opened to wider participation (currently 95 member organisations) and has delivered a so-called Strategic Research Agenda showing a well elaborated common European way of working together for the healthcare of the future trying to match the high expectations that nanomedicine has raised so far. In 2009 the ETP 62
  • 63. N & N i n S p a i npublished the Nanomedicine roadmap 2020: plans on certain strategic issues to be solved in(www.etp-nanomedicine.eu/public). the medium to long term. (www.nanomedspain.net).The Spanish Technology Platform onNanoMedicine (STPNM) is a joint initiative The INGENIO 2010 programme aims to achievebetween Spanish industries and research centres a gradual focus of these resources on strategicworking on nanotechnologies for medical actions to meet the challenges faced by the NANOMEDICINEapplications. This initiative is supported by the Spanish Science and Technology System. ThisSpanish government through the Centre for gradual focus will be achieved by allocating aIndustrial Technology Development (CDTI) and significant portion of the minimum annualthe Spanish Ministries of Science and Innovation increase of 25% in the national R&D and(MICINN), Industry, Tourism and Trade (MICyT), Innovation budget to strategic initiativesand Health (MSC). grouped in three major lines of action:The main objectives of the Platform are: • The CENIT Program (National Strategic Technological Research Consortiums) to• Improve the collaboration within the stimulate R&D and Innovation collaboration Nanomedicine community in Spain avoiding among companies, universities, public fragmentation and lack of coordination, research bodies and centres, scientific and technological parks and technological centres.• Promote the participation of Spanish The CENIT program cofinance major public- stakeholders in international initiatives, from private research activities. These projects will transnational cooperations to European last a minimum of 4 years with a minimum projects, especially regarding the European annual budgets of 5 million euros, where i) a Technology Platform, minimum of 50% will be funded by the private• Establish recommendations concerning sector, and ii) at least 50% of the public strategic research lines in the Nanomedicine financing will go to public research centres or field, technological centres.• Dissemination of Nanomedicine results to the • The CONSOLIDER Program to reach critical scientific community and society-at-large. mass and research excellence. CONSOLIDER Projects offers long-term (5-6 years), largeThe focus of the Spanish Platform, with more scale (1-2 million euros) financing forthan 150 members, is divided in five strategic excellent research groups and networks.priorities: Nanodiagnostics; Regenerative Research groups may present themselves inMedicine; Drug Delivery; Toxicity and all areas of know-how of the National R&DRegulation; and Training and Communication. and Innovation Program.This activity has facilitated a wide participationof Platform members in Spanish strategic • CIBER Projects promote high quality researchresearch programmes run by the Spanish in Biomedicine and Health Sciences in thegovernment through the Ingenio 2010 initiative. National Health Care System and the NationalIn September 2006 the Spanish Platform R&D System, with the development and en-published a report focused on current status of hancement of Network Research Structures.Nanomedicine in Spain “strategic vision of The CIBER-BBN is one of the new CIBERnanomedicine in Spain” in order to establish consortia in Spain, to encourage qualityresearch and development priorities and action research and create a critical mass of 63
  • 64. N & N i n S p a i n researchers in the field of Biomedicine and Glossary Healthcare Sciences. The scientific areas 1 represented within the CIBER-BBN are: PET: Positron Emission Tomography 2 Bioengineering and biomedical imaging, MRI: Magnetic Resonance Imaging 3 Biomaterials and tissue engineering and SPECT: Single Photon Emission Computed Nanomedicine, and the Center’s research is Tomography 4 focused on the development of prevention, US: Ultra SoundNANOMEDICINE 5 diagnostic and follow-up systems and on MPI: Magnetic Particle Imaging 6 technologies related to specific therapies such CT: Computed Tomography as Regenerative Medicine and Nanotherapies. (www.ciber-bbn.es). In addition to these three main programs, new research centers supported by regional administrations, support actions to increase human resources creating new stable research positions and a strategic scientific and technological infrastructures program are also included in the Ingenio 2010 initiative and in the research and innovation plan from the autonomous regions. 5. Conclusions Nanotechnology will have direct applications in medicine by contributing to improvements in health and life quality, while decreasing the economic impact. The report concludes that Spain can play a relevant role in the development of this field because it has cutting-edge research centres, industrial and pharmaceutical sectors interested in using these new technologies as well as a health care system based on a network of hospitals with a very good basic and clinical research, interested in the development of translational research programs. Taking into account that the participation in the different instruments is in many cases incompatible, and the calls were open to all the Spanish science and technology system, these results confirm that the nanomedicine is a research priority in Spain and that exists a potentially strong sector to be developed in the next years. 64
  • 65. N & N i n S p a i n 65
  • 66. > EMILIO PRIETO Place and date of birth Madrid (Spain), 1956 Education Mechanical Engineer by both ICAI-UPC (1981) and the Polytechnic University of Madrid (1982). Ph.D. by the Polytechnic University of Madrid, Department of Physics applied to Engineering (2007). Professional Career • In 1982 joined the National Commission of Metrology and Metrotecnics. Since 1994, Head of Length Area at the Spanish Centre of Metrology. • Member of the Consultative Committees for Length (CCL) and Units (CCU), of the International Committee of Weights and Measures (CIPM). • Length Contact Person in EURAMET, Member of the International Society for Optical Engineering (SPIE), the Scientific Committee of NanoSpain, the Dimensional Metrology Committees from ENAC and AENOR CTN 82 and Chairman of the AENOR GET 15 Committee on Standardization on Nanotechnologies. eprieto@cem.mityc.es 66
  • 67. N A N O M E T R O L O G Y, N A N O - E C O - T O X I C O L O G Y A N D S TA N D A R D I Z AT I O N1. Introduction such dimensions. To get quantitative measurements is essential to count with accurateNanotechnologies enable scientists to and traced measuring instruments, together withmanipulate matter at the nanoscale (size range validated measurement procedures widelyfrom approximately 1 nm to 100 nm) 1. Within accepted 2.this size region, materials can exhibit new andunusual properties, such as altered chemical Geometric features decisive for nanotechnologyreactivity, or changed electronic, optical or applications include 3D objects like largemagnetic behaviour. Such materials have molecules (e.g. DNA), clusters of atoms (e. g.applications across a breadth of sectors, ranging bucky balls), nanoparticles (like TiO2 particlesfrom healthcare to construction and electronics. added to products to improve reflectivity), nanowires (like carbon nanotubes (CNT), single-Quantitative determination of properties of walled CNT (SWCNT), multi-walled CNTmicro and nanostructures is essential in R&D and (MWCNT)), surfaces structures (super-a pre-requisite for quality assurance and control hydrophobic surfaces, riblets) and thin filmsof industrial processes. The determination of covering large surfaces (hardness, scratch-critical dimensions of nanostructures is resistance, reflectivity, wetting properties …) 3.important because the linking to many otherphysical and chemical properties depending on So, nanometrology, the science of measurement applied to the nanoscale plays a key role in the production of nanomaterials and nanometre devices. This has been recognized by many Governments, Research Institutions and the Private Sector across the World 4,5,6. There is no knowledge without accurate mesurements. Most of the today’s efforts in Research are not successful and they won’t be if there is no transfer to industrial applications. In fact, nanotechnology has not yet emerged as massive production due to both the difficulty of developing a solidFigure 1: 2D Standard nanometrology infrastructure and the lack of 67
  • 68. N & N i n S p a i nNANOMETROLOGY, NANO-ECO-TOXICOLOGY AND STANDARDIZATION awareness about it by researchers, product following specific R&D Programmes, as the developers and R&D funders. European Metrology Research Programme (EMRP) 8, a long-term programme for high quality But apart of potential benefits to consumers, joint R&D amongst the metrology community in nanotechnologies may also present new risks Europe, with a Phase 1 which started in 2007, that it is necessary to study, as a result of their supported by the European Commission through novel properties. A report by the European ERA-NET Plus, and a Phase 2 starting in 2010, Union Scientific Committee on Emerging and supported through Article 169 of the European Newly Identified Health Risks (SCENIHR) Treaty. published in 2009, listed a number of physical and chemical properties which affect the risk Some of the EMRP Joint Research Projects (JRP) associated with nanomaterials 7, among them related to nanometrology are: Traceable size, shape, solubility and persistence, chemical Characterization of Nanoparticles, New and catalytic reactivity, anti-microbial effects or Traceability Routes for Nanometrology or aggregation and agglomeration. This is Nanomagnetism and Spintronics. The Spanish particularly important in the Food Sector. The Centre of Metrology (CEM) participates since European Union has provided €40 million in 2008 in some of these EMRP Projects. funding for nanomaterials safety research in the last three years, along with another €10 million in 2009. Studies on nano-eco-toxicology, together with standardization issues, are then important and urgent matters today at international level. 2. State of the Art 2.1 Nanometrology Instruments and techniques used today at the nanoscale are many and varied: exploration probes, ion beams, electronic beams, optical means, X-Ray, electromagnetic means, Figure 2: Z-AXIS Step grating mechanical techniques, etc. New instruments offer every day better capabilities but such A very important initiative on this field of many equipments should be correctly calibrated in NMIs since 2000 has been the development of order to maintain their metrological capabilities metrological atomic force microscopes (MAFM). (traceability, accuracy) so guarantying the Today, there exist about 20 MAFM and 10 under reliability of the results, something crucial in construction all over the world. R&D and industrial production. In Spain, CEM is also funding and running its own Creation of metrological infrastructure, including the development of new calibration standards project to build a MAFM for the calibration of and measurement and characterization methods standards used at the nanoscale, integrating is not an easy task but it is intended for years by near field microscopy and high resolution most of National Metrology Institutes (NMIs), interferometric techniques based on stabilized 68
  • 69. N & N i n S p a i n NANOMETROLOGY, NANO-ECO-TOXICOLOGY AND STANDARDIZATIONlaser sources traced to the national standard of Spain is participating in some of the OECDlength, for the benefit of Institutes, R&D Committees and Working Groups related toCentres, Universities and Industry. A EURAMET nanotechnology:Workshop with participation of all teams • Working Party on Chemicals, Pesticides andcurrently working on - or that have worked on - Biotechnology,metrological AFM, will be held soon. • Working Party on Manufactured Nanomaterials. • Working Party on Nanotechnology. REACH—European Community legislation concerned with chemicals and their safe use— plays also a role, albeit limited, in regulating nanomaterials. The general opinion today is that REACH can adequately regulate nanomaterials, but there is a need for future revisions of REACH to move the focus of regulation from the size/shape of nanomaterials to also theirFigure 3: Grid Calibration AFM (Nanotec) functionality 9. 2.3 StandardizationVery important also is the series of Conferences“NanoScale” (www.nanoscale.de) where, since There is a key role for standardization as regards1995, the main developments on quantitative measurement and testing of the characteristicsmeasurements at the nanoscale have taken and behaviour of nanomaterials and theplace. These seminars on Quantitative exposure assessment, complementing the workMicroscopy and Nanoscale Calibration being carried out in the framework of the OECDStandards and Methods, taking place every two and in the context of the implementation ofyears, with open workshops of European REACH. The European Commission thereforeresearch projects related to the Coordination of requests CEN, CENELEC and ETSI to developNanometrology, have developed an increased standardization deliverables applicable to a)number of methods and calibration standards to Characterization and exposure assessment ofbenefit all users aware of instrumentation, no nanomaterials and b) Health, Safety &matter where they work (R&D, industry, Environment.Universities, etc.) helping them to maintain thetraceability and accuracy of their instruments, Specifically:and the reliability of the results.2.2 Risk Assessment 1. Methodologies for nanomaterials characterization in the manufactured form andA forum where international coordination is before toxicity and eco-toxicity testing.taking place is the OECD. At the present time theOECD plays a central role in the coordination of 2. Sampling and measurement of workplace,research efforts for the development of test consumer and environment exposure tomethodologies for risk assessment which will nanomaterials.underpin the regulation of nanotechnologies. 69
  • 70. N & N i n S p a i nNANOMETROLOGY, NANO-ECO-TOXICOLOGY AND STANDARDIZATION 3. Methods to simulate exposures to Propiedades físicas y aplicaciones de nanomaterials. materiales Spain is participating in the works of ISO/TC 229, • INASMET Tecnalia, Centro Tecnológico CEN/TC 352 and IEC/TC 113 Committees through the AENOR GET 15 Committee. • Instituto de Bioingeniería, Univ. Miguel Hernández Matter under study is divided into four main • Instituto Nacional de Seguridad e Higiene en fields: 1) Terminology and Nomenclature, 2) el Trabajo (INSHT), Min. Trabajo e Inmigración Measurement and Characterization, 3) Health, • LABEIN Tecnalia, Centro para la Aplicación de Safety and Environment and 4) Material los Nanomateriales en la Construcción Specifications. Many technical Specifications and • Meggitt International Standards are under production (about 40) [see Annex]. • Nanogap • Nanotec Electrónica S.L. AENOR GET 15 Committee is composed at the moment by individual voluntary representatives • Nanozar of the following Institutions: • Plasticseurope • Profibra, Asociación de productores de hilos y • AENOR, Asociación Española de fibras sintéticas, celulósicas y polímeros Normalización y Certificación (Host) • Univ. Alcalá de Henares, Dpto. Química • CEM, Centro Español de Metrología Inorgánica (Chairmanship) • ACCIONA Infraestructuras But it is important to involve many other • Alphasip Spanish Institutes, Platforms and stakeholders • Avanzare working in different aspects of nanotechnology to improve the coordination and contribute to • CIC nanoGUNE, Centro de Investigación en produce the best technical specifications for the Nanociencia ulterior benefit of Spanish industries and citizens. • CCMA, Centro de Ciencias Medioambientales (CSIC) 3. Most relevant international publications in • CEPCO, Confederación Española de the field (2007-2009) Asociaciones de Fabricantes de Productos de Construcción Some of the international publications with the • FEIQUE, Federación Empresarial de la highest impact factor are the following ones. Industria Química Española Nanometrology • Fundación LEIA, Centro de Desarrollo Tecnológico • An Assessment of the United States • Fundación TEKNIKER Measurement System: Addressing Measurement Barriers to Accelerate • GAIA, Asociación de Industrias de Tecnologías Electrónicas y de la Información del País Vasco Innovation, NIST Special Publication 1048, Jan 2007. • Univ. Pública de Navarra, Grupo de 70
  • 71. N & N i n S p a i n NANOMETROLOGY, NANO-ECO-TOXICOLOGY AND STANDARDIZATION• Journal of Research of the National Institute •Feynman’s Challenge: Building Things From of Standards and Technology, US, Will Future Atoms – One by One, E.C. Teague, Measurement Needs of the Semiconductor Proceedings of the euspen International Industry be Met?, Jan 2007. Conference – Zurich - May 2008.• Nanometrology of microsystems: traceability •Metrology at the nanoscale: what are the problem in nanometrology, Iuliana Iordache, grand challenges?, Kevin W. Lyons, Michael T. D. Apostol, O. Iancu, et al., SPIE Proceedings, Postek, SPIE Proceedings, Vol. 7042: Vol. 6635: Advanced Topics in Instrumentation, Metrology, and Standards Optoelectronics, Microelectronics, and for Nanomanufacturing II, 704202, September Nanotechnologies III, 663503, May 2007. 2008.•Instrumentation, Metrology, and Standards •Digital Surf Newsletter: Focus on Spanish / for Nanomanufacturing, Michael T. Postek; French nanometrology programmes, Special John A. Allgair, Editors, SPIE Proceedings Vol. Issue on Nanometrology, Nov 2008. 6648, September 2007. •White light interferometry applications in•Length calibration standards for nano- nanometrology, V. S. Damian, M. Bojan, P. manufacturing, David C. Joy; Sachin Deo; Schiopu, et al., SPIE Proceedings, Vol. 7297: Brendan J. Griffin, SPIE Proceedings Vol. 6648, Advanced Topics in Optoelectronics, September 2007. Microelectronics, and Nanotechnologies IV, 72971H, January 2009.•Measurements of linear sizes of relief elements in the nanometer range using a scanning •Experimental study of nanometrological AFM electron microscope, V. P. Gavrilenko; M. N. based on 3-D F-P interferometers, Yu Huang, Filippov; Yu. A. Novikov; A. V. Rakov; P. A. Todua, Ruogu Zhu, SPIE Proceedings, Vol. 7133: Fifth SPIE Proceedings Vol. 6648, September 2007. International Symposium on Instrumentation Science and Technology, 71334F, January•Real-time sensing and metrology for atomic 2009. layer deposition processes and manufacturing, Laurent Henn-Lecordier, Wei •OECD review of current science, technology Lei, Mariano Anderle, and Gary W. Rubloff, J. and innovation policies for nanotechnology Vac. Sci. Technol. B 25, 130 (2007). (Includes details on nanometrology, quality and standards activities), Inventory of•Nanometrology based on white-light spectral National Science, Technology and Innovation interferometry in thickness measurement, Policies for Nanotechnology 2008, July 2009. Huifang Chen, Tao Liu, Zhijun Meng, SPIE Proceedings, Vol. 6831: Nanophotonics, •UK Technology Strategy Board publication, Nanostructure, and Nanometrology II, Nanoscale Technologies: Strategy 2009-2012 683108, January 2008. Nov 2009.•Roadmap of European standardization, •Co-Nanomet publication, European metrology and pre-normative research work Nanometrology Foresight Review, Dec 2009. for Nanotechnologies, NANOSTRAND Final Report, April 2008. 71
  • 72. N & N i n S p a i nNANOMETROLOGY, NANO-ECO-TOXICOLOGY AND STANDARDIZATION Nanotoxicity nanomatearials in the workplace: Compilation of existing guidance, Series on the safety of •Toxicology of nanoparticles: A historical manufactured nanomaterials, Number 11, perspective, Günter Oberdörster, Vicki Stone, ENV / JM / MONO (2009) 16, June 2009. Ken Donaldson, Nanotoxicology, 2007, Vol. 1, No. 1: Pages 2-25. •Report of an OECD Workshop on exposure assessment and exposure mitigation: •Toxicologically Relevant Characterization of Manufactured nanomaterials, Series on the Carbon Nanomaterials, Robert Hurt and safety of manufactured nanomaterials, Agnes Kane, Division of Engineering Number 13, ENV / JM / MONO(2009)18, July Department of Pathology and Laboratory 2009. Medicine, Brown University, Providence, Rhode Island, Tri-National Workshop on •Nano-silver-a review of available data and Standards for Nanotechnology, National knowledge gaps in human and environmental Research Council, Ottawa, February 2007. risk assessment, Susan W.P. Wijnhoven, Willie J.G.M. Peijnenburg, Carla A. Herberts, Werner •Ecotoxicology of Nanoparticles: Issues and I. Hagens, Agnes G. Oomen, Evelyn H.W. Approaches, Geoffrey Sunahara, Ph.D., Heugens, Boris Roszek, Julia Bisschops, Ilse Applied Ecotoxicology Group, Biotechnology Gosens, Dik Van De Meent, Susan Dekkers, Research Institute, Montreal, PQ, Canada, Tri- Wim H. De Jong, Maaike van Zijverden, National Workshop on Standards for Adriënne J.A.M. Sips, Robert E. Geertsma, Nanotechnology, National Research Council, Nanotoxicology, 2009, Vol. 3, No. 2 : Pages Ottawa, February 2007. 109-138. •Biological activity of nanoparticles - •Nanotoxicology-A New Frontier, Lawrence J. mechanisms of recognition and toxicity, Prof. Marnett, Chem. Res. Toxicol., 2009, 22 (9), p Valerian Kagen, Univ. of Pittsburgh, 1491, DOI: 10.1021/tx900261y, Publication Nanotech/DIT, Dublin, November 2007. Date (Web): August 20, 2009, Copyright © 2009 American Chemical Society. •Physical and chemical indicators of nanoparticle toxicity, Dr Gordon Chambers, •Analytical methods to assess nanoparticle Dublin Institute of Technology, Nanotech/DIT, toxicity, Bryce J. Marquis, Sara A. Love, Dublin, November 2007. Katherine L. Braun and Christy L. Haynes, Analyst, 2009, 134, 425–439. •Nanomaterials and nanoparticles: Sources and toxicity, Cristina Buzea, Ivan I. Pacheco, and Standardization Kevin Robbie, Biointerphases 2, MR17 (2007). •ISO/TR 27628:2007 Workplace atmospheres - •Toxicology steps up to nanotechnology safety, Ultrafine, nanoparticle and nano-structured Teeguarden JG, A Gupta, Escobar, P., Jackson, aerosols - Inhalation exposure characterization M. 2008. Research & Development magazine and assessment, 2007. 50(1):28-29. PNWD-SA-7902. •ISO/TS 27687:2008 Nanotechnologies - •Emmission assessment for identification of Terminology and definitions for nano-objects - sources and release of airborne manufactured Nanoparticle, nanofibre and nanoplate, 2008. 72
  • 73. N & N i n S p a i n NANOMETROLOGY, NANO-ECO-TOXICOLOGY AND STANDARDIZATION•International Workshop on Documentary the concept of “uncertainty of measurement” is Standards for Measurement and Characterization not well known yet. in Nanotechnologies, NIST, Gaithersburg, Maryland, USA, 26–28 February 2008. Other problem is that current measurement methods and standards are focused on relatively•Voluntary Measures in Nano Risk Governance, simple, idealised measurement situations. But 4th International “Nano-Regulation“ Conference, there is room as well as a need to improve the 16–17 September 2008, St.Gallen (Switzerland), basic metrological understanding of methods Conference Report, Christoph Meili, Peter and standards. Hürzeler, Stephan Knébel, Markus Widmer, The Innovation Society, Ltd, St.Gallen, Switzerland, At the same time, research and standardization www.innovationsociety.ch, September 2008. need to focus on more application oriented investigations of complex systems, and this will•German Federal Institure for Materials Research necessitate face a number of interdisciplinary and Testing (BAM), List of Currently Available issues. Nanoscaled Reference Materials, Jan 2009. The Spanish High Council on Metrology (RD•Documentary Standards Activity for Scanned 584/2006, 12th May) advises and coordinates the Probe Microscopy, Ronald Dixson, NIST, 3rd Tri- full metrology in Spain in their scientific, technical, National Workshop on Standards for historical and legal aspects. At this High Council all Nanotechnology, February 2009. Spanish Ministries are represented and, specifically, those responsible of Industry, Trade, Environment,•Versailles Project on Advanced Materials and Food, Health, Science and Innovation; i.e., all those Standards (VAMAS), Technical Working Areas involved in nanotechnology and managing the including Nanomaterials (Provides surveys of National R&D Programmes. availability, consistency, repeatability and reproducibility of a range of material test So, there is a nice opportunity to connect methods), June 2009. metrology to nanotechnology.•International Organisation for Standardization - Possible suggested actions are: Technical Committee 24, Subcommittee 4 (TC24/SC4: Particle Characterisation) Standards • For the coming years the State’s effort to on Particle Characterisation, June 2009. enhance and coordinate all national activities related to nanotechnology (nanometrology,4. Actions to develop in Spain within the period basic and applied R&D, risk assessment, standardization, etc.) must continue, but also2010-2013 involving the High Council on Metrology and AENOR.A general problem, not only in Spain, is thatmany people involved in nanotechnology are • The different MICINN Strategic Actions can notnot aware about metrology and they do not be independent, because matters have manyfeel the need of maintaining the traceability faces (research, metrology, standardization). So,of their measuring instruments to support National Strategic Actions (for instance, Healththe reliability of their results which, in and Nanotechnology) should be connected. Theproduction, causes a lack of reproducibility creation, as in other industrialized countries,and inhomogeneous products. For instance, of an Observatory for analysing periodically such connexion lines together with other 73
  • 74. N & N i n S p a i nNANOMETROLOGY, NANO-ECO-TOXICOLOGY AND STANDARDIZATION aspects and needs of nanotechnology would of Institutions (State Agencies, OPIs, be welcome. Technological Centres, CEM, etc.) should not prevent their coordination searching for • Incorporate the metrological component in reaching national objectives. all R&D projects. This is, for instance, mandatory for any new proposal on • Industry should make an effort to understand characterization methods submitted to ISO TC and integrate metrology in the productive 229, being necessary to fill out a metrology processes, in order to get traceability, more check list in order to judge the proposal with accurate and reliable results and respect to the reliability of the results for homogeneous devices and products. guarantying the ulterior fulfilment of specifications. • Industry must participate in the standardization process. It is the only way of • Standardization is also a reliable and efficient maintaining updated on the coming standards tool to accelerate the dissemination of R&D affecting their productive sectors and also results to the market. Consequently, it is them to contribute to the standards and necessary to promote the incorporation of a technical specifications under development, standardization component in R&D projects, modifying these to align to their productive and to establish the required communication processes. channels between R&D projects and AENOR’s AEN/GET 15 Committee “Nanotechnologies” • AENOR should make a call to the concerned to foster the development of standards and Ministries and stakeholders (producers, users, guidelines that contribute to provide the technology developers, researchers, social necessary tools to producers and confidence agents, consumer organizations, etc.) asking to users and consumers. for increasing the participation of members and experts in the GET 15 Committee • Increase the support and funding of “Standardization on nanotechnologies” and metrological infrastructures able to produce primary standards, measurement services and through this, into CEN and ISO Committees. It technical expertise, as required by edge is crucial to build and defend a solid national technology and measurements at the position in the process of developing written nanoscale 10 after agreement of the involved standards and technical specifications, before Ministries. these being mandatory in Spain. • Maintaining the launching of singular and 5. Infrastructure needed to meet objectives strategic coordinated projects, with participation of Public and Private Sectors, but within the period 2010-2013 covering wider multidisciplinary aspects of nanotechnology and, as much as possible, • Existing infrastructure based on Technological metrology and standardization. Platforms, Networks, Universities, SMEs, etc., is valid and should be maintained but • Support of MITYC (funding and recruitment of increasing the dissemination of knowledge technicians and post-Docs) for increasing the and the coordination of actions, mainly when participation of CEM and their Associated the actors belong to different Ministries and Laboratories into the EMRP Programme, by Institutions, as it is the case. the way of Article 169 of the European Treaty. • Organization of national and regional 6. Initiatives coordinated activities of Knowledge Transfer to disseminate the metrological principia and The Spanish Centre of Metrology (CEM) criteria to Academia, Research Community and Industry. The existence of different type (www.cem.es). Embedded in the structure of 74
  • 75. N & N i n S p a i n NANOMETROLOGY, NANO-ECO-TOXICOLOGY AND STANDARDIZATIONMITYC, among their missions are: keeping, There are also Courses on calibration andmaintaining and disseminate the national estimation of uncertainties, together withstandards of the SI Units, to provide traceability to programmed subjects in technical careers,the society (calibration and test laboratories, mainly in Engineering and Physics.industry, etc.), executing R&D projects on In Europe there is a great variety of initiativesmetrology, training specialists in metrology and and platforms, with origin in the Europeanrepresenting Spain in front of international Commission (EMRP and others), in Nationalmetrology organizations. Metrology Institute Networks (EURAMET) and in Private Companies, Research Centres andAENOR/GET 15: Spanish Standardization Group Technical Universities.on NanotechnologiesStructurally divided into 4 Working Groups: The main initiative related to nanometrology isTerminology and Nomenclature, Measurement Co-Nanomet, a programme of activities fundedand Characterization, Health, Safety and under the 7th Framework Programme of theEnvironment, Materials Characterization, it isthe mirror Group of ISO/TC 229 and CEN/TC 352 European Commission, addressing the need“Standardization on nanotechnologies” and within Europe to develop the requiredIEC/TC 113 “Nanotechnology Standardization in measurement frame to successfully support theelectric and electronic equipment”. development and economic exploitation of nanotechnology.Doctorate and Masters on metrology: Co-Nanomets activities focus on theMaster on Metrology by the Spanish Centre of nanometrology needs of European Industry andMetrology (CEM) and the Polytechnic University are addressed through 4 key actions: Strategyof Madrid (UPM), 2 years, 60 ECTS credits. definition, Action Groups (EngineeredThematic Units: Foundations of Metrology, Nanoparticles, Nanobiotechnology, Thin FilmsPhysics, Statistics, Models for measurements and and Structured Surfaces, Critical Dimensions andcalibrations, Organization and Management of Scanning Probe Techniques, Modelling andMetrology, Legal Metrology, Length Metrology, Simulation), Coordination of Education & Skill andTemperature, Mass and derived quantities, Exploitation & Development of Infrastructures.Electrical Metrology, Chemical Metrology, Othermetrologies. With respect to standardization and activities related to Environment, Health and Safety (EHS),Integral Doctorates are less frequent although the main Organizations involved are:there are some. These are of general type, notspecifically oriented to nanotechnology. Some • CEN, European Committee for Standardizationof them are: (www.cen.eu), with the following Committees involved in nanotechnology: CEN/TC 137• Metrology and Industrial Quality, UNED - Assessment of workplace exposure to National University of Distance Education. chemical and biological agents, CEN/TC 352 Nanotechnologies, IEC/TC 113• Design and Fabrication Engineering, UNIZAR – Zaragoza University. Nanotechnologies standardization for electrical and electronic products and systems.• Doctorate on Metrology, ETSII – Polytechnic Univ., Madrid, Dept. of Applied Physics. • OECD, Organisation for Economic Co- operation and Development (www.oecd.org). 75
  • 76. N & N i n S p a i nNANOMETROLOGY, NANO-ECO-TOXICOLOGY AND STANDARDIZATION • JRC,Joint Research Centre, European toxicological and standardization aspects of the Commission (www.jrc.ec.europa.eu). nanotechnology, and not only those specifically scientific or technological. • VAMAS, Versailles Project on Advanced Collaboration CEM - Academia - Industry should Materials and Standards (www.vamas.org). be enhanced as a way to detect measurement and characterization problems and needs as a • ECOS, European Environmental Citizens previous step to invest on designing and Organisation for Standardisation manufacturing of “metrological” measurement (www.ecostandard.org). instruments and standards, traceable and accurate, as an answer to such needs. 7. Conclusions Creation and funding of some infrastructure for A lot of effort has been made in the last years in CEM, their Associated Laboratories and AENOR Spain to reduce the delay with respect to other to disseminate the knowledge on last European countries. The level of knowledge, developments in metrology and development and involvement in R&D projects standardization at the nanoscale, for the benefit of all Spanish stakeholders. has grown and also the results and the rate of return of investments. Establishing and funding of Educational Programmes to improve capabilities of But still remains a lack of information and Universities and companies by creating coordination between all interested parties multidisciplinary communities involved in working in nanotechnology. Also, some matters research on nanotechnology and metrology as metrology and standardization are not applied to the nanoscale. sufficiently considered in the projects and industrial applications. So, a bigger The next conclusions have been adapted from a dissemination of the knowledge among all recent Report on Nanotechnologies and Food 11, interested parties is needed together with a but we see applicable to the Spanish situation coordination of efforts. too: Government should take steps to ensure the establishment of research collaborations It is crucial the creation of a Spanish between industry, academia and other relevant Observatory on Nanotechnology to support bodies at the pre-competitive stage in order to Spanish decision-makers with information and promote the translation of basic research into analysis on developments in nanoscience and commercially viable applications of nanotechnology, coordinate all existing nanotechnologies. information, facilitate the strategic decisions of the Administration and to involve companies Government should work more closely with other and society in the projects on which it is EU Member States on research related to the health necessary to focus the attention in the coming and safety risks of nanomaterials to ensure that years. knowledge gaps are quickly filled without duplication of effort, while continuing to support coordinated In such Observatory, all interested parties research in this area at an international level through (Technological Platforms, Networks, the High appropriate international organisations including the Council on Metrology, AENOR GET 15 International Organization for Standardization and Committee, etc.) must be represented. Organisation for Economic Cooperation and Discussions should also include metrological, Development. 76
  • 77. N & N i n S p a i n NANOMETROLOGY, NANO-ECO-TOXICOLOGY AND STANDARDIZATIONGovernment should establish an open discussion assessment of products of nanotechnologies,group to discuss on the application of 19 January 2009, pp 15-16.nanotechnologies in the different sectors, 8including food. This group should contain The European Metrology Research Programmerepresentatives from Government, academia (EMRP) is a metrology-focused Europeanand industry, as well as representative groups programme of coordinated R&D facilitating afrom the public such as consumer groups and closer integration of national researchnon-governmental organisations. programmes and ensuring the collaboration between National Measurement Institutes,References reducing duplication and increasing impact.1 9 Definition 2.1, ISO TS 27687:2008, Royal Commission on Environmental PollutionNanotechnologies – Terminology and (RCEP), UK, Novel Materials in thedefinitions for nano-objects – Nanoparticle, Environment: The case of nanotechnology, pnanofibre and nanoplate, 1st ed., 15-08-2008. 64, Nov. 2008.2 10 Nanoscale Metrology, Editorial, Meas. Sci. Australian Government, National MeasurementTechnol. 18 (2007). Institute, Technical Report 12, Nanometrology: The Critical Role of Measurement in Supporting3 Scanning Probe Microscopy, Scanning Electron Australian Nanotechnology, Dr John Miles, FirstMicroscopy and Critical Dimension: edition, November 2006.Nanometrology: Status and Future Needs 11within Europe, European Nanometrology House of Lords, Session 8th January 10,Discussion Papers, Co-Nanomet, November Science and Technology Committee, First2009. Report on Nanotechnologies and Food.4 The National Nanotechnology Initiative:Research and Development Leading to aRevolution in Technology and Industry (2006)Subcommittee on Nanoscale Science,Engineering and Technology, Committee onTechnology, National Science and TechnologyCouncil (www.nano.gov/NNI_07Budget.pdf).5 Eighth Nanoforum Report on Nanometrology,Julio 2006 (www.nanoforum.org).6 Towards a European Strategy forNanotechnology (2004) European Commission,Brussels (ftp://ftp.cordis.europa.eu/pub/nanotechnology/docs/nano_com_en.pdf).7 SCENIHR (Scientific Committee on Emergingand Newly Identified Health Risks), Risk 77
  • 78. N & N i n S p a i nNANOMETROLOGY, NANO-ECO-TOXICOLOGY AND STANDARDIZATION ADDENDUM LIST OF STANDARDS AND TECHNICAL SPECIFICATIONS UNDER DEVELOPMENT WITHIN ISO/TC 229 ISO/WD TS 10797, Nanotubes - Use of ISO/CD TS 11308, Nanotechnologies - Use of transmission electron microscopy (TEM) in walled thermo gravimetric analysis (TGA) in the purity carbon nanotubes (SWCNTs). evaluation of single-walled carbon nanotubes (SWCNT). ISO/CD TS 10798, Nanotubes - Scanning electron microscopy (SEM) and energy dispersive X-ray ISO/CD TR 11360, Outline of a Method for analysis (EDXA) in the characterization of single Nanomaterial Classification. walled carbon nanotubes (SWCNTs). ISO/AWI TR 11808, Nanotechnologies - Guidance ISO/DIS 10801, Nanotechnologies - Generation of on nanoparticle measurement methods and their metal nanoparticles for inhalation toxicity testing limitations. using the evaporation/condensation method. ISO/NP TR 11811, Nanotechnologies - Guidance ISO/DIS 10808, Nanotechnologies - on methods for nanotribology measurements. Characterization of nanoparticles in inhalation exposure chambers for inhalation toxicity testing. ISO/CD TS 11888, Determination of mesoscopic shape factors of multiwalled carbon nanotubes ISO/AWI TS 10812, Nanotechnologies - Use of (MWCNTs). Raman spectroscopy in the characterization of single-walled carbon nanotubes (SWCNTs). ISO/AWI TS 11931-1, Nanotechnologies - Nano- calcium carbonate - Part 1: Characteristics and ISO/CD TS 10867, Nanotubes - Use of NIR- measurement methods. Photoluminescence (NIR-PL) Spectroscopy in the characterization of single-walled carbon ISO/NP TS 11931-2, Nanotechnologies - Nano- nanotubes (SWCNTs). calcium carbonate - Part 2: Specifications in selected application areas. ISO/CD TS 10868, Nanotubes - Use of UV-Vis-NIR absorption spectroscopy in the characterization of ISO/AWI TS 11937-1, Nanotechnologies - Nano- single-walled carbon nanotubes (SWCNTs). titanium dioxide - Part 1: Characteristics and measurement methods. ISO/CD TR 10929, Measurement methods for the characterization of multi-walled carbon ISO/NP TS 11937-2, Nanotechnologies - Nano- nanotubes (MWCNTs). titanium dioxide - Part 2: Specifications in selected application areas. ISO/CD TS 11251, Nanotechnologies - Use of evolved gas analysis-gas chromatograph mass ISO/CD 12025, Nanomaterials - General spectrometry (EGA-GCMS) in the characterization framework for determining nanoparticle content of single-walled carbon nanotubes (SWCNTs). in nanomaterials by generation of aerosols. 78
  • 79. N & N i n S p a i n NANOMETROLOGY, NANO-ECO-TOXICOLOGY AND STANDARDIZATIONISO/CD TR 12802, Nanotechnologies - ISO/CD TS 80004-3, Nanotechnologies -Terminology - Initial framework model for core Vocabulary - Part 3: Carbon nano-objects.concepts. ISO/AWI TS 80004-4, Nanotechnologies -ISO/AWI TS 12805, Nanomaterials - Guidance on Vocabulary - Part 4: Nanostructured materials.specifying nanomaterials. ISO/AWI TS 80004-5, Nanotechnologies -ISO/AWI TS 12901-1, Nanotechnologies - Vocabulary - Part 5: Bio/nano interface.Guidance on safe handling and disposal ofmanufactured nanomaterials. ISO/AWI 80004-6, Nanotechnologies - Vocabulary - Part 6: Nanoscale measurement andISO/NP TS 12901-2, Guidelines for occupational instrumentation.risk management applied to engineerednanomaterials based on a "control banding ISO/AWI TS 80004-7, Nanotechnologies -approach". Vocabulary - Part 7: Medical, health and personal care applications.ISO/AWI TR 13014, Nanotechnologies - Guidanceon physico-chemical characterization of ISO/NP TS 80004-8, Nanotechnologies -engineered nanoscale materials for toxicologic Vocabulary - Part 8: Nanomanufacturingassessment. processes.ISO/AWI TR 13121, Nanotechnologies -Nanomaterial Risk Evaluation Framework.ISO/NP TS 13126, Artificial gratings used innanotechnology - Description and measurementof dimensional quality parameters.ISO/NP TS 13278, Carbon nanotubes -Determination of metal impurities in carbonnanotubes (CNTs) using inductively coupledplasma-mass spectroscopy (ICP-MS).ISO/NP TR 13329, Nanomaterials - Preparation ofMaterial Safety Data Sheet (MSDS).ISO/DIS 29701, Nanotechnologies - Endotoxintest on nanomaterial samples for in vitro systems- Limulus amebocyte lysate (LAL) test.ISO/AWI TS 80004-1, Nanotechnologies -Vocabulary - Part 1: Core terms. 79
  • 80. > NIEK VAN HULSTPlace and date of birthNijmegen (The Netherlands), 1957EducationStudy: Astronomy and Physics, at University of Nijmegen, the Netherlands.PhD: in molecular physics, at University of Nijmegen, the Netherlands.Experience• Senior group leader “Molecular NanoPhotonics”,ICFO – The Institute of Photonic Sciences, Castelldefels - Barcelona, Spain. • ICREA research professor, ICREA - Catalan Institute for Research and Advanced education, Barcelona, Spain. • Full Professor Nano-Optics, MESA+ group leader, Dept. Science & Technology, MESA+ Institute for Nano-Technology, the Netherlands • Assistant Professor, Applied Optics group, University of Twente, the Netherlands • Lecturer/Researcher, Applied Optics group, University of Twente, the Netherlands •Postdoctoral Researcher, Opto-Electronics, (Technical) University of Twente, the Netherlands Niek van Hulst has a background in molecular physics, non-linear optics, scanning probe microscopy and nanophotonics. He develops advanced optical nano-antennas, for applications both in chemistry and biology and in advanced integrated optical devices. His group developed the technique of optical phase mapping and pulse tracking which lead to the first direct observation of slow light in photonic crystals. Also the group demonstrated the first λ/4 monopole optical antenna probe with <20 nm field localization. Current activities are on the control of single quantum systems by phase shape pulses and dedicated optical antennas. Niek van Hulst is coordinator of the Spanish Consolider program “NanoLight.es”. niek.vanhulst@icfo.es 80
  • 81. NANOOPTICS AND NANOPHOTONICS1. Introduction combination with ultrafast laser spectroscopy opens many possibilities for light control andPhotonics - the scientific study and application of nonlinear ultrafast optics, all on the nanoscale.light - has evolved to become a key technologybehind many devices found in the modern home, Throughout the past decade NanoPhotonicsfactory and research lab. Today, photonics is a research in Spain has build-up a strongmultibillion-dollar industry, underpinning international reputation. Particularly research onapplications such as telecommunications, data photonic crystals was initiated early, while thestorage, flat-panel displays and materials understanding of the physics behindprocessing. Nanometer scale optical extraordinary transmission in metallicarchitectures play an essential role in future nanostructures has been largely driven bydense optical circuits, optical data storage and Spanish theory. More recently research inmaterials chemistry. To this end both plasmonics and metamaterials is growing rapidlynanostructured (top-down) and colloidal and being recognized internationally. While(bottom-up) architectures are pursued in parallel. based on a traditionally and continuously strong position in theory, it is interesting to see howIndeed the optical response of nanostructures several new experimental institutes and researchexhibits fascinating new entries: sub- groups with high scientific profile and amplewavelength spatial variation of the field, nano-facilities for NanoPhotonics are gettingenabling nanoscale imaging; strong local field shape (Barcelona, San Sebastian and Valencia).enhancement with respect to the incident wave,allowing nanoscale lasing, trapping and heating; The new initiatives often find their origin in thelocal fields with polarization, magnetic and comunidades (Antonomous Regions), whilespatial components that are not present in the being strengthened by national mechanisms,incident light; extraordinary transmission, such as the Plan Nacional and especially thenegative index and negative refraction, sparking CONSOLIDER program. Future perspective foroff the new field of optical “meta”materials. Spanish NanoPhotonics is definitely positive on the short term, however the horizon beyond 2All these phenomena are important for or 3 years remains unclear, also due to recentapplications in the area of nanophotonic circuits cuts in research budget.[4, 5], biology, medicine and environmentalenergy issues. For example, the sub-wavelength 2. State of the artvariation is exploited for nanoscale optical circuitsand for nanoantennas that enable high spatial NanoPhotonics is currently a very active andresolution in imaging and sensing. Moreover, the competitive research field with rapid 81
  • 82. N & N i n S p a i n developments. The current state-of-the-art of completely new arena of controlling light at theNANOOPTICS AND NANOPHOTONICS nanofabrication allows to fabricate new nanoscale comes at hand. To date the research generations of optical nanostructures, field is very active, as negative and zero-index (meta)materials and optical antennas, with new meta-materials offer unique prospects for properties by proper engineering of the electro- superlensing, optical tunnelling devices, compact magnetic fields on the nanometre scale. At the resonators and highly directional sources, etc. same time a broad range of applications is opened up ranging from quantum-information 2.2 Plasmonic nanolasers to light harvesting and energy conversion to bio- sensing and optical imaging with nanometric Truly nanometre-scale lasers has long been one resolution. Here developments in a selection of of the main goals of nanophotonics research. NanoPhotonics topic are sketched: Despite early theory on the concept of surface plasmon lasers, so-called Spasers, ohmic losses 2.1 Metamaterials at optical frequencies have long inhibited the realization of plasmonic nanolasers. Hybrid Novel electro-magnetic properties, such as a plasmonic-photonic waveguides allow to reduce negative refractive index, can be achieved by significantly the losses while maintaining clever engineering of artificial composite (meta)- ultrasmall modes. Indeed recently the first materials, building on sub-wavelength experimental demonstration of nanometre-scale structures. The new properties are not plasmonic lasers was reported using a nanowire attainable with naturally occurring “bulk” separated from a metallic surface by a nm-scale materials. Functional negative-index insulating gap, generating optical modes a metamaterials were first demonstrated for hundred times smaller than the diffraction limit. microwave frequencies, immediately opening The plasmonic modes have no cut-off, therefore the search for analogous materials at optical the dimensions can be even further down-scaled. frequencies. Indeed first principle of optical negative refraction and super-lensing were Plasmonic lasers thus offer the possibility of demonstrated using thin metal films, however exploring extreme interactions between light challenging fabrication of nanometrically flat and matter, opening up new avenues in the films and the enormous energy dissipation in fields of active photonic circuits, bio-sensing and metals are an obstacle for practical application. quantum information technology. Novel strategies combining nanocontrolled 2.3 Optical Antennas metallic and dielectric structures are required to optimize between negative permittivity and the Antennas play a key role in our modern wireless concomitant losses. Interest has turned to three- society, as they mediate between free dimensional optical metamaterials, based on electromagnetic waves and electronic circuitry, layered semiconductor metamaterials or thus enabling mobile phone, internet, etc. Only magnetic metamaterials in the infrared in recent years the crucial role of “nano-optical frequencies, indeed showing negative refraction. antennas” as a transducer between the high Recently relatively low-loss metamaterial have frequency (~500 THz) optical near and far field been presented, based on the so-called of was realized. In fact the extensive library of cascaded ‘fishnet’ structures, possessing a antenna shapes and sizes, optimized to increase negative index over a broad spectral range, and the amount of radiated power for a given accessibility from free space. Clearly the novel frequency band and specific emission direction, design of negative index metamaterials is can be scaled down to the optical regime for challenging both from the theoretical and nanoscale optics. However there is no “simple nanofabrication point-of-view. If successful a downscaling”, as the physics of nanoantennas is 82
  • 83. N & N i n S p a i nmuch richer. First, one has to take into account This opens the route towards space-time-resolved NANOOPTICS AND NANOPHOTONICSthe plasmonic properties of metals at optical spectroscopy with direct observation offrequency. Second, nanoscale optical sources are nanoscopic energy transport. The challenge lies inatoms, organic molecules or semiconductor the optimization of a number of near-fieldquantum dots (Q-dots), i.e. quantum systems; observables, exploiting properly shaped lasertherefore one enters the quantum regime of pulses, to achieve ultimate spatial control oversingle photon emitters. Finally optical nano- linear and nonlinear electromagnetic flux, the localantennas are truly small, with dimensions spectrum, and the local temporal intensity profile.between 30 and 500 nm, posing challenges bothto fabrication and novel methods to drive and 2.5 Imaging and sensingtune such antennas. In recent years “nanoscopy” optical microscopyNano-optical antennas offer unique new with 10-30 nm detail, has become a reality. Byopportunities. They do allow confining and proper engineering of the microscopical pointcontrolling optical fields truly on the nanometer spread function, in combination with non-linearscale. Even more, in close proximity to photon response, the effective resolution is now anemitters, such as molecules, Q-dots or color order of magnitude below the diffraction limit.centers, nano-antennas are particularly promising. Particularly STimulated Emission DepletionFirst, they boost the radiative rate far over intrinsic (STED) microscopy has moved into activenon-radiative decay, thus with the potential to applications, mainly in biology.generate super-emitters with ps photo-cyclingtimes. Indeed 100-fold lifetime reduction to 10 ps In parallel the controlled photo activation ofregime was reported recently. Second, nano- single molecules has allowed the concept ofantennas funnel the incident far field efficiently to Photo-Activation Localisation Microscopydedicated antenna mode maxima thus nano- (PALM), with effective resolution reaching the 20focusing the incident light on e.g. a Q-dot. Last, not nm, a method finding applications extremelyleast, antennas redirect all photon emission in a rapidly. At the same time strong attention is ondedicated direction with narrow angle. Indeed resonant metallic particles that enhance thecomplete redirection of radiation patterns over 90 local field enhancement and on nano-antennadegrees was reported recently. configurations which afford improved coupling efficiency. Several types of antenna geometries2.4 Phase control of nanoscale optical fields are being pioneered for nanoscaling imaging in biology and technical application, again withBy exploiting the interplay between the resolution in the 20 nm range. In parallel, newnanostructure and the spatio-temporal light physics routes are explored throughfield a high degree of control is attainable. Size superlensing by negative index (meta)materials,and shape of the nanostructure play a vital role. where the evanescent decay is locally invertedFor example theoretical modelling has shown to gain; unfortunately, material losses arethat the field distribution of a tapered competing heavily with the superlensingnanostructure depends directly on the linear efficiency.chirp of a femtosecond excitation pulse. Thusthe light is slowed down and ultimately stopped 2.6 Nanophotonic manipulationor trapped. Recently first results were reportedthat shaping allows specific control over the Small particles can be trapped by optical fields,spatio-temporal nanoscopic field. Thus, pulse the so-called “optical tweezers”. The near fieldsequences can be generated in which local photonic forces generated at nanostructures orexcitations occur at specific time and position arrays of nanoholes provide a novel route ofwith sub-diffraction resolution. control, to trap nanoparticles in nanochannels, 83
  • 84. N & N i n S p a i n in direct competition with Brownian motion, to of plasmonic particle can directly excite electron-NANOOPTICS AND NANOPHOTONICS develop extremely sensitive sensors for detecting hole pairs in an indirect gap semiconductor even the binding of (bio)molecules to the particles. without phonon assistance, increasing light Control and understanding of the conditions for absorption per unit thickness. the efficient trapping of the nanoparticles in the near field of such nanoholes, requires detailed Finally charge-carrier can be injected directly insight in the light interactions between the from the nanoparticle into the semiconductor. nanoparticles and the hole walls. Nanoparticle assisted solar cells are currently a very active research subject. Once mastered, the detection of the binding of a single molecule to a trapped particle could be 3. International publications realized, through enhanced surface Raman scattering by particle plasmon resonances. •R. F. Oulton , V. J. Sorger, T. Zentgraf, R. M.Ma, Moreover for extraordinary optical transmission, C. Gladden, L. Dai, G. Bartal , X. Zhang. the extreme field concentrations close to the Plasmon lasers at deep subwavelength scale. hole will have dramatic effects on the strength Nature Vol. 461, Issue: 7264, 629-632, of these forces that broaden the range of Published: Oct 1 2009. applications. Indeed successful nanoscale optical trapping on both resonant nanoparticles and •J. Valentine, S. Zhang, T. Zentgraf, E. Ulin-Avila, nanoholes has been reported, while applications D. A. Genov, G. Bartal and X. Zhang. are being explored. Three Dimensional Optical Metamaterial Exhibiting Negative Refractive Index. Metallic nanoparticles are generally lossy. Thus, Nature, Vol. 455, 376, 2008. besides forces, the resonantly driven nanostructures will heat up. Here the losses can •M. A. Noginov, G. Zhu , A. M. Belgrave , R. be used into advantage for dedicated nanoscale Bakker, V. M. Shalaev, E. E. Narimanov, S. heating. When used in combination with proper Stout, E. Herz, T. Suteewong, U. Wiesner. biochemical recognition methods one can Demonstration of a spaser-based nanolaser. envision localized heating and even destruction NATURE Vol. 460, Issue: 7259, 1110-U68, of selected biomaterial. Indeed plasmonic Published: Aug 27, 2009. heating therapies are currently passing through the clinical test phase. •S. Lal, S. E. Clare, N. J. Halas. Nanoshell-Enabled Photothermal Cancer 2.7 Nanophotonics for energy Therapy: Impending Clinical Impact. Accounts of Chemical Reserarch, Vol. 41, In traditional solar cells photovoltaics is to use Issue: 12, 1842-1851, Published: Dec 2008. light for generating charge carriers in a semiconductor, where the spatial separation of •S. Noda, M. Fujita, T. Asano. the charge carriers defines a current in an Spontaneous-emission control by photonic external circuit. For maximum efficiency it is crystals and nanocavities. important to absorb most of the incoming Nature Photonics, Vol. 1, Issue: 8, 449-458, radiation. Plasmonic nanoparticles have large Published: Aug 2007, Times Cited: 90. optical cross-sections and can efficiently collect and scatter photons into the far field. Thus first •H. J. Lezec, J. A. Dionne, H. A. Atwater. an increased effective optical path length and Negative refraction at visible frequencies. greater photon absorption probability are Science, Vol. 316, Issue: 5823, 430-432, achieved. Secondly, the spatially localized near Published: Apr 20, 2007. field photons created in the immediate vicinity 84
  • 85. N & N i n S p a i n•M. Burresi, D. Van Oosten, T. Kampfrath, H. Nano-optical trapping of Rayleigh particles and NANOOPTICS AND NANOPHOTONICS Schoenmaker, R. Heideman, A. Leinse, L. Escherichia coli bacteria with resonant optical Kuipers. antennas. Probing the Magnetic Field of Light at Optical Nano Letters 9, 3387-3391 (2009). Frequencies. Science, Vol. 326, Issue: 5952, 550-553, •E.Rittweger, K. Y. Han, S. E. Irvine, C. Eggeling, Published: Oct 23, 2009. S. W. Hell. STED microscopy reveals crystal colour•T. H. Taminiau, F. D. Stefani, F. B. Segerink, N. F. centres with nanometric resolution. Van Hulst. Nature Photonics, Vol. 3, Issue: 3, 144-147 Optical antennas direct single-molecule Published: Mar, 2009. emission. Nature Photonics, Vol. 2, Issue: 4, 234-237, •A. Kinkhabwala, Z. F. Yu, S. H. Fan, Y. Published: Apr, 2008. Avlasevich, K. Mullen, W. E. Moerner. Large single-molecule fluorescence•T. Baba. enhancements produced by a bowtie Slow light in photonic crystals. nanoantenna. Nature Photonics, Vol. 2, Issue: 8, 465-473, Nature Photonics, Vol. 3, Issue: 11, 654-657 Published: Aug, 2008. Published: Nov, 2009.•L. Novotny. •M. Schnell, A. García-Etxarri, A. J. Huber, K. Effective wavelength scaling for optical Crozier, J. Aizpurua, R. Hillenbrand. antennas. Controlling the near-field oscillations of Physical Review Letters, Vol.98, Issue: 26, Article loaded plasmonic nanoantennas. Number: 266802, Published: Jun 29, 2007. Nature Photonics, Vol. 3, Issue: 5, 287-291, Published: May 2009.•N. I. Zheludev, S. L. Prosvirnin, N. Papasimakis, V. A. Fedotov. •Stockman M. I. Lasing spaser. Criterion for negative refraction with low Nature Photonics, Vol. 2, Issue: 6, 351-354, optical losses from a fundamental principle of Published: Jun, 2008. causality. Physical Review Letters, Vol. 98, Issue: 17,•A. Alu, N. Engheta. Article number: 177404, Published: Apr 27, Tuning the scattering response of optical 2007. nanoantennas with nanocircuit loads. Nature Photonics, Vol. 2, Issue: 5, 307-310, 4. Actions to be developed in Spain Published: May, 2008. Focus and mass: NanoScience and Technology is•T. V. Teperik, F. J. García De Abajo, A. G. Borisov, rather scattered in Spain. Many “nano”-centers M. Abdelsalam, P. N. Bartlett, Y. Sugawara & J. do exist or are in planning, where typically every J. Baumberg. Autonomous Region will have its own Omnidirectional absorption in nanostructured nanocenter, while Madrid, Catalunya, Basque metal surfaces. country have multiple nanocentres. It is essential Nature Photonics 2, 299 - 301 (2008). to refocus this trend from quantity towards quality.•M. Righini, P. Ghenuche, S. Cherukulappurath, V. Myroshnychenko, F. J. García de Abajo, R. A differentiation is needed to fight the Quidant. fragmentation and to justify the large number of 85
  • 86. N & N i n S p a i n centres: each centre should focus on a well- necessary for a nanophotonics laboratory. InNANOOPTICS AND NANOPHOTONICS chosen specialism, thus proving its uniqueness parallel a wide range of sensitive optical and quality. Only this way focus, critical mass methodologies is essential: broad band and collaboration can be guaranteed. For the spectroscopy, confocal microscopy, near field specific case of NanoPhotonics, concentrated microscopy, single molecule/quantum-dot research activities at 2 or 3 centres would be detection, non-linear optics, ultrafast sufficient to keep focus and critical weight. excitation/detection, etc. Platform: NanoPhotonics is an active research field in Spain, carried by a large variety of institutions, foundations, and research programs. Researchers meet regularly on various types of conferences, schools and progress meetings. The exchange of information and level of collaboration is quite satisfactory but has room for further improvement. It will be useful to study the added value and necessity of a national platform for NanoPhotonics Funding: Nanophotonics research is financed through Plan Nacional, through CONSOLIDER programs and complemented by European projects. Long term structural financing is lacking and the horizon beyond 2011 remains unclear. Therefore it is paramount to launch a nanoscience research funding platform, with a Figure 1. Paired nanowires make robust plasmotic waveguides. clear focus on the various most promising and tactical nano-research directions. Herein NanoPhotonics should be one of the focus areas. 6. Existing initiatives Knowledge and Technology Transfer: Finally of In the European 7th framework “Photonics” is course it is essential to stimulate actively one of the topics with special attention, in view connections between nanotechnology research of its importance for European industry and to and the various types of industrial activities, to safeguard the European photonic strength in promote spin-off companies, joint ventures and competition with Asia and United States. In 2005 increase awareness of intellectual property. Photonics21 (www.photonics21.org), a European Technology Platform, was founded 5. Necessary infrastructure to achieve objectives aiming at coordinating education, research, training, and development activities in the field NanoPhotonics research relies on two types of of photonics in Europe. infrastructure: nanofabrication and advanced optical methods. For the nanofabrication are Currently, it has over 1400 stakeholders from 49 essential: UV-lithography, e-beam lithography, countries. Fotónica21 (www.fotonica21.org) is ion-beam milling, thin film depositions, the analogue Spanish Photonics Technology dedicated etching, electron microscopy, atomic Platform. EPIC, the European Photonics Industry force microscopy, near field microscopy, surface Consortium, is working with industries, chemistry and colloidal chemistry. Thus in universities, and the European Commission to practice a well-equipped clean room is build a more competitive photonics industrial 86
  • 87. N & N i n S p a i nsector. In parallel the NanoPhotonics Association technology for applications in sensing, NANOOPTICS AND NANOPHOTONICSEurope (www.nanophotonics europe.org), was nanoimaging, optical circuitry and data storage.initiated (coordinated by ICFO Barcelona), ICFO group leader Niek van Hulst is coordinatorinvolving the major European research centres, of the NanoLight project, which involves ICFO,to create a common voice for NanoPhotonics several CSIC, institutes in Madrid, Valencia,particularly. Zaragoza, and groups at the Autonomous University of Madrid. The NanoLight ScientificSpanish NanoPhotonics research is strong in Advisory Board has members from England,Europe. Already in 6th Frame work Spanish France, Germany, Italy, the Netherlands and thegroups contributed substantially to Networks of USA. In parallel the CONSOLIDER-programExcellence “PlasmoNanoDevices”, “MetaMaterials” aims at design realization and“PhOREMOST” and “MetaMorphose”; and to application of MetaMaterials both at microwaveSTREP programs “Pleas”, “Spans” and and optical frequencies. Javier Marti, director of“PlasmoCom”. In Framework 7 Spain coordinates the NanoPhotonic Technology Center at thethe NoE NanoPhotonics for Energy Efficiency Politechnical University of Valencia coordinates(Gonçal Badenes, ICFO) and STREP program the MetaMaterials program.SPEDOC (Romain Quidant, ICFO). The EuropeanIntegrated Activity, LaserLab-Europe has A first Spanish conference on NanoPhotonics,expanded in the 7th Framework with the CEN2008 “Conf. Española de Nanofotónica” wasinclusion of Spanish laboratories: CLPU- organized in Tarragona 2-4 April 2008; in JuneSalamanca and ICFO-Barcelona. 2010 a 2nd meeting CEN2010 took place in Segovia. Finally NanoPhotonics is one of theThe European Science Foundation (ESF) program focus areas of the platform “NanoSpain” asPlasmon-BioNanoSense, with 6 Spanish groups managed by the Phantoms Foundation. Both theand coordination by Stefan Maier (Imperial national annual NanoSpain conference and theCollege, London) and Niek van Hulst (ICFO international TNT (Trends in NanoTechnology)Barcelona). The network provides the means conference series have dedicatedand resources for Spain to play a leading and NanoPhotonics sessions.guiding role in the future European researchagenda in plasmonics, nanophotonics and 7. Conclusionsbiosensing; all fields of strong activity andimmediate importance for industrial NanoPhotonics is a very active research fieldapplications. opening several new horizons, such as controlled single photon sources for quantum-information;Nationally the CONSOLIDER program light harvesting; energy conversion; efficient bio-“NanoLight” aims at developing nanoscale light sensors; optical imaging with 10 nm resolution. The Spanish role in international NanoPhotonics research is currently quite strong and it will be important to consolidate or improve this position towards the future. For future actions it is important to keep scientific focus and mass, to guarantee long term funding and to enforce the connection with industry.Figure 2. NanoParticles trapping with resonant optical antennas. 87
  • 88. > RICARDO GARCÍAPlace and date of birthLeón (Spain), 1960Academic career• Professor of Scientific Research, CSIC. • Research Scientist, CSIC. • Tenure Scientist, CSIC. • Research Associate at the Instituto de Microelectrónica de Madrid (CSIC). • Post-doctoral associate, University of Oregon (USA). • Post doctoral fellow, University of New Mexico (USA). • PhD in Physics, Universidad Autónoma de Madrid (Spain) . • Master in Physics, Universidad de Valladolid (Spain). Experience García applies a combined theoretical and experimental approach to develop multipurpose tools for quantitative analysis and manipulation of molecules, materials and devices in the 1 to 100 nm length scale. A key feature of RG’s approach is that nanoscale control and device performance should be compatible with operation in technological relevant environments (air or liquids). He has contributed to the emergence and optimization of a versatile nanolithography for the fabrication of nano-scale devices based on the spatial confinement of chemical reactions (local chemical nanolithography). He has also contributed to the development, understanding and optimization of amplitude modulation AFM (tapping mode AFM). In particular, he participates in the development of multifrequency AFM as a unifying scheme for topography and quantitative mapping of material properties with sub-1 nm resolution. ricardo.garcia@imm.cnm.csic.es 88
  • 89. SCANNING PROBE MICROSCOPY1. Introduction In addition, Madrid has hosted the first two conferences on Multifrequency AFM (15thIn the eighties research on scanning tunneling September 2008, 15-16 June 2009).microscopy (STM) was at its apogee. A Spanishinstitution, the Universidad Autónoma deMadrid was at the forefront of the STM activity.This early start in the development of one of theinstruments that epitomizes the emergence ofnanoscience was the result of the continuouseffort of several professors, scientists andgraduate students. In particular, credit must begiven to the vision and perseverance of NicolásGarcía, Arturo Baró and Fernando Flores.Since then, two generations of Spanish scientistshave kept an internationally competitive level. In Figure 1. Scheme of the cantilever oscillation in bimodal AFM (R.G.)some topics, it could be argued that Spain’s leadsthe way. This claim is supported by the number, An estimation of the size of Spain’s SPMimpact and quality of the contributions that are community can be obtained from the number oforiginated from Spain’s scientific institutions. But participants in the Spanish conference on SPM,it can also be gauged by the fact that in the period called Fuerzas y Túnel. This is a biannual meetingcovered by this report (2007-2009), three major that in 2008 had 109 attendees with 37 oralconferences on SPM has been held in Spain. presentations and 45 posters. Right now there are about 25 groups that actively work on either theBarcelona hosted the 1st AFMBioMed development of applications of probe techniques.conference with about 200 participants. Then, Those groups cover almost all the range technicalMadrid hosted the two major international applications and developments. Madrid andconferences on atomic force microscopy (the Barcelona are the poles of this activity.11th Non Contact, Madrid 16-19 September2008; 11th International Scanning Probe Shortly, Madrid’s activity shows a balanceMicroscopy, Madrid 17-19, June 2009). About among instrumentation, applications and200 scientists attended each conference. The theoretical methods. The activity in Barcelona isscientific board of both conferences has more oriented towards applications. Thesemembers based on Spain. range from cell biology to materials science or microelectronics. 89
  • 90. N & N i n S p a i n A welcome event in this period has been the compatible with Windows operative system. The incorporation to some Spanish institutions of impact of the WSxM software has been several scientists with considerable SPM outstanding. In a single year (2009) theSCANNING PROBE MICROSCOPY expertise, notably Rainer Hillebrand, Nicolás publication has been cited 297 times. Another Lorente, Fernando Moreno or Esther Barrena. highlight was the development of bimodal AFM (2-3). This method improves the sensitivity of It has to be emphasized that the strength and tapping mode AFM by 10-100 times. As a vigor of the scientific activity is not the result of consequence, it makes compatible high a concerted effort by Spanish agencies to resolution imaging while applying very small support SPM. Mostly, it has been driven by the forces. This technique belongs to the vision and the curiosity of some scientists. Multifrequency AFM concepts that are one of the current poles of AFM research. 2. State of the art San Paulo, Bachtold and colleagues (CSIC) have The analysis is divided in three sections: atomic exploited the high sensitivity of bimodal force microscope (AFM), STM and a brief section excitation for imaging the vibration modes of devoted to the theory applied to explain several nanoelectromechanical systems such as scanning probe microscopy experiments. suspendend carbon nanotubes or graphene resonators (4). Noteworthy is the collaboration 2.1 Atomic force microscopy established between A. Asenjo and colleagues (CSIC) and a company (Nanotec Electronica) to The AFM shows an admirable vitality. Twenty implement a magnetic force microscope years after the invention of the instrument and adapted to the operation under external there is still plenty of room for innovative magnetic fields. dynamic AFM approaches. Applications. Instrumentation. The imaging as well as the spectroscopy In this period there are two major milestones in capabilities of the AFM has been widely AFM methods. The collaboration between Julio exploited to study a wide range of materials: Gómez and José M. Gómez groups (UAM) gave rise biomolecules, nanotubes, semiconductors to to the WSxM software (1). name a few. It is worth to mention the pioneering attempts to manipulate the This is a free software designed to run a wide mechanical flexibility of virus capsids by a team variety of SPM configurations and that is of UAM and CSIC scientists (5). Figure 2. Image of the vibrational modes of a carbon nanotube (Cour- Figure 3. Section of a silicon nanowire transistor fabricated by AFM tesy A. San Paulo) nanolithography (Courtesy R.G.) 90
  • 91. N & N i n S p a i nThe unique ability of the AFM to provide Gambardella and colleagues have imaged withspatially resolved electrical measurements has atomic resolution supramolecular layers. Thebeen exploited to measure the electrical images have contributed to understand the SCANNING PROBE MICROSCOPYproperties of different nanotubes (6-7). origin of the magnetic anisotropy in two-Regarding the nanofabrication potential of AFM, dimensional iron arrays (10). Hermann Suderowit is worth to mention the introduction of dip-pen and colleagues have fully exploited thenanolithography in Spain by the AFM community spectroscopy capabilities to image a(D. Maspoch and D. Ruiz-Molina). The maturity superconducting vortex lattice (11). Theyof AFM oxidation as an alternative reported one of the first images of a twonanolithography has been illustrated by the dimensional melting transition. In anotherfabrication of sub-5 nm silicon nanowire relevant study, Vazquez and colleagues havetransistors (see figure). Cantilever-based applied the imaging and spectroscopynanomechanical sensing implements some AFM capabilities of the STM to characterize thetechnology to detect with a exceedingly good formation of a periodically rippled graphenesensitivity mass changes of or interactions. Javier surface (13).Tamayo’s group (CSIC) has proposed a novelscheme to the development of a label-free DNA 2.3 Theorybiosensor that can detect single mutations (8). New codes to interpret STM images have been2.2 Scanning tunneling microscopy proposed (J.M. Soler), however, the current theoretical activity is applied to explain theThe use of the STM in ultra high vacuum experimental data based on previous theoreticalconditions has been crucial to determine the developments (J. Cerdá, N. Lorente). Thegrowth conditions of different nanoscale capability of the AFM to investigate the electricalsystems. and mechanical properties of nanoscale systemsInstrumentation.The most noticeable instrumental developmenthas been the design and construction of a lowtemperature (4K) ultra high vacuum STM by J.M.Gómez-Rodríguez and colleagues. Thisinstrument has been used to study differentsurface diffusion studies of single molecules andnanostructures on solid surfaces.Applications.The atomic resolution of the STM has beenexploited for addressing several key studies innanoscience (9-13). Martin-Gago and colleagueshave followed in-situ chemical reactions oncatalytic surfaces. In particular, they havesuccessfully synthesized both fullerene, C60, andtriazafullerene, C57N3, with yields close to 100per cent by means of a surface catalyzeddehydrogenation process from theircorresponding planar polycyclic aromaticprecursors (9). Figure 4. Scheme of the synthesis of C60 (Courtesy J. A. Martin-Gago) 91
  • 92. N & N i n S p a i n has motivated an intense theoretical activity (F. •P. Sundqvist, F. J. García-Vidal. F. Flores, M. Flores and colleagues, P.A. Serena). First Moreno-Moreno, C. Gómez-Navarro, J. S. principle calculations are extensively been used Bunch, J. Gómez-Herrero, Voltage and length-SCANNING PROBE MICROSCOPY to explain the electrical and mechanical dependent phase diagram of the electronic properties of nanosystems. In particular, the transport in carbon nanotubes, Nano Letters collaboration of R. Pérez with Morita’s group in 7, 2568 (2007). Japan has produced fruitful results to explain atomic-scale manipulation experiments (14-15). •J. Merteens, C. Rogero, M. Calleja, D. Ramos, The emergence of multifrequency AFM methods J. A. Martín-Gago, C. Briones, J. Tamayo, Label- has prompted a theoretical framework to explain free detection of DNA hybridization based on the experiments (2). Some theoretical aspects of hydration-induced tension in nucleic acid phase imaging have also been revisited (J. J. films, Nature Nanotechnology 3, 301 - 307 Sáenz, R. García). (2008). 3. International Publications •G. Otero, G. Biddau, C. Sánchez-Sánchez et al. Fullerenes from aromatic precursors by •I. Horcas, R. Fernández, J.M. Gómez- surface-catalysed cyclodehydrogenation , Rodríguez, J. Colchero, J. Gómez-Herrero, Nature 454, 865 (2008). A.M. Baró, WSxM: A software for scanning probe microscopy and a tool for •P. Gambardella, S. Stepanow, A. Dmtriev, J. nanotechnology, Review Scientific Honolka et al., Supramolecular control of the Instruments 78, 013705 (2007). magnetic anisotropy in two-dimensional high- spin Fe arrays at a metal interface, Nature •J. R. Lozano, R. García, Theory of Materials 8, 189 (2009). multifrequency AFM, Physical Review Letters 100, 076102 (2008). •I. Guillamon, H. Suderow, A. Fernández- Pacheco, J. Sese, R. Cordoba, J.M. de Teresa, •R. García, R. Magerle, R. Pérez, Nanoscale M.R. Ibarra, S. Vieira, Direct observation of compositional mapping with gentle forces, melting in a two-dimensional Nature Materials 6, 405 (2007). superconducting vortex lattice, Nature Physics 5, 651 (2009). •D. García-Sánchez, A. San Paulo, M.J. Espandiu, F. Pérez-Murano, L. Forró, A. •I. Fernández-Torrente, S. Monturet, K.J. Franke, Aguasca, A. Bachtold, Mechanical detection of J. Fraxedas, N. Lorente, J.I. Pascual, Long-range carbón nanotube resonator vibrations, repulsive interaction between molecules on a Physical Review Letters 99, 085501 (2007). metal surface induced by charge transfer, Physical Review Letters 99, 176103 (2007). •C. Carrasco, M. Castellanos, P.J. de Pablo, M.G. Mateu, Manipulation of the mechanical •A. L. Vázquez, F. Calleja, B. Borca, M.C.G. properties of a virus by protein engineering, Passaseggi, J.J. Hinarejos, F. Guinea, R. Proc. Natl. Acad. Sci. USA 105, 4150 (2008). Miranda, Periodically rippled graphene: Growth and spatially resolved electronic •B. Pérez-García, J. Zuniga-Pérez, V. Muñoz- structure, Physical Review Letters 100, 056807 Sánjose, J. Colchero, E. Palacios-Lidon, (2008). Formation and rupture of Schottky nanocontacts on ZnO naocolumns, Nano •O. Custance, R. Pérez, S. Morita, Atomic force Letters 7, 1505 (2007). microscopy as a tool for atom manipulation, Nature Nanotechnology 4, 803 (2009). 92
  • 93. N & N i n S p a i n•Y. Sugimoto, P. Pou, O. Custance, P. Jelinek, M. collaborative project that has an emphasis on Abe, R. Pérez, S. Morita, Complex patterning SPM applications (Nanoobjetos). Within the by vertical interchange atom manipulation European Union, the European Science SCANNING PROBE MICROSCOPY using atomic force microscopy, Science 322, Foundation sponsors or has sponsored several 413 (2008). networks where the AFM has a key role such as Friction and Adhesion in Nanomechanical4. Proposed actions in Spain Systems (FANAS) or Nanotribology (Nanotribo).Spain’s international prominence on SPM has 7. Conclusionmostly been driven by the curiosity of thescientists. This is, somehow regrettable, because In the reporting period, some significantthe involved technologies are one of the pillars advances in scanning probe microscopythat sustain the advance on nanotechnology. instrumentation and applications haveSPM projects are currently funded by the main happened in. The SPM activity shows scientificprograms of the MICINN. However, those vitality, strength and growth. It can be said thatprograms allocated a limited amount of funds history of the SPM activity is a history of awhat limits the scope of the projects. If Spain is double success. First, because an activity thatto maintain a leadership in new generation of started about 25 years ago has kept a very highscanning probe microscopes, SPM projects scientific profile. Second, for the first time inshould be present on the large scientific modern Spanish science, a scientific activity hasprograms such as CONSOLIDER or other more kept an internationally competitive level in thetechnology oriented actions. three major aspects: instrumentation, applications and theory.5. Infrastructure In fact, this success is the result of several factorsThe profile of the scientists involved in SPM such as the vision of the pioneers, the existenceactivities can be divided into three major groups: of a sizeable group of experts that cover alldevelopers of SPM methods, experts that topics from instrumentation to theory and theperform sophisticated measurements and users financial support by the Spanish fundingaiming nanoscale characterization. Those agencies. If the next evolution in nanoscalescientists and technologists have different needs instrumentation is not to be missed, the fundingand expectations from the technique. To agencies should consider the opportunity toproperly address those needs and to identify stimulate and fund a large collaborative projectpotential new users, it would be helpful compile in this field. To some extent, it is odd that thea database of the instruments devoted to each Consolider-Ingenio 2010 program does notactivity. included a project specifically devoted to novel scanning probe microscopy methods.6. Other initiativesCurrently, there are two master courses that givea central role to SPM techniques: MasterInteruniversitario en Nanociencia yNanotecnología molecular (coordinated by theUniversidad de Valencia) and Master en Física dela Materia Condensada y Nanotecnología(coordinated by the Universidad Autónoma deMadrid). The Comunidad de Madrid supports a 93
  • 94. > ADRIAN BACHTOLDPlace and date of birth: London (UK), 1972Education: University of Basel (Switzerland), Ph.D. Physics, 1999. Summa Cum LaudeExperience• Professor of ICN at the CIN2(ICN-CSIC) in Barcelona.• Professor of CSIC at the CIN2(ICN-CSIC) in Barcelona.• Principal investigator of the Quantum NanoElectronics group.• Chargé de recherche CNRS (permanent position) at the Ecole Normale. Supérieure in Paris• Post doctoral Research, Delft university of technology.• Post doctoral Research, University of California at Berkeley.• PhD Research and Teaching Fellow, University of Basel.Research Field• Nanophysics, quantum transport.• Novel fabrication techniques at the nanometer scale.• Carbon nanotubes, graphene.• Electron transport at helium temperatures in nanostructures contacted by electrodes.• Scanned probe microscopy of nanostructures.adrian.bachtold@cin2.es> FRANCISCO GUINEA Place and date of birth: Madrid (Spain), 1953 Experience • Research scientist (permanent staff since 1987), Spanish National Research Council (CSIC) . Work in material models and nanoscopic devices, especially in graphene and related materials. • About 300 scientific articles published. paco.guinea@icmm.csic.es > WOLFGANG MASER Place and date of birth: Koblenz (Germany), 1963 Education • Diploma in Physics by University of Bonn (1990). • PhD thesis performed at Max-Planck-Institute for Solid State Research (1990-1993). • PhD in Natural Science of University of Tübingen (1993). Experience • Postdoctoral stays at: Univ. of Sussex, 1993-1994), University of Montpellier (1994-1997) and the Instituto de Carboquímica (CSIC) (1997-2002). • Research Scientist at Instituto de Carboquímica (CSIC) since 2002. Co-founder and scientific advisor of Nanozar S.L. (2005). • Research topics cover low dimensional systems based on fullerenes, nanotubes, intrinsically conducting polymers and more recently graphene focussing on control of structure and property relationship. Current research relates to functional carbon nanotubes/graphene based composite materials. Author of more than 150 research articles. Conference chair of intern. ChemOnTubes 2008 conference. Board member of GDRI Graphene and Nanotubes. wmaser@icb.csic.es > STEPHAN ROCHE Place and date of birth: Grenoble (France), 1969 Education: Ph.D. in Physics Experience • Centre de Investigació en Nanociència i Nanotecnologia Barcelona, Spain. • Institute for Materials Science, TU-Dresden Dresden, Germany. • Commissariat à l’Energie Atomique Grenoble, France. • Departamento de Física Teórica, Universidad de Valladolid Valladolid, Spain. • Department of Applied Physics, University of Tokyo Tokyo, Japan European Postdoc Fellow (EU-JSPS and EU-STF programmes). • Centre National de Recherche Scientifique, CNRS Grenoble, France. • Ph.D. Candidate Sept. 1993 - Sept. 1996. sroche@cin2.es 94
  • 95. CARBON NANOTUBES AND GRAPHENE1. Introduction below 50 €/kg for multi-wall carbon nanotubes (MWNTs). Driving force is the demand for novelCarbon nanotubes and graphene are nanoscale advanced composite materials with applicationsobjects of great scientific and technological in automotive, aeronautics, sport goods, textilesinterest due to a combination of extraordinary and the field of energy. Several companies haveproperties (metal or semiconductor for brought already advanced nanotube-compositenanotubes, high mobility, good thermal materials on the market. While research onconductor, stiff, light, tough, high surface, etc.). It MWNTs more concentrates on dispersion andis a field of research which has experienced an processing technologies towards advancedexplosive growth since the discovery of functional composites, there is an importantnanotubes in 1991 and graphene in 2004. The research effort on single-wall carbon nanotubesWeb of Science shows over 10771 scientific towards improving growth, sorting (metal frompapers published in 2008, and at least 11178 in semiconducting nanotubes) and assembling2009, see Figure 1. The topics of research are technologies. As for graphene, the first fabricatedvery vast, including physics, chemistry, layers were separated from graphite in a simpleengineering, toxicology, and biomedicine. and inexpensive way using scotch tape. Other fabrication techniques were developed that are suitable for large-scale production, such as evaporation of SiC surfaces and chemical vapour deposition. Exfoliation methods leading to water soluble graphene oxide sheets which can be chemically reduced to graphene sheets open a broad ground for chemists and material scientists. Surprisingly, already there are severalFigure 1. Papers published worldwide since 2005 (date: 20 December2009). companies commercializing graphene based products such as Graphene Laboratories Inc.Today, various major international companies (USA), GrapheneEnergy (USA), Graphenearound the globe (European ones as major Industries (UK) and Vorbeck Materials (DE).players) produce nanotubes on a severalhundred tons/year scale and further up-scaling Products based on nanotube are alreadyis still projected with a price expectation of commercialized, such as batteries (longer life 95
  • 96. N & N i n S p a i n time). Large electronic companies used nanotube with other materials, in topics such asCARBON NANOTUBES AND GRAPHENE field-emitters to produce prototypes of flat displays mesoscopic magnetism, or “strain engineering”. that can be rigid or flexible. Composite materials Another important emerging direction of made with graphene or nanotubes are promising research concerns spin injection in graphene and for electric charge dissipation, electromagnetic nanotubes as well as spin manipulation shielding, reinforcement, thermal stability, high possibilities. Although spin injection through porosity. Scientific advances with potential ferromagnetic metal/semiconductor interfaces applications include drug delivery, cell growth and remains a great challenge, a spectacular advance repair, and transparent thin film network made in 2007 demonstrated the strong transistors. capability of carbon nanotubes for converting the spin information into large electrical signals. There has been an intense activity in the last two The observation of relatively long spin relaxation years on the transport properties of graphene. times suggested that graphene could add some The first experiments on graphene showed that novelty to carbon-based spintronics. For samples with dimensions of the order of 1-10 instance, taking advantage of the long electronic microns could be deposited on substrates above mean free path and negligible spin-orbit metallic gates. The carrier mobilities in the first coupling, the concept of a spin field-effect samples, μ=103 cm2 s-1 V -1, was about two orders transistor with a 2dimensional graphene channel of magnitude lower than those achieved in Si or has been proposed with an expectation of near- GaAs devices. Nevertheless, the early samples ballistic spin transport operation. showed the Integer Quantum Hall Effect, making them comparable in this respect to the best 2. Recent advances in Spain materials based on doped semiconductors. Large experimental effort ensued for improving the There are a number of very active research mobility (up to μ=2*105 cm2 s-1 V -1). Suspended groups on graphene and nanotubes in Spain, graphene recently showed the Fractional with a significant recognition in the field. The Quantum Hall Effect. Finally, the combination of Web of Science reports a substantial activity as the electric and chemical properties of graphene shown in Figure 2. Interestingly, it can be seen allowed to use it as a detector of chemical that while on a worldwide level the publication species. activity in the last 4 years for nanotubes has less than doubled and almost reaches a saturation Nanoelectromechancial systems (NEMS) with level, Spanish publication activity has more than nanotubes and graphene have recently attracted tripled without reaching a saturation level. In the a lot of interests. Mechanical resonators were case of graphene, a rapidly increasing worldwide fabricated that can be operated at ultra high publication activity (ten-fold increase) can be frequencies and that can be used as noticed, while Spain merely doubled its ultrasensitive inertial mass sensors. The coupling publication activity in this field in the same time of the mechanical and the charge degrees of frame. The situation is comparable to the freedom in nanotube resonators is strikingly beginning of nanotube research in Spain and strong as well as widely tuneable. Besides, it was underlines Spanish symptomatic weakness in shown that graphene can withstand up to 10% rapidly conquering a new field of research of strain. Elastic strains change the dynamic of great scientific and technological importance and carriers in a similar way to a magnetic field. It marking the pace from the very beginning on. may lead to novel uses of graphene, not possible 96
  • 97. N & N i n S p a i n from aquous dispersions into the forms of films, CARBON NANOTUBES AND GRAPHENE fibers and masterbatches. 2. Polymeric Modification of Graphene through Esterification of Graphite Oxide and Poly(vinyl alcohol). H.J. Salavagione, M.A. Gómez, G.Martínez.Figure 2. Papers from Spain published since 2005 (date: 20 December J. Materials Chemistry 19, 5027-5032 (2009).2009). In this work novel poly(vinylalcohol)/reducedIt is a difficult exercise to summarise the activity graphite oxide nanocomposites are presented.on nanotube and graphene in Spain, especially Synthesis is performed by reducing graphite oxide insince we (the authors of this report) are active the presence of the polymer matrix and coagulatingplayers in the field. We choose to select a set of the systems with 2-propanol. Interactions betweenpublished works that have in our opinion an polymer and reduced graphite oxide layers, mainlyimportant impact in the scientific community. by hydrogen bonding, are observed.Growth/synthesis The interactions are responsible for remarkable changes in the thermal behaviour of the1. Nanofibrillar polyaniline direct route to carbon nanocomposites. In addition, high electricalnanotubes water dispersions in high conductivity has been achived at concentrationsconcentrations beyond 7.5 wt% of reduced graphite oxideP. Jiménez, W.K. Maser, P. Castell, M.T. (about 0.1 S/cm) with a percolation thresholdMartínez, A.M. Benito between 0.5 and 1 wt%.Macromolecular Rapid Communications 30(6),418 (2009) 3. Ultralong natural graphene nanoribbons and their electrical conductivity.In this work the synthesis of a novel nanofibrilar M. Moreno-Moreno, A. Castellanos-Gómez, G.polyaniline/nanotube water dispersible Rubio-Bollinger, J. Gómez-Herrero, N. Agraït.nanocomposite is presented. The composite is Small 5(8):924-7 (2009).easily dispersible in water at high concentrationsup to 10 mg/ml even at highest nanotube In this work reported by groups in UAM (Madrid), aloadings of 50 wt%. The in-situ polymerization new method for graphene flake deposition onhas been carried out under nanofibrilar surfaces based on silicone stamps is presented.conditions resulting in an intrinsically Using high resolution optical and atomic forcenanostructured composite materials responsible microscopy (AFM), the topography and electronicfor the dispersibility in aquous dispersions. On conductance of ultralong graphene nanoribbonsthe other hand, the synthesis represents a novel with length greater than 30 μm and minimumand direct route for obtaining nanotube width below 20 nm are characterized. As thedispersions at high concentrations without the ribbons are consequence of the cleaving processuse of any surfactant or stabilizers. (natural GNR) clean edges along the crystallographic graphene directions are expected,The findings are an important step towards an in contrast with those fabricated by lithographyeasy processing of nanotubes and composites techniques. 97
  • 98. N & N i n S p a i n Applications Nanoube Based Potentiometric Aptasensor.CARBON NANOTUBES AND GRAPHENE G.A. Zelada-Guillén, Jordi Riu, Ali Düzgün, F. 4. Subnanometer Motion of Cargoes Driven by Xavier Rius. Thermal Gradients along Carbon Nanotubes. Angewandte Chemie, 48, 7334 (2009). A. Barreiro, R. Rurali, E.R. Hernández, J. Moser, T. Pichler, L. Forró, A. Bachtold. In this work, it is demonstrated that easy-to-build Science 320, 775 (2008). aptamer-based SWCNT potentiometric sensors are highly selective and can be successfully used An important issue in nanoelectromechanical to detect living microorganisms in an assay in close systems is developing small electrically driven to real time, thus making the detection of motors. The authors report on an artificial pathogens as easy as measuring the pH value. An nanofabricated motor in which one short carbon aptamer attached to an electrode coated with nanotube moves relative to another coaxial single-walled carbon nanotubes interacts nanotube. A cargo is attached to an ablated outer selectively with bacteria. The resulting wall of a multiwall carbon nanotube that can electrochemical response is highly accurate and rotate and/or translate along the inner nanotube. reproducible and starts at ultralow bacteria The motion is actuated by imposing a thermal concentrations, thus providing a simple, selective gradient along the nanotube, which allows for method for pathogen detection. The most sub-nanometer displacements, as opposed to an important strength of this biosensor is that simple electromigration or random walk effect. positive/negative tests can be carried out in real zero-tolerance conditions and without cross 5. Lable-Free DNA Biosensors Based on reaction with other types of bacteria. The ease Functionalized Carbon Nanotube Field Effect with which measurements are taken in Transistors. potentiometric analysis opens the door to greater M.T. Martínez, Y-Chih Tseng, Nerea Ormategui, simplicity in microbiological analysis. Iraida Loinaz, Ramón Eritja, Jeffrey Bokor. Nano Letters 9(2), 530 (2009). 7. Impedimetric genosensors employing COOH- modified carbon nanotube screen-printed In this work a new approach to ensure the electrodes. specific adsorption of DNA to nanotubes is A. Bonanni, M. J. Esplandiu, M. del Valle. presented. A carbon nanotube transistor array Biosensors & Bioelectronics 24 (9), 2885-2891. was used to detect DNA hybridization. A polymer poly(methylmethacrylate-co-poly In this work screen-printed electrodes modified (ethyleneglycol)methacrylate-co-N-succinimidyl with carboxyl functionalized multi-walled carbon nantoubes were used as platforms for methacrylate) was synthesized and bonded impedimetric genosensing of oligonucleotide noncovalently to the nanotube. Aminated single- sequences specific for transgenic insect resistant strand DNA was then attached covalently to the Bt maize. After covalent immobilization of polymer. After hybridization statistically aminated DNA probe using carbodiimide significant changes were observed in key chemistry, the impedance measurement was transistor parameters. Hybridized DNA traps both performed in a solution containing the redox electrons and holes, possibly caused by the marker. A complementary oligomer target was charge-trapping nature of the base pairs. added, its hybridization promoted. Changes in charge transfer resistances between solution and 6. Immediate detection of Living Bacteria at electrode surface confirm the hybrid formation. Ultralow Concentrations Using a Carbon 98
  • 99. N & N i n S p a i nElectron transport 10. Midgap states and charge inhomogeneities CARBON NANOTUBES AND GRAPHENE in corrugated graphene.8. Giant Magnetoresistance in Ultrasmall F. Guinea, M. I. Katsnelson, M. A. H. Vozmediano.Graphene Based Devices. Phys. Rev. B 77, 075402 (2008).F. Muñoz-Rojas, J. Fernández-Rossier, and J. J.Palacios. The authors study the changes induced by thePhys. Rev. Lett. 102, 136810 (2009). effective gauge field due to ripples on the lowBy computing spin-polarized electronic transport energy electronic structure of graphene. Theyacross a finite zigzag graphene ribbon bridging two show that zero-energy Landau levels can formmetallic graphene electrodes, devices featuring due to the smooth deformation of the graphene100% magnetoresistance are demonstrated to be layer. The existence of localized levels gives riseachievable built entirely out of carbon. In the to a large compressibility at zero energy and toground state a short zigzag ribbon is an the enhancement of instabilities arising fromantiferromagnetic insulator which, when electron-electron interactions includingconnecting two metallic electrodes, acts as a tunnel electronic phase separation. The combinedbarrier that suppresses the conductance. Theapplication of a magnetic field makes the ribbon effect of the ripples and an external magneticferromagnetic and conductive, increasing field breaks the valley symmetry of graphene,dramatically the current between electrodes. Large leading to the possibility of valley selection.magnetoresistance is found in this system at liquidnitrogen temperature and 10 T or at liquid helium 11. Ab initio study of transport properties intemperature and 300 G. defected carbon nanotubes: an O(N) approach. B. Biel, F. J. García-Vidal, A. Rubio, F. Flores.9. Carbon Nanoelectronics: Unzipping Tubes into Journal Of Physics Condensed Matter 20,Graphene Ribbons. 294214 - 8 (2008).H. Santos, L. Chico, and L. Brey.Phys. Rev. Lett. 103, 086801 (2009). This work by B. Biel (currently at the University of Granada) and coworkers reports on aThis paper reports on a theoretical study of combination of ab initio simulations and linear-transport properties of novel carbon scaling Greens functions techniques to analyzenanostructures made of partially unzipped the transport properties of long (up to onecarbon nanotubes, which can be regarded as a micron) carbon nanotubes with realistic disorder. The energetics and the influence of single defectsseamless junction of a tube and a nanoribbon. (mono- and di-vacancies) on the electronic andGraphene nanoribbons are found to act at transport properties of single-walled armchaircertain energy ranges as perfect valley filters for carbon nanotubes are analyzed as a function ofcarbon nanotubes, with the maximum possible the tube diameter by means of the local orbitalconductance. These results show that a partially first-principles Fireball code.unzipped carbon nanotube is a magnetoresistivedevice, with a very large value of Efficient O(N) Greens functions techniques framedmagnetoresistance. The properties of several within the Landauer-Buttiker formalism allow astructures combining nanotubes and graphene statistical study of the nanotube conductancenanoribbons are explored, demonstrating that averaged over a large sample of defected tubesthey behave as optimal contacts for each other, and thus extraction of the nanotubes localizationand opening a new route for the design of mixed length. Both the cases of zero and roomgraphene-nanotube devices. temperature have been addressed. 99
  • 100. N & N i n S p a i n Nanoelectromechanical systems possible to control its properties by subjecting it toCARBON NANOTUBES AND GRAPHENE mechanical strain. New analysis indicates not only 12. Ultra Sensitive Mass Sensing with a this, but that pseudomagnetic behaviour and even Nanotube Electromechanical Resonator. zero-field quantum Hall effects could be induced in B. Lassagne, D. García-Sánchez, A. Aguasca, and graphene under realistic amounts of strain. A. Bachtold. Nano Letters 8, 3735 (2008). Spintronics Shrinking mechanical resonators to 15. Transformation of spin information into large submicrometer dimensions has tremendously electrical signals using carbon nanotubes improved capabilities in sensing applications. In L. E. Hueso, J. M. Pruneda, V. Ferrari, G. Burnell, this letter, the authors go further in size reduction using a 1 nm diameter carbon nanotube as a J. P. Valdés-Herrera, B. D. Simons, P. B. Littlewood, mechanical resonator for mass sensing. E. Artacho, Albert Fert & Neil D. Mathur, Nature 445, 410 (2007). The performances, which are tested by measuring the mass of evaporated chromium atoms, are In this paper, L. Hueso (currently head of the exceptional. The measured mass responsivity and nanodevice groups at CIC-NANOGUNE in San mass resolution are excellent; they surpass the Sebastian) and coworkers have demonstrated the values reported previously for resonators made strong potential of carbon based materials for the of nanotube and of any other material. development of coherent spintronics. Indeed, due to the intrinsically spin orbit coupling, very long 13. Coupling Mechanics to Charge Transport in spin diffusion lengths were obtained, allowing for Carbon Nanotube Mechanical Resonators. giant magnetoresistance signals to be measured. B. Lassagne, Y. Tarakanov, J. Kinaret, D. García- Simulations performed by Miguel Pruneda (now Sánchez, A. Bachtold. Science 325, 1107 (2009). permanent research at CIN2-Barcelona) have confirmed the good interface matching between Nanoelectromechanical resonators have potential metals and nanotubes. applications in sensing, cooling, and mechanical signal processing. An important parameter in these 3. Selection of International Publications systems is the strength of coupling the resonator (2007-2009) motion to charge transport through the device. Authors investigate the mechanical oscillations of a Growth/chemistry suspended single-walled carbon nanotube that also acts as a single-electron transistor. •A Chemical Route to Graphene for Device Applications. The coupling of the mechanical and the charge degrees of freedom is strikingly strong as well as S. Glje, S. Han, M. Wang, K. L. Wang, R.B. Kaner widely tuneable. Nano Letters, 7(11), 3394 (2007). •Charting Large-Area Synthesis of High-Quality 14. Energy gaps, topological insulator state and and Uniform Graphene Films on Copper Foils. zero-field quantum Hall effect in graphene by X. Li, Weiwei Cai, Jinho An, S. Kim, J. Nah, D. strain engineering. Yang, R. Piner, A. Velamakanni, I. Jung, E. Tutuc, F. Guinea, M. I. Katsnelson, A. K. Geim. S. K. Banerjee, L. Colombo, and R. S. Ruoff Nature phys. 6, 30 (2009). Science 324, 1312 (2009). Owing to the fact that graphene is just one atom •Preferential Growth of Single-Walled Carbon thick, it has been suggested that it might be Nanotubes with Metallic Conductivity. 100
  • 101. N & N i n S p a i n A.R. Harutyunyan, G. Chen, T.M. Paronyan, Nanoelectromechanical systems CARBON NANOTUBES AND GRAPHENE E.M. Pigos, O.A. Kuznetsov, K. Hewaparakrama, S.M. Kim, D.Zakharov, E.A. •An atomic-resolution nanomechanical mass Stach, G.U. Suanasekera. sensor. Science, 326, 116 (2009). K. Jensen, K. Kim, and A. Zettl. Nature Nanotech. 3 (9), 533-537 (2008).Applications •Measurement of the elastic properties and intrinsic strength of monolayer graphene.•Transparent, Conductive Graphene Electrodes Lee, C., Wei, X., Kysar, J., Hone J. for Dye-sensitized Solar Cells. Science 321, 385-388 (2008). X. Wang, L. Zhi, K. Müllen. Nano Letters 8(1), 323 (2008). •Coupling Mechanics to Charge Transport in Carbon Nanotube Mechanical Resonators.•Lable-Free DNA Biosensors Based on B. Lassagne, Y. Tarakanov, J. Kinaret, D. García- Functionalized Carbon Nanotube Field Effect Sanchez, A. Bachtold. Transistors Science 325, 1107 (2009). M.T. Martínez, Y-Chih Tseng, Nerea Ormategui, Iraida Loinaz, Ramón Eritja, Jeffrey •Energy gaps and a zero-field quantum Hall Bokor. effect in graphene by strain engineering. Nano Letters 9(2), 530 (2009). Guinea F., Katsnelson, M. I., Geim, A. K., Nature Phys. 6, 30 (2009).Electron transport Spintronics•Approaching ballistic transport in suspended graphene. •Transformation of spin information into large Xu, D., Skachko, I., Barker, A., Andrei, E. Y. electrical signals using carbon nanotubes. Nature Nano 3, 491-495 (2008). L. E. Hueso, J. M. Pruneda, V. Ferrari, G. Burnell, J.P. Valdes-Herrera, B. D. Simons, P.B.•Observation of a Mott Insulating State in Littlewood, E. Artacho, Albert Fert & Neil D. Ultra-Clean Carbon Nanotubes. Mathur. V. V. Deshpande, B. Chandra, R. Caldwell, D. Nature 445, 410 (2007). Novikov, J. Hone, M. Bockrath. Science 323, 106 (2009). •Electronic spin transport and spin precession in single graphene layers at room•Fractional quantum Hall effect and insulating temperature. phase of Dirac electrons in graphene. N. Tombros, C. Jozsa, M. Popinciuc, H.T. X. Du, I. Skachko, F. Duerr, A. Luican, E. Y. Andrei Jonkman, B.J.V Wees. Nature 462, 192 (2009). Nature 448, 571 (2007).•Observation of the fractional quantum Hall effect in graphene. 4. Proposed actions to initiate in Spain K.I. Bolotin, F. Ghahari, M. D. Shulman, H.L. Stormer, P. Kim. Actions proposed are related to the following Nature 462, 196 (2009). problems encountered in the field of graphene and nanotube research. 101
  • 102. N & N i n S p a i n Lack of Support the creation of spin-off companies asCARBON NANOTUBES AND GRAPHENE important technology platform which provides • critical mass carrying out high gain/high risk new impulses to industry in different sectors. research in a topic of importance at the forefront of science, 5. Future infrastructures (2010-2013) • sufficient funding for research projects in a topic at the forefront of science, especially • Creation of multiple medium-size clean rooms with respect to contracting qualified personal through the country within existing research (PhD and postdocs), centres. This will allow for increased flexibility • international initiatives and visibility, of operation as well as better access. Typical budgets could range between 1 and 3 M€. One • private R&D support, or two technicians can be enough. • efficient (rapid and flexible) instruments to • Increase of the number of highly qualified support new research developments. technical personnel. To overcome these problems, the following • Improvement of institutional links between actions are proposed: educational programs and research centers. There are several emerging research centers in • More generous funding of strategic research Spain that are attracting excellence and develop projects (graphene, nanotubes), especially new initiatives to foster the development of with respect to have available funds for nanoscience and nanotechnology. However, contracting PhD students or postdocs as well there is a clear problem to attract Spanish as leading senior scientist to gain the citizens to do a PHD or a post doc. necessary critical mass for carrying out research at the forefront of science. ERC-type One solution is to foster (or create) masters in grants at the national level should be nanoscience by suited reinforcement of launched (well funded grants for single technical and administrative personal, as well as groups). teaching assistants and research staff. A • Active participation and funding of coordination, or even networking, of international research initiatives (related to Nanoscience educational programs at the graphene and carbon nanotubes) such as ESF national level would be desirable. programmes. 6. Relevant Initiatives • Promote formation of young researchers in field of nanotubes and graphene by corresponding 6.1 Spain PhD scholarships, introducing the topic in Master Courses in Nanotechnology. • NANOSPAIN Network. • Enhance visibility of Spanish research in field • TNT conference. of graphene and nanotubes by promoting and generously supporting international • Sociedad de Materiales Española. events on these. • Red Española de Micro y Nanosistemas • Promote private R&D effort in fields related to IBERNAM. graphene and nanotube related research. • ChemOnTubes Conference. 102
  • 103. N & N i n S p a i n• Plataforma Tecnológica Española de CARBON NANOTUBES AND GRAPHENE Materiales Avanzados y Nanomateriales.• CSIC Research centres (CIN2, CNM, ICB, ICMM, ICTP, IFM-UPV).• Regional Research centres (CIC-Nanogune, ICN, Imdea).• Universities (Alicante, Barcelona, Madrid, Salamanca, Zaragoza).• Private research centres (AlphaSip S.L. in Madrid, DropSens S.L. in Oviedo, Nanoinnova SL in Madrid, Nanozar S.L. in Zaragoza).6.2 Europe Figure 3. Suspended graphene structured in a Hall bar (J. Moser and A. Bachtold, CIN2-Barcelona)• GDR Network. This is an international research network supported by CSIC and various industrial sectors as shown by the other institutions in the world, such as the creation of several Spanish spin-off companies. CNRS in France and Cambridge in the UK.• TNT conference. The golden opportunities nanotube and graphene research offer should not be missed7. Conclusions and thus more generous funding for corresponding research projects is required asSpanish research contributes with important well as the promotion of private R&D initiativesresults to the field of carbon nanotubes and and fostering the link between academics andgraphene. The number of publications in industry.international journals has increased over the lastyears. Here, the activity on theory produceshighest impact publications. On theexperimental side high impact research is carriedout by few groups but lack of critical mass,funding and proper early initiatives are seriousand continuous danger for being competitivewith large international research teams.Visibiltiy of Spanish research has increased (also byinternational networking), but a satisfactory levelof international recognition is not reached yet.On the other hand, solid results of nanotube andgraphene research produced in field of materialsscience, chemistry and energy bear a highpotential for direct technology transfer towards 103
  • 104. > JUAN JOSÉ SÁENZPlace and date of birthMadrid (Spain), 1960EducationProfessor at the Condensed Matter Physics Department of the Universidad Autónoma de Madrid(UAM). Since 1993 he runs the Moving Light and Electrons (MoLE) group at UAM.Experience He joined the UAM as Assistant Professor in 1982 where he worked on the stability and equilibrium properties of small clusters and crystals in Prof. N. García’s group. He was also involved in the first works on magnetic force microscopy (MFM) in collaboration with Prof. Güntherodt’s group in Basel. In 1987 he obtained his PhD from UAM. During his post-doc, he worked on electron field emission from nanotips in Dr. H. Rohrer’s group at IBM-Zürich. From 1989 to 2006 he was Associate Professor at UAM. Since 2007 he is Full Professor at UAM. At present his research interests include theoretical modelling of scanning probe microscopies (SPM), quantum electron transport through nanocontacts and wave transport and molecular imaging through complex media. In 2003 he was Invited Professor in the EM2C-(CNRS) Lab. at École Centrale Paris working on nanoscale thermal transport and nano-optics. He has published over 120 papers (among them 26 in Physical Review Letters) with more than 2300 citations and presented more than 150 communications in international conferences. He is co-organizer of the “Trends in Nanotechnology” (TNT) conference series. He is involved in the European FP7 “NANOMAGMA” (NANOstructured active MAGneto- plasmonic Materials) project and coordinates the Comunidad de Madrid Program “MICROSERES”. juanjo.saenz@uam.es 104
  • 105. T H E O R Y A N D S I M U L AT I O N1. Introduction new integrated approach to modelling at the nanoscale is needed. A hierarchy of multi-scaleDuring the past 20 years, the fundamental tools must be set up, in analogy with whattechniques of theory, modelling, and simulation already exists for microelectronics, although withhave undergone a revolution that parallels the a more complex structure resulting from theextraordinary experimental advances on which more intricate physical nature of the devices.the new field of nanoscience is based. Thisperiod has seen the development of density 2. State of the art1functional algorithms, quantum Monte Carlotechniques, ab initio molecular dynamics, Although the required integrated platforms needadvances in classical Monte Carlo methods and to be developed, the efforts made in the last fewmesoscale methods for soft matter, and fast- years by the modelling community have yieldedmultipole and multigrid algorithms. significant advances in terms of quantitatively reliable simulation and of ab-initio capability,Dramatic new insights have come from the which represent a solid basis on which a trueapplication of these and other new theoretical multi-scale, multi-physics hierarchy can be built.capabilities. Simultaneously, advances in hardwareincreased power by more than four orders of 2.1 Electronic transport simulations andmagnitude. The combination of new theoretical industrial needsmethods together with increased computingpower has made it possible to simulate systems The most widely used codes for ab-initiowith millions of degrees of freedom. simulations of solids and extended systems rely on the use of the Density Functional Theory (DFT),Although theory and modelling has played a key rather than on Quantum Chemistry methods.role in the development and improvement of Many of them have been developed in Europe,industrial applications, so far modelling at the and some of them are commercial, although theirnanoscale has been mainly aimed at support use is mostly limited to the academic community.research and at explaining the origin of observed Among the most popular DFT codes using localphenomena. This is certainly the most important atomic orbitals as a basis set we can mention therole in fundamental science. However, in order order-N code SIESTA2 which uses a basis set ofto meet the needs of the industry and to make numerical atomic orbitals.practical exploitation of new device and solid-state or molecular material concepts possible, a 105
  • 106. N & N i n S p a i n In response to the industrial need of new studies also implies that a much more simulation tools, a class of quantum and interdisciplinary approach than in the past is transport solvers is emerging. However, they do needed, with close integration between not include any inelastic scattering mechanism, chemistry, physics, engineering, and, in aT H E O R Y A N D S I M U L AT I O N and thus are not suitable for the calculation of growing number of cases, biology. transport properties in near-future devices. On the other hand, high-level device simulation 2.3 Carbon-based electronics and spintronics tools are at an early stage of development in universities and research institutions. However, Amongst the most promising materials for the such simulation tools are in general difficult to development of beyond CMOS nanoelectronics, use in an industrial environment, in particular Carbon Nanotubes & Graphene-based materials because of a lack of documentation, support and and devices deserve some particular graphical user interface. consideration. Indeed, their unusual electronic and structural physical properties promote 2.2 Material Science and devices carbon nanomaterials as promising candidates for a wide range of nanoscience and For most emerging devices, the distinction nanotechnology applications. To date, the between material and device simulation is development of nanotubes and graphene getting increasingly blurred, because at low science have been strongly driven by theory and dimensional scales the properties of the material quantum simulation. sharply diverge from those of the bulk or of a thin film and become strongly dependent on the The great advantage of carbon-based materials detailed device geometry. Computational and devices is that, in contrast to their silicon- physics and quantum chemistry researchers based counterparts, their quantum simulation have been developing sophisticated programs to can be handled up to a very high level of explicitly calculate the quantum mechanics of accuracy for realistic device structures. The solids and molecules from first principles. complete understanding and further versatile monitoring of novel forms of chemically- Since quantum mechanics determines the modified nanotubes and graphene will however charge distributions within materials, all lead to an increasing demand for more electrical, optical, thermal and mechanical sophisticated computational approaches, properties, in fact any physical or chemical combining first principles results with advanced property can in principle be deduced from these order N schemes to tackle material complexity calculations. However, even at the DFT level, ab and device features, as developed in some initio calculations are computationally too recent literature (see below). demanding to perform realistic simulations of devices. 2.4 Nano-Bio modelling Therefore, it is necessary to develop more The theoretical understanding of the approximate methods and, finally, to combine bio/inorganic interface is in its infancy, due to them in the so-called multi-scale approaches, in the large complexity of the systems and the which different length scales are described with variety of different physical interactions playing different degrees of accuracy and detail. This a dominant role. Further, state of the art convergence between material and device simulation techniques for large biomolecular 106
  • 107. N & N i n S p a i nsystems are to a large degree still based on it possible to implement a variety of tunableclassical physics approaches (classical molecular and/or switchable field effects at the nanoscale.dynamics, classical statistical physics); while this Thus, a magnetoelectric multiferroic can be usedcan still provide valuable insight into many to control the spin polarization of the current T H E O R Y A N D S I M U L AT I O Nthermodynamical and dynamical properties, a through a magnetic tunnel junction by merelycrucial point is nevertheless missing: the applying a voltage; or a piezoelectric layer canpossibility to obtain information about the be used to exert very well controlled epitaxial-electronic structure of the biomolecules, an like pressures on the adjacent layers of aissue which is essential in order to explore the multilayered heterostructure.efficiency of such systems to provide chargemigration pathways. These are just two examples of many novel applications that add up to the more traditionalMoreover, due to the highly dynamical ones -as sensors, actuators, memories, highly-character of biomolecular systems -seen e.g. in tunable dielectrics, etc.- that can now be scaledthe presence of multiple time scales in the down to nanometric sizes by means of modernatomic dynamics- the electronic structure is deposition techniques. The contribution fromstrongly entangled with structural fluctuations. simulations to resolve more applied problemsWe are thus confronting the problem of dealing (e.g, that of the integration with silicon) is justwith the interaction of strongly fluctuating starting, and it is a major challenge that willcomplex molecules with inorganic systems certainly generate a lot of activity in the coming(substrates, etc). years.2.5 Thermoelectric energy conversion 2.7 NanophotonicsThe importance of research on thermoelectric Another example where multi-scale and multi-energy conversion is growing in parallel with the physics simulations become essential isneed for alternative sources of energy. With the represented by the effort to merge electronicsrecent developments in the field, thermoelectric with nanophotonics. The integration of CMOSenergy generators have become a commercial circuits and nanophotonic devices on the sameproduct in the market and their efficiencies are chip opens new perspectives for opticalimproving constantly, but the commercially interconnections as well as in the data processing.available products did not take the advantage ofnano-technology yet. In fact, thermoelectricity These involve the modelling of “standard”is one of the areas in which nano-scale passive components, such as waveguides,fabrication techniques offer a breakthrough in turning mirrors, splitters and input and outputdevice performances. couplers, as well as active elements, such as modulators and optical switches. This requires2.6 Multifunctional oxides the development of new numerical tools able to describe electromagnetic interactions and lightMultifunctional oxides, ranging from propagation at different length scales. Theypiezoelectrics to magnetoelectric multiferroics, should be able to describe the electromagneticoffer a wide range of physical effects that can be field from the scale of a few light wavelengthsused to our advantage in the design of novel (already of the order of the whole micro-device)nanodevices. For example, these materials make down to the nanometer scale elements. 107
  • 108. N & N i n S p a i n These new tools should include a realistic quantum dots and spintronic and light interaction description of the optical properties including with nanostructures to mention a few. electro- and magneto-optical active nanostructures and plasmonic elements which •A.H. Castro Neto, F. Guinea, N. M. R. Peres, et al.T H E O R Y A N D S I M U L AT I O N are expected to be key ingredients of a new The electronic properties of graphene. generation of active optoelectronic components. Reviews of Modern Physics, 81 (1), 109-162 (Jan 2009). 2.8 NEMO devices •J. C. Meyer, A. K. Geim, M. I. Katsnelson, et al. The structure of suspended graphene sheets, A mayor challenge of the “multi-physical” Nature, 446 (7131), 60-63 (Mar 2007). modelling will be to simulate a full nano-device where electronics, mechanics and photonics •A. I. Hochbaum, R. K. Chen, R. D. Delgado, et al meet at the nanoscale. The interaction of an Enhanced thermoelectric performance of optical field with a device takes place not only rough silicon nanowires. through the electromagnetic properties, but also Nature, 451 (7175), 163-U5 (Jan 2008). through the mechanical response (radiation • B. Z. Tian, X. L. Zheng, T. J. Kempa, et al. pressure forces). Coaxial silicon nanowires as solar cells and nanoelectronic power sources. The physical mechanisms and possible Nature, 449 (7164 ), 885-U8 (Oct 2007). applications of optical cooling of mechanical •A. I. Boukai, Y. Bunimovich, J. Tahir-Kheli, et al. resonators are being explored. Modelling Nano- Silicon nanowires as efficient thermoelectric Electro-Mechano-Optical (NEMO) devices is materials. going to play a key (and fascinating) role in the Nature, 451 (7175), 168-171 (Jan 2008). development and optimization of new transducers and devices. •C. W. Nan, M. I. Bichurin, S. X. Dong, et al. Multiferroic magnetoelectric composites: Thus, one of the main challenges for modelling Historical perspective status and future in the next few years is the creation of well directions. organized collaborations with a critical mass Nature Nanotechnology, 3 (1), 31-35 (Jan 2008). sufficient for the development of integrated •C. A. Schuh, T. C. Hufnagel, U. Ramamurty. simulation platforms and with direct contacts Overview No.144 - Mechanical behavior of with the industrial world. amorphous alloys. Acta Materialia, 55 (12) 4067-4109 (Jul 2007). 3. Some relevant publications (2007-2009) •R. Hanson, L. P. Kouwenhoven, J. R. Petta, et al. Spins in few-electron quantum dots. We have selected 10 publications related with Reviews of moderm Physics, 79 (4), 1217-1265 theory and modelling relevant in Nanoscience (Oct 2007). and Nanotechnology in the period 2007-2009 based on data from ISI Web of Knowledge3: The •J. C. Charlier, X. Blase, S.Roche. publications cover most of the hot topics in Electronic and transport properties of Nanoscience from the electronic properties of nanotubes. graphene, thermal transport and energy Reviews of moderm Physics, 79 (2), 677-732 harvesting with nanowires, new nanostructured (Apr 2007). multiferroic composites and metallic alloys, 108
  • 109. N & N i n S p a i n•F. Krausz, M. Ivanov. European initiatives and networks must be Attosecond physics. performed, and de-fragmentation of such Reviews of moderm Physics, 81 (1), 163-234 activities undertaken. A pioneer initiative has (Jan 2009). been developed in Spain through the M4NANO T H E O R Y A N D S I M U L AT I O N database (www.m4nano.com) gathering all4. Networking for modelling in Spain, Europe nanotechnology-related research activities inand the United States modelling at the national level. This Spanish initiative could serve as a starting point toIn the United States, the network for extend the database to the European level.computational nanotechnology (NCN) is a six- Second, clear incentives need to be launcheduniversity initiative established in 2002 to within the European Framework programmes toconnect those who develop simulation toolswith the potential users, including those in encourage and sustain networking andacademia, and in industries. The NCN has excellence in the field of computationalreceived a funding of several million dollars for nanotechnology and nanosciences. To date, no5 years of activity. One of the main tasks of NCN structure such as a Network of Excellence existsis the consolidation of the nanoHUB.org within the ICT programme, although thesimulation gateway (http://nanohub.org/home), programme NMP supported a NANOQUANTAwhich is currently providing access to NoE in FP6, and infrastructural funding has beencomputational codes and resources to the provided to the newly established ETSFacademic community. (European Theoretical Spectroscopy Facility, www.etsf.eu). This network mainly addressesThe growth of the NCN is likely to attract optical characterization of nanomaterials, andincreasing attention to the US computational provides an open platform for European users,nanotechnology platform from all over the that can benefit from the gathered excellenceworld, from students, as well as from academic and expertise, as well as standardizedand, more recently, industrials researchers. In computational tools. There is also a coordinatedEurope an initiative similar to the nanoHUB, but initiative focused on the specific topic ofon a much smaller scale, was started within the electronic structure calculations, the Psi-kPhantoms network of excellence network (www.psi-k.org).(http://vonbiber.iet. unipi.it) and has beenactive for several years; it is currently being 5. Specific actions to be undertakenrevived with some funding within the EU- (2010-2013)NanoICT coordinated action. An extension of the M4NANO initiative couldIn a context in which the role of simulation might pave the way towards the development of abecome strategically relevant for the European Modelling Database. An initiativedevelopment of nanotechnologies, molecular similar to the American NCN would also benanosciences, nanoelectronics, nanomaterial needed in Europe in conjunction between thescience nanophotonics and EU’s ICT and NMP programs, since the full scopenanobiotechnologies, it seems urgent for Europe from materials to devices and circuits should beto set up a computational platform infrastructure addressed.similar to NCN, in order to ensure its positioningwithin the international competition. The needs These novel initiatives should be able to bridgeare manifold. First, a detailed identification of advanced ab-initio/atomistic computational 109
  • 110. N & N i n S p a i n approaches to ultimate high-level simulation interface that is not suitable for usage in an industrial tools such as Technology Computer-Aided environment. Design (TCAD) models that are of crucial importance in software companies. Many fields There is therefore a need for integration of advancedT H E O R Y A N D S I M U L AT I O N such as organic electronics, spintronics, beyond modelling tools into simulators that can be CMOS nanoelectronics, nanoelectromechanical proficiently used by device and circuit engineers: devices, nanosensor or nanophotonics devices they will need to include advanced physical models definitely lack standardized and enabling tools and at the same time be able to cope with variability that are however mandatory to assess the and fluctuations, which are expected to be among potential of new concepts, or to adapt processes the greatest challenges to further device and architectures to achieve the desired downscaling. functionalities. The European excellence in these fields is well known and in many aspects It is clear that the time is ripe for a new generation overcomes that of the US or of Asian countries. of software tools, whose development is of essential importance for the competitiveness and sustainability of European industry, and which requires a coordinated effort of all the main players. Figure 1. Functionalized graphene nanoribbons can be used to de- tect organic molecules. 6. Conclusions Recent advances in nanoscale device technology Figure 2. The classical diffusion of a small particle in a fluid can be have made traditional simulation approaches greatly enhanced by the light field of two interfering laser beams. obsolete from several points of view, requiring the Langevin Molecular Dynamics simulations show that radiation pres- sure leads to a giant acceleration of free diffusion. [Albaladejo et al., urgent development of a new multiscale modelling Nano Letters 9, 3527 (2009)] (Courtesy of Silvia Albaladejo). hierarchy, to support the design of nanodevices and nanocircuits. References This lack of adequate modeling tools is apparent not only for emerging devices, but also for aggressively 1 Based on M. Macucci et al, Status of modelling scaled traditional CMOS technology, in which novel for nanoscale and information processing and geometries and novel materials are being storage devices, E-Nano Newsletter 16, 5 (2009). introduced. New approaches to simulation have (www.phantomsnet.net/files/E_NANO_NEWS/ been developed at the academic level, but they are E_NANO_Newsletter_Issue16.pdf). usually focused on specific aspects and have a user 110
  • 111. N & N i n S p a i n2 J. M. Soler, E. Artacho, J. D. Gale, A. García, J.Junquera, P. Ordejón, D. Sánchez-Portal, “TheSIESTA method for ab initio order-N materialssimulations”, Journal of Physics: Condensed T H E O R Y A N D S I M U L AT I O NMatter 14, 2745(2002). (www.icmab.es/siesta).3 Data obtained by on-line search in the ISI Web ofKnowledge among the most cited papers publishedin the period “2007-2009” (Publication year) havingmore than 48 citations per year. The list wascompleted by searching (in topic) for “nano* andsimul*”, “nano* and theor*” and “nano* andmodel*”. 111
  • 112. Emerging N&N Centers in Spain • IMDEA Nanociencia • CIC nanoGUNE Consolider • Instituto Català de Nanotecnologia (ICN) • Instituto de Nanociència i Nanotecnologia (CIN2- UB) • The Institute of Photonic Sciences (ICFO) • Institute of Nanoscience of Aragon (INA) • Andalusian Centre for Nanomedicine and Biotechnology (BIONAND) • International Iberian Nanotechnology Laboratory (INL) • Valencia Nanophotonics Technology Center (NTC)• Nanomaterials and Nanotechnology Research Center (CINN) 112
  • 113. N & N i n S p a i n NANOSCIENCE & NANOTECNOLOGY IN SPAIN: CENTERSIMDEA Nanociencia (Madrid Institute for Opening: The building of IMDEA NanocienceAdvanced Studies in Nanosciences) Institute, located in the UAM Cantoblanco campus, will be operative in October 2011. Provisional headquarter: UAM. Facultad de Ciencias; Módulo C-IX. 3rd floor. CENTERS Activity AreasFacultad de Ciencias; Módulo C-IX, 3ª plantaAvda. Fco. Tomás y Valiente, 7 Program 1. Molecular nanoscienceCiudad Universitaria de Cantoblanco • Design and Synthesis of Molecular28049 Madrid Nanostructures and Nanomaterials.Tel +34 91 497 6849 / 51 • Atomic and Molecular Self-assembly at Surfacese-mail: contacto.nanociencia@imdea.org and Spectroscopy on Molecular Systems.web: www.nanociencia.imdea.org Program 2. Scanning Probe Microscopies and Surfaces • Advanced Microscopies and Local Spectroscopies. • Inelastic Spectroscopy at Surfaces. Program 3. Nanomagnetism • Magnetic Nanomaterials. • Biomedical Applications. Program 4. Nanobiosystems: Biomachines and Manipulation of Macromolecules • Single-molecule Analysis of Macromolecular Aggregates.Summary: The IMDEA Nanociencia Foundation, • Organization of Macromolecular Aggregatescreated by a joint initiative of the regional on Defined Substrates.Government of Madrid and the Ministry ofScience and Education of the Government of Program 5. Nanoelectronic and superconductivitySpain, manages the IMDEA Nanociencia Institute. • Electric Transport in Nanosystems.This new interdisciplinary research centre aims at • Superconducting Nanostructures.becoming a flexible framework to create newinternationally competitive research groups by Program 6. Semiconducting Nanostructures andhybridizing some of the best scientists in Madrid Nanophotonicsdedicated to the exploration of basic nanoscience • Semiconducting Nanostructures for Quantumwith recognized researches recognized elsewhere Information.recruited on an internationally competitive basis. • Nanophotonics. 113
  • 114. N & N i n S p a i n Horizontal Program on Nanofabrication and CIC nanoGUNE Consolider Advanced Instrumentation Employees Researchers (including associated) 19 / PostDoctoral Researches 6 / PhD students 6 / Tolosa Hiribidea, 76 Management Staff 3. For more information see E-20018 Donostia - San Sebastián web www.nanociencia.imdea.org Tel. 943 574 000CENTERS Contact person / e-mail Infrastructure (from 100.000€) José María Pitarke de la Torre/ jm.pitarke@nanogune.eu Low-Temperature Scanning Tunnelling Effect web: www.nanogune.eu Microscope (STM); Femtosecond spectroscopic instrumentation; Atomic Force and Fluorescence Microscope. Projects / Funding • DOTUBE (FP7- Marie Curie Actions-PEOPLE- ERG-2008). • BIONANOTOOLS (FP7- Marie Curie Actions- PEOPLE-IRG-2008). • Crecimiento y caracterización de nuevos nanomateriales basados en el Summary: The CIC nanoGUNE Consolider is a newly autoensamblado de puntos cuanticos y established Center created with the mission of nanotubos de carbono sobre superficies addressing basic and applied world-class research sólidas (MAT2009-MICINN). in nanoscience and nanotechnology, fostering high- standard training and education of researchers in • AMAROUT (FP7-Marie Curie Actions-PEOPLE- this field, and promoting the cooperation among COFUND-2008) (IMDEA Nanociencia as a the different agents in the Basque Science, part). Technology, and Innovation Network (Universities and Technological Centers) and between these 2008 annual budget in M€ (including salaries) agents and the industrial sector. and an estimation when fully operating. This information is subject to the Spanish Legislation Opening date: 30th January 2009 on Privacy (Ley Orgánica 15/99 –LOPD) and could not be provided. Activity Areas NANOMAGNETISM GROUP – CIC1 • Magnetization reversal, dynamics, and related characterization methods. 114
  • 115. N & N i n S p a i n• Fabrication and magnetic properties of Forecast 2015 multilayered magnetic materials. Staff: 35• Fabrication and characterization of magnetic Others: 65 nano-structures. Infrastructure (from 100.000€)NANOOPTICS GROUP – CIC2 • 150TWO Ultra High Resolution E-Beam Tool• Ultra-broadband near-field optical • Deposition System microscopy. • Vibrating Sample Magnetometer QD-SQUID• Near-field optical characterization of nanoscale VSM CENTERS materials and semiconductor devices. • QD-PPMS (Phiysical Property Measurement• Near-field characterization of photonic System) structures. • Laser Confocal Microscope • WITec Confocal Raman Microscope SystemSELF-ASSEMBLY GROUP – CIC3 Alpha300 R Em-CCD• Plant viruses as scaffolds for nanoscale • ATC 2200 UHV Sputtering System structures. • Scanning Near-field Optical Microscope• Electrospinning of self-assembling material to System wires . • EVG620 Double Side Mask • AFM/STM Microscope Agilent 5500NANOBIOTHECNOLOGY GROUP – CIC4 • Univex 350 for Thermal and E-Beam• Energy transfer processes in hybrid materials Evaporation for chemical and biological fuel production, • Base, Acid and Solvent Wetbench biophotonic and photovoltaic applications. • HF Probe Station from Lake Shore• Biomedical diagnostics using the energy • 4¨ALD system Savannah 100 transfer processes. • Fisher equipment• Ultrasensitive nanocrystal-based pathogen • Flux Cytometer CyAn-ADP from Beckman coulter detection employing the energy transfer processes. Nanofabrication tools • Ion Beam Etching SystemNANODEVICES GROUP – CIC5 • UHV Ebeam Thermal Deposition System• Carbon-based spintronics • Reactive Ion Etcher• Multifunctional devices • Ultra High Resolution E-Beam Lithography Tool• Nanofabrication • UHV Sputtering System • Mask AlignerEmployees • Atomic Layer Deposition System2009 Characterization toolsStaff: 22 • High Resolution (Scanning) TransmissionOthers: 18 Electron Microscope • Environmental Scanning Electron Microscope2010 (SEM/ESEM)Staff: 23 • Dual-Beam Focused Ion BeamOthers: 30 • X-Ray Diffractometer • FTIR Spectrometer 115
  • 116. N & N i n S p a i n • Confocal Raman Microscope Institut Català de Nanotecnología (ICN) • Laser Confocal Microscope • Physical Properties Measurement System (PPMS/QD-SQUID) • Scanning Near-field Optical Microscope • AFM/STM Microscopes • Cytometer Projects / FundingCENTERS • MAGNYFICO Magnetic nanocontainers for Campus de la Universidad Autónoma de combined hyperthermia and controlled drug Barcelona – Facultad de Ciencias release (EU, 2008) Edificio CM7 08193 Bellaterra • Pulsos Magneticos Intensos Inducidos por Tel: +34 93 581 44 08 / Fax: +34 93 581 44 11 paredes de dominio moviles: Aplicaciones a la Contact person / e-mail dinamica Ultrarrápida (MICINN, 2009) Jordi Pascual / Jordi.pascual.icn@uab.es, icn@uab.es • Nanoantenna: Development of a high web: www.nanocat.org sensitive and specific nanobiosensor based on surface enhanced vibrational spectroscopy Summary: The ICN is a non-profit research dedicated to be the in vitro proteins detection institute, created in 2003 by the Catalan and diases diagnosis (EU, 2009). Government and the Autonomous University of Barcelona (UAB), who remain its patrons. The ICN 2008 annual budget in M€ (including salaries) works concurrently in Scientific Research and an estimation when fully operating (Nanoscience, primarily via European and national Budget 2008: 2 M € collaborative projects), and in Technology Budget 2009: 3 M € Research (Nanotechnology, in areas of internal Budget forecast 2015: 4 M € expertise and co-development with private industry). In addition to its own research activities, the Institute also engages in collaborative research, dissemination, educational and managerial activities with other institutions such as universities, scientific institutes, ministries and private companies, at regional, national and international levels. Opening date: July 2003 Activity Areas Atomic Manipulation and Spectroscopy 116
  • 117. N & N i n S p a i nInorganic Nanoparticles Centro de Investigación en Nanociencia yMagnetic Nanostructures Nanotecnología (CIN2)Nanobioelectronics & BiosensorsPhononic and Photonic NanostructuresPhysics and Engineering of Nanoelectronic DevicesQuantum NanoElectronicsNanoscience Instrument Development LaboratoryEmployees CENTERS ETSEActual: 100 (80 researchers, 20 administratives Campus UABand technicians) Building Q - 2nd FloorFuture: 150-200 total 08193 Bellaterra info@cin2.esInfrastructure (from 100.000€) Tel. 93 581 49 69 Fax 93 586 80 20The ICN has specialised facilities, some uniquein Spain, including a powerful electron Contact person / e-mailmicroscopy laboratory, FIB-SEM, electron-beam Albert Figueras / albert.figueras@cin2.esevaporators, nanoimprint lithographies, low and web: www.cin2.esvariable temperature STMs, magneticcharacterization (Nano- MOKE, SQUID), AFM,SNOM, dip pen nanolithography, cryogenic andvery low temperature cryogenic (< 20 mK)systems, X-Ray diffraction and spectroscopysystems, Pulsed Laser Deposition (PLD)chambers, optical spectroscopy (Raman, IRFT,UV-VIS) and more.Projects / FundingBudget 2008: 3,8 M €Budget forecast: 12 M € Summary: Located in the Barcelona area, CIN2 is a key action for the development of Nanoscience and Nanotechnology in Catalonia and Spain, aiming to be an international referent of scientific excellence. CIN2 is a mixed center formed by the Consejo Superior de Investigaciones Científicas (CSIC) and the Institut Català de Nanotecnologia (ICN). This joint intellectual adventure spans from fundamental research in nanoscience to appplications of nanotechnology, interfacing with 117
  • 118. N & N i n S p a i n the industrial enviroment. We promote both local Employees and international collaborations, and our research ranges from focused lines to transversal activities. At this time the center has about 175 people, Excellence and dedication are the pillars and within months the number will grow with supporting the activity of this research center. the move to new building. Opening The research staff represents the 80%, either employed or in training. The rest are CIN2 exists as a center since January 2008. Since administrative staff and technicians.CENTERS then, it has been temporarily located in several buildings around the UAB Campus. The permanent Infrastructure (from 100.000€) headquarters of the center are under constructions in the same Campus and will open by 2011. • Dual System FIB-SEM • XPS/UPS System ICN 05/08 Activity Areas • X-Ray Difraction (capes primes (cu) I (co) ICN04/08 • SQUID CIN2 (CSIC-ICN) counts with five research lines. • Mid-far IR Spectometer (ICN 08/08) Theory and simulation at the nanoscale, • EVAPORADOR DE MATERIAL MAGNÈTIC Scanning probe microscopy and synchrotron • EVAPORADOR DE FEIX DIONS STANDARD radiation spectroscopy, Physical properties of • Axio Observer Fabricated nanostructures, Chemical approaches • NANOMAN -01 to nanostructured functional materials and • DILUTION REFRIGERATOR AND MAGNET devices and Nanobiosensors devices. Each one of - MICROSCOPI PICO PLUS AFF/STM these areas has its sublines. - DPN-0002-01 DPNWRITER TM NSCRIPTOR - Microscopi Pico PLUS AFM/STM At present, there are 13 research sublines of - Pulsed Laser Deposition (PLD) investigation. - UV RAMAN (ICN010/08) • Atomic manipulation and spectroscopy - Multiview 4000 Microscope System • Inorganic nanoparticles - NANOMOKE2 • Magnetic nanostructures - MICROSC. LT STM DE BAJA TEMPER • Nanobioelectronics & biosensors - Microscopi STM 150 Aarhus • Nanobiosensors and molecular nanobiophysics • Nanophononics and nanophotonics Projects / Funding • Nanostructured functional materials • Novel energy-oriented materials EURYI – ‘Quantum probes based on Carbon • Physics and engineering of nanodevices (pen) Nanotubes’ – Prof. Adrian Bachtold, Leader of • Pld & nanoionics the Quantum Nanoelectronics Group at CIN2. • Quantum nanoelectronics UE. • Small molecules on surfaces in ambient and pristine conditions Specific agreement on management of • Theory and simulation technology transfer in the field of biotechnology between CSIC and Fundación Marcelino Botin. Laura Lechuga, Leader of the Nanobiosensors and Molecular Nanobiophysics Group at CIN2 118
  • 119. N & N i n S p a i nNOMAD - Nanoscale Magnetization Dynamic ICFO-The Institute of Photonic SciencesERC-SIG-203329 (2008-2013). PMT-UPCP. Gambardella, leader of the Atomic andSpectroscopy Group at CIN2 (ICN-CSIC).Budget 2008: 2 M €. CENTERS Avda. del Canal Olímpico s/n 08860 Castelldefels (Barcelona) Tel 93 553 40 01 Contact Person / e-mail: Gonçal Badenes / Goncal.Badenes@icfo.es web: www.icfo.es Summary: The Institute of Photonic Sciences, was created in 2002 by the regional Government of Catalonia, Spain - through the Department of Universities and Research - and the Technical University of Catalonia. ICFO is a research centre of excellence devoted to the study of the optical sciences, with the mission to become one of Europe’s foremost photonics research centres. The centre has a triple mission of frontier research, post-graduate education, and knowledge and technology transfer. ICFO collaborates actively with many leading research centres, universities, hospitals, health care 119
  • 120. N & N i n S p a i n centres, and a variety of private corporations INSTITUTE OF NANOSCIENCE OF ARAGON worldwide. Opening: April 2002 Activity Areas Research at ICFO is organized in four wide-scope areas: Nonlinear Optics, Quantum Optics, Nano-CENTERS Photonics and Bio-Photonics. EDIFICIO I+D Employees Campus río Ebro, Universidad de Zaragoza At present, ICFO hosts 17 research groups that c/ Mariano Esquillor, s/n 50018 Zaragoza work in 50 laboratories and one Nano-Photonics Tel 976 762 777 fabrication facility, all hosted in a 9000 sq.m Contact Person / e-mail dedicated building based at the Mediterranean Ricardo Ibarra (Director) / ina@unizar.es Technology Park, in the Metropolitan Barcelona web: www.unizar.es/ina area. ICFO is currently expanding, thus by 2013 the institute will host some 350 researchers organized in 25 groups. Infrastructure (from 100.000€) • Optical and electron beam lithography • Sputtering • Thermal and electron-beam evaporation • Plasma etching (RIE+ICP) • Atomic Layer Deposition • Spectroscopic ellipsometry Projects / Funding Summary: The Institute of Nanoscience of Aragon is an interdisciplinary research institute • Nanophotonics for Energy Efficiency- of the University of Zaragoza (Spain) created in nanophotonics4energy (NoE, UE). 2003. Our activity is focused on R+D in nanoscience and nanotechnology, based on the • Surface Plasmon early Detection and processing and fabrication of structures at the Treatment Follow-up of Circulating Heat Shock nanoscale and the study of their applications, in Proteins and Tumor Cells-SPEDOC (STREP, UE). collaboration with companies and technological institutes from different areas. • Ultrathin Transparent Metal Conductors (CDTI, CIDEM, MICINN, industrial partners). Opening: The Institute was created the 6th May 2003 (DECRETO 68/2003, de 8 de abril, del Gobierno de Aragón). 120
  • 121. N & N i n S p a i nActivity Areas “top-down” approaches with applications of interest.1. NANOBIOMEDICINE The main research topics in this line are relatedThe Nanobiomedicine line covers different to the preparation and characterization ofaspects of the fields of the diagnosis and therapy, several nanostructures, as well as withwhich involve the use of nanoestructured applications development:materials. - Nanoporous Interphases: CENTERSNanomaterials for Biomedical Applications Microreactors and sensors- Inorganic Nanoparticles - Hybrid Membranes- Organic Nanoparticles - Carbon Nanotubes and Nanofibers- Nanostructures functionalization - Nanocomposites - Organic and organic-inorganic hybrid MonoNanodiagnostics and Multilayers- Magnetic Biosensors - Organic Polymers for Optical Applications- Optic Biosensors - Safety in the handling of nanomaterials- Contrast Agents for medical imaging 3. PHYSICS OF NANOSYSTEMSNanotherapy- Drug Delivery: (i)mobile vectors; (ii)fixed Physical and chemical properties of molecules & platforms; (iii) through biological structures materials at the nanoscale (transfection, using Dendritic Cells)- Hiperthermia • Spintronics • Magnetism in thin filmsNanotoxicity • Materials and molecules structure with STM,- Biocompatibility AFM, MFM, HRTEM, UHRTEM microscopy- Biodistribution • Optic and electronic Nanolithography- Citotoxicity • Nanofabrication through “dual-beam” • MEMs and NEMs (Micro- and NanoelectromechanicalFrom the research in this field the new Spin-off systems)NanoScale Biomagnetics© (nB) has risen. It • Optical and Magnetic sensorsdevelops and commercializes technology and • XAFS espectroscopy quantums dots.equipment for research in biomedicina.www.nbnanoscale.com EmployeesAlso, a new Spin-off, Nanoimmunotech© was A staff of 120 researchers (61 Postdoctoralcreated in 2010. Fellows, 37 PhD Students, 15 Laboratory Technicians, 7 in Administration) are working at2. NANOESTRUCTURED MATERIALS INA. Thanks to our qualified staff and our advanced instruments and infrastructures INA isThe aim of the Nanostructured Materials a benchmark in Europe in the fields ofresearch line is to investigate and develop new Nanoscience and Nanotechnology.materials and devices using “bottom-up” and 121
  • 122. N & N i n S p a i n Infrastructure (from 100.000€) Total grant coordinated by INA: 888.636,00 € Total INA grant: 222.000,00 € The seven laboratories of INA are equipped with Funded by: ERANET a state-of-the-art equipment. Leader: RICARDO IBARRA 1. Local probe microscopy Lab.: Atomic Force Title: Consolider-Nanotecnologies in Biomedicine Microscope (AFM), Dip-Pen, two Scanning Starting date: sept-2006/sept 2011 Tunelling Microscope (STM). Total grant coordinated by INA: 4.500.000,00 € Total INA grant: 800.000,00 €CENTERS 2. Electronic microscopy Lab.: 4 Electronic Funded by: MICINN Transmission Microscopes: TEM 200kW, High Resolution TEM (HRTEM) 300kW, Ultra High Leader: JOSÉ LUIS SERRANO Resolution TEM (UHRTEM) 300kW with probe- Title: Functional liquid cristallyne dendrimers: spherical aberration corrected and UHRTEM Synthesis of new materials, resource for new 300kW with image objective-spherical applications (DENDREAMERS) aberration corrected. Two Scanning Electron Starting-ending date: 01/10/2007-30/09/2011 Microscope (SEM). Total grant coordinated by INA: 4.219.110,00 € Total INA grant: 897.307,00 € 3. Thin films growth Lab.: Equipment for Pulsed Funded by: European Commission Laser Deposition-Magnetron Sputtering (plasma PLD-Sputtering), and another Pulsed Laser 2008 annual budget in M€ (including salaries) Deposition. Molecular Beam Epitaxis (MBE). and an estimation when fully operating The annual budget in 2008 was 8 M€ from 4. Optical and electronic nanolithography Lab. research projects won in public competition plus Clean room 100 m2 class 10000 and 25m2 class also the annual budget given by the Aragon 100.: Electronic Nanolitography with Dual Beam Government. (Nanolab) 5. Characterization of nanostructures Lab.: X-Ray Photoelectron Spectroscopy and Auger Electron Spectroscopy (XPS-Auger), X-Ray Diffraction (XRD). 6. Synthesis and functionalization of nanosystems Lab. 7. Biomedical applications Lab. Projects / Funding Leader: RICARDO IBARRA Title: Multifunctional Gold Nanoparticles for Gene Therapy (NANOTRUCK) Starting date: 01/07/2009-30/06/2012 122
  • 123. N & N i n S p a i nCentro Andaluz de Nanomedicina y BIONAND is the first Spanish nanotechnologyBiotecnología (BIONAND) / Andalusian research centre entirely focused on nanomedicine.Centre for Nanomedicine and BIONAND is born to be the Spanish NanomedicineBiotechnology (BIONAND) reference centre. Opening: End of 2010 Activity Areas CENTERS Nanodiagnostics, Thearapeutic Nanosystems, NanobiotecnologyC/ Severo Ochoa Infrastructure (from 100.000€)Parque Tecnológico de Andalucía (PTA)Málaga, Spain Cell Culture Facilities, Confocal and ElectronicTel +34 955 40 71 39 / +34 955 04 04 50 Microscopy Facilities, Espectroscopy Facilities,Contact Person / e-mail Flow Citometry Facility, Molecular Biology CoreDavid Pozo Perez Facility, Animal facility.david.pozo@juntadeandalucia.esdavid.pozo@cabimer.es Projects / Fundingweb: www.bionand.es 3 2008 annual budget in M € (including salaries) and an estimation when fully operating 2.600.000 €Summary: The Andalusian Centre forNanomedicine and Biotechnology Centre(BIONAND) is conceived as a multidisciplinary spacedesigned for fostering and promoting cutting-edgeresearch in the field of nanobiotechnology appliedto human diseases. The centre is a joint initiative ofthe Regional Ministry of Innovation, Science andEnteprise of Andalusia, the Regional Ministry ofHealth of Andalusia, the University of Malaga andthe Mediterranean Institute for the Advancementof Biotechnology and Health Research (IMABIS). 123
  • 124. N & N i n S p a i n International Iberian Nanotechnology - Nanotechnology applied to food industry, Laboratory food safety and environment control. - Nanomanipulation, molecular devices, using biomolecules as building blocks for nanodevices. - Nanoelectronics: Nanofluidics, CNTs, molecular electronics, spintronics, nanophotonics, NEMS, and otherCENTERS Av. José Mestre Veiga, nanotechnologies used to build nanodevices 4715-310 Braga and system platforms to support the previous Portugal research topics. Tel +351 253 601550 Fax: +351 253 601 559 Employees Contact Person / e-mail: José Rivas (General Director) Staff Currently Expected at full oper. jose.rivas@inl.int Researchers 8 160 web: www.inl.int Administration 6 35 Technicians 6 55 PhD students 18 100 Total 38 350 Infrastructure (from 100.000€) INL is currently purchasing and installing its main equipment. Among the projected equipment, INL include: • Central Micro and Nanofabrication Clean Summary: The International Iberian Room: (Class 100 and 1000 ) with a 400m2 Nanotechnology Laboratory, a recently formed useful area, with an expansion capability to international research organization, is a joint 600 m2. The gross clean room area (bay and research facility created by the Spanish and chase) is around 1100 m2. Portuguese governments to foster Nanotechnology and Nanosciences. INL is The nanolithography area is specially located in Braga, North of Portugal and it expects designed to VC-E vibration specifications to to achieve a research community of around 400 accommodate two e-beam tools (10nm or people at full operation. better feature resolution). The optical lithography bay will include a direct write laser Activity Areas tool and mask aligners. - Nanomedecine; drug delivery systems, • Specialized labs with VC-E or better vibration molecular diagnosis systems, cell therapy and specifications and particular EMI shielding tissue engineering. requirements: Including imaging and 124
  • 125. N & N i n S p a i n characterization tools (HRTEM with spherical as well as for biosensing, exploiting photonic, aberration correction, dual beam FIB/FEG, Bio electrical and magnetic fields in the PAM. This TEM, surface analysis cluster(SIMS, XPS), project is carried out in collaboration with Max shielded rooms. Planck Institute for biophysical Chemistry in• Central Scanning Probe Microscopy Gottingen, Germany. Laboratory: This laboratory will support SPM activity from standard imaging to advanced 3. Investigations in modern electron microscopy interdisciplinary applications and development techniques such as Cs corrected STEM, Cs of new techniques. Corrected TEM, EELS, EDS, holography and CENTERS others to the study of nanoparticles,• Central Biology and Biochemistry facility: to nanostructures and soft nanostructures provide support for groups developing biology (polymers and bio materials). Studies include all and biochemistry activity (cell culture, DNA aspects of image calculations and image manipulation, microspotting, etc.). interpretation. Project carried out in collaboration with the University of Texas at SanAdditionally INL will have 22 to 24 wet and dry PI Antonio.labs that will be gradually equipped (spintronics,NEMS, photonics, high frequency devicecharacterization, nanomaterial synthesis labs,etc…).Projects / Funding1. Study of DNA interactions with inorganicnano-components, and how the morphology ofgenerated self-organized structures can beregulated. The project includes tailoring designof bimolecular shell around nanoparticles andbio-linkers to control particle clustering andphases on surfaces and in bulk. Project incollaboration with Center for FunctionalNanomaterials – Brookhaven NationalLaboratory. New York, US.2. Design, implementation and application of anew microscope for optical sectioning of livecells called the Programmable Array Microscope(PAM). Additionally this project includes thedesign and production of novel biosensors,obtained by combination of organicfluorophores with Nanoparticles.These biosensors might later be employed asreagents to induce biological and physical effects 125
  • 126. N & N i n S p a i n Valencia Nanophotonics We are in a new building for the exclusive use of Technology Center the center inside the UPV Science Park The building measures 3500 square metres with space for 100 professionals, including a 500 square metre cleanroom (class 10-100-10.000). The aim of the NTC and the UPV Science Park is to encourage regional development by transferring university research results to Universidad Politécnica de Valencia industry. The NTC offers an extraordinaryCENTERS Valencia Nanophotonics Technology Center technological potential and is dedicated to Edificio 8F, 2nd floor business development. Camino de Vera, s/n 46022 Valencia Date of Foundation: The governing council of Phone: +34 96 387 97 36 the Technical University of Valencia officially Fax: +34 96 387 78 27 approved the creation of the NTC on 24 July Contact Person / e-mail 2003. Javier Martí, Scientific Director jmarti@ntc.upv.es Research Areas web: www.ntc.upv.es - Optical Networks & Systems - Photonic materials & devices - Micro/Nanofabrication and Facilities The area Optical Networks & Systems is divided into six research lines: • Optical Access and Next-Generation Networks • Optical Networks • Optical Signal Processing • Lasers & Fibre-based Devices • Microwave and Terahertz Photonics Brief Overview • Frequency combs and DWDM sources The area Photonic materials & devices is divided The Valencia Nanophotonics Technology Center into five research lines: (NTC) is a research center inside the Universidad • Metamaterials Politécnica de Valencia (UPV)). The center • Biophotonics includes its own team about 75 researchers. • Optical modulators • Nonlinear Silicon Photonics Our mission is to establish leadership in Europe in • Polymer photonic devices the micro/nanofabrication of silicon structures for the development of nanotechnologies. Our The area Micro/Nanofabrication and Facilities photonics products are applied in sectors such as: is divided into four research lines: optical fibre networks and systems, biophotonics, • Nanofabrication defence, security, and photonic computation. • Coupling and Packaging 126
  • 127. N & N i n S p a i n• Facilities & Equipment CENTURA and P5000.• Photovoltaics Chemical cleaning: FSI Mercury reactor, SEMITOOL organic solvent system.Current and future personnel Physical Caracterization: HITACHI SEM S-4500 electron microscope.Current Personnel Evaporator: Pfeiffer Classic 500 EVG101 Advanced Resist Processing SystemSteering Scientific Committee: 3 Therma-wave Opti-probe 5220Management: 5 Bruker VERTEX 80 FTIR (Fourier Transform CENTERSHuman Resources: 1 InfraRed)Informatics: 3 “Flip-Chip” die attachment equipment SETLab technicians: 6 FC150Area Scientific Leaders: 4Senior Researchers: 10 Most relevant projects, both running orJunior Researchers: 16 approved in 2009.Grant Students: 14Nanofabrication: 13 PROJECT TITLE: Improve Photovoltaic EfficiencyResearchers associated to NTC: 5 by applying novel effects at the limits of light toTotal: 9 persons in management and 71 persons matter interaction.LIMA-FP7-248909.in research Financial Institution: European Commission.Maximum Personnel Coordinator: Universidad Politécnica de Valencia UPVLC.Steering Scientific Committee: 3 Participants: Universidad Politécnica deManagement: 6 Valencia, UPVLC, Spain; Universita degli Studi diHuman Resources: 2 Trento, UNITN (Italy); Fundazione Bruno KesslerInformatics: 3 FBK (Italy); Agencia Estatal Consejo Superior deTechnicians: 8 Investigaciones Científicas, CSIC, Spain;Area Managers: 6 International Solar Energy Research CenterSenior Researchers: 20 Konstanz ISC; Germany, Isofotón SA, ISO Spain;Junior Researchers: 40 University of New South Wales, UNSW, Australia.Grant Students: 20 Team Leader: Guillermo Sánchez.Nanofabrication: 20 Duration: from January 2010 to December 2012Researchers associated to NTC: 5 Budget: 2.375.000 EUR (1.044.691 EUR UPVLC)Total: > 140 PROJECT TITLE: TAILoring photon-phononMost relevant equipments interaction in silicon PHOXonic crystals (TAILFOX) FP7-ICT Project 233883Lithography: Raith 150 e-beam direct writing,Nikon DUV stepper 180 nm, 8-inch wafers, TEL- Financial Institution: European Commission.mark8 Developer, TEL- mark8 Coater. Coordinator: Universidad Politécnica de ValenciaThin Film Deposition: Applied Materials P5000 UPVLC.and Centura Participants: UNIVERSIDAD POLITÉCNICA DEEtch: STS ICP etch tool AOE Multiplex, AMAT VALENCIA, UPVLC, Spain. OTTO-VON-GUERICKE- 127
  • 128. N & N i n S p a i n UNIVERSITAET MAGDEBURG, Germany. Indirect Costs: 595.277,13 € CATALAN INSTITUTE OF NANOTECHNOLOGY, Total: 3.571.662,76 € Spain. NATIONAL CENTER FOR SCIENTIFIC RESEARCH – DEMOKRITOS, Greece. CENTRE Budget for 100% capacity NATIONAL DE LA RECHERCHE SCIENTIFIQUE Personnel Costs: 4.000.000 € (CNRS), France. Operation Costs: 2.500.000 € Team Leader: Alejandro Martínez Abietar Indirect Costs: 1.300.000 € Duration: from May 2009 to April 2012 Total: 7.800.000,00 Budget: 2.595.797 EUR (583.458 EUR UPVLC)CENTERS PROJECT TITLE: CONSOLIDER ENGINEERING METAMATERIALS (EMET) (CSD2008-00066) Financial Institution: Ministerio de Ciencia e Innovación Coordinator: UPV Participants: Universidad Pública de Navarra, Universitat Autòmoma de Barcelona, Universidad de Sevilla, Consejo Superior de Investigaciones Científicas, Universidad de Málaga Universidad, Politécnica de Madrid. Team Leader: Javier Martí Sendra Duration: from December 2008 to December 2013 Budget: 3.500.000 Euros (1.040.076,00 Euros UPVLC) Employees 54 Valencia NTC has a track record in leading European R&D Framework projects in FP5, FP6 and FP7 and also international contract with RTD organizations like European Space Agency, European Southern Observatory and European Defence Agency. Since 2000 NTC has co- ordinated 11 projects and has participated in 28 projects and networks of excellence. Annual Budget (M€) Budget 2009 Personnel Costs: 1.989.683,34 € Operation Expenses: 986.702,29 € 128
  • 129. N & N i n S p a i nCentro de Investigación en Nanomateriales so called “Controlled Design of Multifunctionaly Nanotecnología - Nanomaterials and Multiscaled Materials” which comprises threeNanotechnology Research Center (CINN) research sublines: • Modelling and Simulation • Nanostructured Hybrid Systems • Synthesis and Advanced Characterization of Nanocomposites and Bioinspired Materials CENTERSParque Tecnológico de Asturias EmployeesEdificio Fundación ITMA33428 Llanera - Asturias Personnel (currently): 46Contact Person / e-mail Hired: 16Prof. Ramón Torrecillas San Millán / Training: 12Director.cinn@csic.es Civil Servant: 18web: www.cinn.es Personnel (Planned): 100 Infrastructure (from 100.000€) • Atomic Force Microscopy/ Scanning Tunneling Microscopy • Electron Beam Lithography • Single Cristal and Powder X-Ray DiffractometrySummary: The Nanomaterials and • Nanoindentator Hysitron - TriboLab™Nanotechnology Research Center (CINN) is a joint • Chemical Vapor Deposition (CVD) / Physicalresearch center created in 2007 by institutional Vapor Deposition (PVD)joint initiative between the Spanish Council for • Cryogenic dilatometeScientific Research (CSIC), the Government of • Spark Plasma SinteringAsturias and the University of Oviedo. • Optical Laboratory (Holography) • ElipsometerThe CINN combines interdisciplinary research • Hot Isostatic Pressstrongly competitive at international level withscientific and technological demonstration Projects / Fundingactivities towards enterprises technologicallyadvanced, and has among its main objectives • IP NANOKER “Structural Ceramicthe creation of new technology-based firms. Nanocomposites for top-end Functional Applications”. European Union. SixthOpening: 19th November 2007 Framework Programme. • Nanotechnology for Market (nano4m).Activity Areas European Union. INTERREG IVC. • Desarrollo y Obtención de MaterialesThe Nanomaterials and Nanotechnology Innovadores con Nanotecnologia Orientada –Research Center is focused on one research line DOMINO. MICINN. 129
  • 130. Annex I: NanoSpain Network • Research Topics • Regional distribution of research groups • Total personnel • Members List130
  • 131. N & N i n131 S p a i n N A N O S P A I N N O T W O E R I A LS T A T I S T I C S N A N E M AT R K / S
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  • 137. N & N i n137 S p a i n N A N O S P A I N N O T W O E R I A LS T A T I S T I C S N A N E M AT R K / S
  • 138. N A N O S P A I N N O T W O E R I A LS T A T I S T I C S N A N E M AT R K / S N & N i n138 S p a i n
  • 139. N & N i n139 S p a i n N A N O S P A I N N O T W O E R I A LS T A T I S T I C S N A N E M AT R K / S
  • 140. N A N O S P A I N N O T W O E R I A LS T A T I S T I C S N A N E M AT R K / S N & N i n140 S p a i n
  • 141. N & N i n141 S p a i n N A N O S P A I N N O T W O E R I A LS T A T I S T I C S N A N E M AT R K / S
  • 142. N A N O S PA I N N E T W O R K / S TAT I S T I C S N & N i n142 S p a i n
  • 143. N & N i n S p a i n 143
  • 144. Annex II: R&D Funding • Total Funding • Evolution Total Funding • Evolution Funding Origin144
  • 145. N & N i n S p a i n R & D FUNDING 145
  • 146. N & N i n S p a i nR & D FUNDING 146
  • 147. N & N i n S p a i n R & D FUNDING 147
  • 148. Annex III: Publications / Statistics • No. Publications per Region • No. Publications per Year • No. Publications per Issue148
  • 149. N & N i n149 S p a i n P U B L I C AT I O N S / S TAT I S T I C S
  • 150. P U B L I C AT I O N S / S TAT I S T I C S N & N i n150 S p a i n
  • 151. N & N i n151 S p a i n P U B L I C AT I O N S / S TAT I S T I C S
  • 152. Annex IV: Spain Nanotechnology Companies (Catalogue)152
  • 153. N & N i n S p a i n N A N O S C I E N C E & N A N O T E C H N O L O G Y I N S PA I NThe catalogue, compiled by the Phantoms Foundation The Phantoms Foundation is also coordinator of the(coordinator of the Spanish Nanotechnology action Spanish Nanotechnology Plan funded by ICEXplan funded by ICEX), and published in full version in (Spanish Institute for Foreign Trade, www.icex.es)the E-nano Newsletter (www.phantomsnet.net/ under the program España, Technology for Life, toResources/Catalogue_Companies.pdf) provides a enhance the promotion in foreign markets of Spain’sgeneral overview of the Nanoscience and more Innovative and leading industrial technologiesNanotechnology companies in Spain and in particular and products in order to:the importance of this market research, productdevelopment, etc. 1. Represent the Scientific, Technological andNote: only those contacted companies which provided Innovative agents of the country as a whole.their details are listed. 2. Foster relationships with other markets/countries. 3. Promote country culture of innovation. Edited and Coordinated by 4. Better integrate the Spanish “Science - Technology - Company - Society” system in other countries. 5. Generate and develop scientific and technological knowledge. 6. Improve competitiveness and contribute to theThe Phantoms Foundation based in Madrid, Spain, economic and social development of Spain.focuses its activities on Nanoscience andNanotechnology (N&N) and is now a key actor in Funded bystructuring and fostering European Excellence andenhancing collaborations in these fields. ThePhantoms Foundation, a non-profit organisation,gives high level management profile to National andEuropean scientific projects (among others, the COSTBio-Inspired nanotechnologies, ICT-FET IntegratedProject AtMol, ICT/FET nanoICT Coordination Action,EU/NMP nanomagma project, NanoCode projectunder the Programme Capacities, in the area Sciencein Society FP7…) and provides an innovative platformfor dissemination, transfer and transformation ofbasic nanoscience knowledge, strengthening The Spanish Institute for Foreign Trade ("Institutointerdisciplinary research in nanoscience and Español de Comercio Exterior”) is the Spanishnanotechnology and catalysing collaboration among Government agency serving Spanish companies tointernational research groups. promote their exports and facilitate their international expansion, assisted by the network of SpanishThe Foundation also works in close collaboration with Embassy’s Economic and Commercial Offices and,Spanish and European Governmental Institutions to within Spain, by the Regional and Territorial Offices.provide focused reports on N&N related research It is part of the Spanish Ministry of Industry, Tourismareas (infrastructure needs, emerging research, etc.). and Trade ("Ministerio de Industria, Turismo y Comercio").The NanoSpain Network (coordinated by thePhantoms Foundation and the Spanish NationalResearch Council, CSIC) scheme aims to promote Contact detailsSpanish science and research through a multi-nationalnetworking action and to stimulate commercial Phantoms FoundationNanotechnology applications. NanoSpain involves Calle Alfonso Gomez 17about 310 research groups and companies and more 28037 Madrid (Spain)than 2000 researchers. www.phantomsnet.net 153
  • 154. N A N O S C I E N C E & N A N O T E C H N O L O G Y I N S PA I N N & N i n154 S p a i n
  • 155. N & N i n155 S p a i n N A N O S C I E N C E & N A N O T E C H N O L O G Y I N S PA I N
  • 156. Annex V: NanoSpain Conferences156
  • 157. N & N i n S p a i nAnnex V: NanoSpain ConferencesAs a direct and most effective way to enhance the interaction between our network members, a firstnetwork meeting was organised in San Sebastián (March 10-12, 2004) with around 210 participants N A N O S PA I N C O N F E R E N C E Sregistered. Due to this success, the network decided organising its annual meeting, Barcelona(March 14-17,2005), Pamplona (March 20-23, 2006), Sevilla (March, 12-15, 2007), Braga-Portugal(April 14-18, 2008), Zaragoza (March 09-12, 2009) and Málaga (March 09-12, 2010) with a similarformat. Its objective was also to facilitate the dissemination of knowledge and promote interdisci-plinary discussions among the different NanoSpain groups. In order to organise the various sessionsand to select contributions, the meeting was structured in the following thematic lines, but inter-actions among them were promoted:1. Advanced Nanofabrication Methods2. NanoBiotechnology3. NanoMaterials4. NanoChemistry5. NanoElectronics / Molecular Electronics6. Scanning Probe Microscopies (SPM)7. Nanophotonic & Nanooptic8. Scientific infrastructures and Scientific Parks9. Simulation at the nanoscaleIn 2008, Spain, Portugal and France (through their respective networks NanoSpain, PortugalNanoand C’Nano GSO) decided to join efforts in order that NanoSpain events facilitate the disseminationof knowledge not only in Spain but among the different groups from Southern Europe.A list of all institutions involved in the organisation of the Nanospain conference series, is providedin the next table: 157
  • 158. N A N O S PA I N C O N F E R E N C E S N & N i n158 S p a i n
  • 159. N & N i n159 S p a i n N A N O S PA I N C O N F E R E N C E S
  • 160. Annex VI: Maps for relevant Spanish initiatives • Emerging N&N Centers in Spain. • Unique Research and Technology Infrastructures supporting nanotechnology research / ICTS. • Other initiatives (networks, platforms, regional programmes, conferences, etc.) related to nanotechnology promotion.160
  • 161. N & N i n S p a i n MAPS 161
  • 162. N & N i n S p a i nMAPS 162
  • 163. N & N i n S p a i n MAPS 163

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