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On the history and future of ALD: VPHA, conformality analysis, mechanisms

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Invited presentation at the HERALD COST MP1402 event in Riga (Riika), Latvia, May 22-23, 2017.
Topics:
1) History of atomic layer deposition (ALD)
2) Conformality analysis of ALD and other thin films
3) Surface chemistry questions in ALD

Presentation dedicated to the memory of Mr. Sven Lindfors, pioneer in building ALD reactors, close collaborator of Dr. Tuomo Suntola from 1975.

Published in: Science
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On the history and future of ALD: VPHA, conformality analysis, mechanisms

  1. 1. VTT TECHNICAL RESEARCH CENTRE OF FINLAND LTD On the history and future of ALD: VPHA, conformality analysis, mechanisms HERALD COST action workshop ALD nanotechnology: advances, prospects and applications May 22-23, 2017, Riika, Latvia Dr. (Prof.) Riikka Puurunen, VTT Technical Research Centre of Finland Aalto University, School of Chemical Engineering
  2. 2. 2 Puurunen, HERALD COST action event Riika, May 22, 2017 22/05/2017 2 Thank you for the invitation! Three topics: Virtual Project on the History of ALD  Baltic ALD 2016, St. Petersburg, http://www.bald2016.ru/  Slides: http://vph-ald.com/VPHApublications/VPHA-Puurunen- etal_FINAL_2016-10-03.pdf  Video record (partial) in Youtube: https://youtu.be/DIArUktQ8xs ALD conformality testing with microscopic lateral structures  On-going work at VTT, http://pillarhall.com  Presentations to come at EuroCVD-BalticALD 2017, ALD 2017, EuropaCat 2017, AVS64 Surface reaction mechanisms in ALD - open questions  ALD 2016, http://ald2016.com/  SlideShare: https://www.slideshare.net/RiikkaPuurunen/presentation-at-ald- 2016-by-puurunen-comparison-of-al2o3-chemistry-interpretations- final-20160723
  3. 3. 3 Puurunen, HERALD COST action event Riika, May 22, 2017 22/05/2017 3 Presentation dedicated to the memory of Mr. Sven Lindfors, 1945-2017  25.11.1945 Helsinki - 15.4.2017 Espoo  Pioneer of ALD reactors  Founder of Picosun Photo: Magnus Löfving FinALD40 exhibition Photo from 1978
  4. 4. 4 Puurunen, HERALD COST action event Riika, May 22, 2017 About Prof. Riikka Puurunen • LinkedIn: Riikka Puurunen, Twitter: @rlpuu, Aalto people • ORCID, Hirsch index: 22 (ISI Web of Science, May 21, 2017) • Working with ALD since 1998 • 1998, Microchemistry, Espoo, Finland (master’s thesis) • 1999-2002 Helsinki University of Technology / Fortum Oil and Gas (doctorate) • 2003-2004 IMEC, Leuven, Belgium • 2004-2017 VTT, Finland • 2017 Aalto University, Associate Prof. Catalysis Science & Technology • http://cmet.aalto.fi/icc, Twitter: @AaltoCatalysis • Part-time 40% at VTT Feb-Jul 2017 • Major ALD reviews: JAP 2005 (OA) JAP 2013 (OA), JVSTA 2017 (OA) • JAP 2005 & JAP 2013 contain the ”periodic table of ALD” • Coordinator of the Virtual Project on the History of ALD (2013-) Photo: Erkki Pöytäniemi
  5. 5. 5 Puurunen, HERALD COST action event Riika, May 22, 2017 22/05/2017 5 Photo by Kaupo Kukli On the history of ALD and the VPHA project Riikka L. Puurunen,1 Yury Koshtyal,2 Henrik Pedersen,3 J. Ruud van Ommen,4 Oksana Yurkevich,5 Jonas Sundqvist6 Baltic ALD 2016, St. Petersburg, October 2016 1 Link Full version in * vph-ald.com * Youtube (SlideShare to come)
  6. 6. Puurunen, Teaching demonstration, 11.12.2014, Aalto UniversityPuurunen et al. Baltic ALD 2016, 2016-10-03, St. Petersburg On the History of ALD and the VPHA project The 14th International Baltic Conference on Atomic Layer Deposition Riikka L. Puurunen,1 Yury Koshtyal,2 Henrik Pedersen,3 J. Ruud van Ommen,4 Oksana Yurkevich,5 Jonas Sundqvist6 1 VTT Technical Research Centre of Finland, Espoo, Finland 2 Ioffe Institute, St. Petersburg, Russia 3 Linköping University, Linköping, Sweden 4 Delft University of Technology, Delft, the Netherlands 5 Immanuel Kant Baltic Federal University, Kaliningrad, Russia 6 System Integration and Technology Transfer, Fraunhofer Institute for Ceramic Technologies and Systems IKTS, Dresden, Germany
  7. 7. Puurunen, Teaching demonstration, 11.12.2014, Aalto UniversityPuurunen et al. Baltic ALD 2016, 2016-10-03, St. Petersburg ALD cycle Reactant A Reactant B By-product Substrate before ALD Step 2 /4 purge Step 4 /4 purge Step 1 /4 Reactant A Step 3 /4 Reactant B Reactant A Reactant B By-product Adapted with permission from: Aarik et al., Thin Solid Films 340 (1999) 110. * saturating, irreversible chemisorption reactions * repeated Atomic Layer Deposition (ALD): a chemical gas-phase technique for thin film growth
  8. 8. Puurunen, Teaching demonstration, 11.12.2014, Aalto UniversityPuurunen et al. Baltic ALD 2016, 2016-10-03, St. Petersburg Source: review by Miikkulainen, Leskelä, Ritala, Puurunen, J. Appl. Phys. 113, 021301 (2013); >2000 references. http://dx.doi.org/10.1063/1.4757907 !Drozd Many classes of materials have been studied by ALD: oxides, nitrides, sulfides, metals, …
  9. 9. Puurunen, Teaching demonstration, 11.12.2014, Aalto UniversityPuurunen et al. Baltic ALD 2016, 2016-10-03, St. Petersburg • Atomic layer epitaxy (ALE), Finland, 1974  • Molecular layering (ML), Soviet Union, 1960s  • Молекулярное наслаивание (МН), transliterated as molekulyarnoye naslaivanie • Especially ML has remained poorly known and cited Virtual Project on the History of ALD (VPHA) 4 ALD discovered & developed independently under two names Goal of this presentation: summarize the of key achievements in VPHA 2013-2016
  10. 10. Puurunen, Teaching demonstration, 11.12.2014, Aalto UniversityPuurunen et al. Baltic ALD 2016, 2016-10-03, St. Petersburg 5 Web of Science, Sept. 30, 2016 Knez, Nielsch, Niinistö, Adv. Mat. 2007 • “Atomic layer deposition (ALD), originally called Atomic layer epitaxy (ALE), was developed in the 1970s by Suntola and Antson…” (Times cited: 426) George, Chemical Reviews 2010 • ”The history of ALE and ALD dates back to the 1970s in Finland.” (Times cited: 1340)
  11. 11. Puurunen, Teaching demonstration, 11.12.2014, Aalto UniversityPuurunen et al. Baltic ALD 2016, 2016-10-03, St. Petersburg 6 Puurunen, J. Appl. Phys. 2005 • “TABLE I. Some Soviet–Russian ALD investigations.” Ritala, M. & Leskelä, M. Nalwa, H. S. (Ed.) Atomic Layer Deposition Handbook of Thin Film Materials, Academic Press, 2002, 1, 103-159 Puurunen, Doctoral thesis, Helsinki University of Technology, 2002 ”Early work on Atomic Layer Deposition cited” Malygin, Smirnov, Solid State Technology, 2002, March, p. 14
  12. 12. Puurunen, Teaching demonstration, 11.12.2014, Aalto UniversityPuurunen et al. Baltic ALD 2016, 2016-10-03, St. Petersburg 7 Puurunen, J. Appl. Phys. 2005 • “According to the more commonly acknowledged origin, ALD was developed under the name “atomic layer epitaxy (ALE)” in Finland by Suntola and co- workers. “ • “The less commonly acknowledged origin of ALD dates back to … the Soviet Union … 1960s … group of Professor Aleskovskii.” (Times cited: 1017) Web of Science, Sept. 30, 2016 Knez, Nielsch, Niinistö, Adv. Mat. 2007 • “Atomic layer deposition (ALD), originally called Atomic layer epitaxy (ALE), was developed in the 1970s by Suntola and Antson…” (Times cited: 426) George, Chemical Reviews 2010 • ”The history of ALE and ALD dates back to the 1970s in Finland.” (Times cited: 1340)
  13. 13. Puurunen, Teaching demonstration, 11.12.2014, Aalto UniversityPuurunen et al. Baltic ALD 2016, 2016-10-03, St. Petersburg 8 LinkedIn ”ALD - Atomic Layer Deposition” group https://www.linkedin.com/groups/1885076/1885076-238399494 LinkedIn question May 6, 2013
  14. 14. Puurunen, Teaching demonstration, 11.12.2014, Aalto UniversityPuurunen et al. Baltic ALD 2016, 2016-10-03, St. Petersburg 9 Atomic layer deposition (ALD) has become a technique that, for its part, changes the world we live in. As for any significant technology, it is interesting and important to know where the technique came from. How was the concept developed? What were the first ALD experiments? When, where and by whom were they made? Why were they made? 1. First, we should generate a complete list of early ALD publications. 2. Second, interested individuals should pick up some of the early publications, read them, and comment on the work. For example: was ALD made (i.e., do you recognize the work as ALD), and if yes, which process it was; and other noteworthy things. 3. Third, the individual should share their comments with others, and the comments of different people should be collected together. Atmosphere of Openness, Respect, and Trust LinkedIn question May 6, 2013 VPHA opened July 25, 2013 + ALD 2013 San Diego http://vph-ald.com/Introduction%20and%20invitation%20to%20participate.html
  15. 15. Puurunen, Teaching demonstration, 11.12.2014, Aalto UniversityPuurunen et al. Baltic ALD 2016, 2016-10-03, St. Petersburg 10 ALD-history-evolving-file Early ALD literature up to 1986 Curretly: ~300 pages VPHA opened July 25, 2013 + ALD 2013 San Diego https://docs.google.com/document/d/1AlJg29dJM2if4SGzMJSSmwZskCNaAMQMO9LU6UYPios/
  16. 16. Puurunen, Teaching demonstration, 11.12.2014, Aalto UniversityPuurunen et al. Baltic ALD 2016, 2016-10-03, St. Petersburg 11 Announcement made by the conference chair Prof. Kim VPHA opened July 25, 2013 + ALD 2013 San Diego http://www2.avs.org/conferences/ALD/2013/index.html
  17. 17. Puurunen, Teaching demonstration, 11.12.2014, Aalto UniversityPuurunen et al. Baltic ALD 2016, 2016-10-03, St. Petersburg 12 Parsons, Elam, George, Haukka, Jeon, Kessels, Leskelä, Poodt, Ritala, Rossnagel, JVST A 2013 • “The ALD principle… was first published under name “molecular layering” in the early 1960s” • “A planar thin film was not produced or evaluated.” Published: 16.8.2013 (Times cited: 12) Puurunen, J. Appl. Phys. 2005 • “According to the more commonly acknowledged origin, ALD was developed under the name “atomic layer epitaxy (ALE)” in Finland by Suntola and co- workers. “ • “The less commonly acknowledged origin of ALD dates back to … the Soviet Union … 1960s … group of Professor Aleskovskii.” (Times cited: 1017) Web of Science, Sept. 30, 2016 Knez, Nielsch, Niinistö, Adv. Mat. 2007 • “Atomic layer deposition (ALD), originally called Atomic layer epitaxy (ALE), was developed in the 1970s by Suntola and Antson…” (Times cited: 426) George, Chemical Reviews 2010 • ”The history of ALE and ALD dates back to the 1970s in Finland.” (Times cited: 1340) VPHA opened July 25, 2013 + ALD 2013 San Diego
  18. 18. Puurunen, Teaching demonstration, 11.12.2014, Aalto UniversityPuurunen et al. Baltic ALD 2016, 2016-10-03, St. Petersburg 14 Malygin laboratory LinkedIn question May 6, 2013 Publication Plan October 18, 2013 (updated Jan 13, 2014 & April 5, 2015) VPHA opened July 25, 2013 + ALD 2013 San Diego Puurunen visit to St. Petersburg November 2013
  19. 19. Puurunen, Teaching demonstration, 11.12.2014, Aalto UniversityPuurunen et al. Baltic ALD 2016, 2016-10-03, St. Petersburg ”Suntola’s ALE essay” published Oct 15, 2014 & FinALD40 release 18 Times cited: 7 1978 Sven Lindfors & flow reactor Suntola Antson Lindfors Pakkala SID conf. 1981 Microchemistry's at the MRS 1994, Boston European SEMI Award to Suntola 2004 10.1002/cvde.201402012/full
  20. 20. Puurunen, Teaching demonstration, 11.12.2014, Aalto UniversityPuurunen et al. Baltic ALD 2016, 2016-10-03, St. Petersburg 21 http://www.ald-mipt.ru/ald-russia.html http://aldhistory.blogspot.fi/2015/11/ald-russia-2015-travel-report-Puurunen.html ALD Russia Moscow + Baltic ALD Tartu Sep-Oct 2015 George Puurunen, Malygin, Parsons ALD Russia 2015 group photo
  21. 21. Puurunen, Teaching demonstration, 11.12.2014, Aalto UniversityPuurunen et al. Baltic ALD 2016, 2016-10-03, St. Petersburg 23 LinkedIn question May 6, 2013 Publication Plan October 18, 2013 (updated Jan 13, 2014 & April 5, 2015) VPHA opened July 25, 2013 + ALD 2013 San Diego Puurunen visit to St. Petersburg November 2013 Baltic ALD 2014 Helsinki: VPHA poster + FinALD40 exhibition ALD 2014 Kyoto: history tutorial + two posters ALD Russia Moscow + Baltic ALD Tartu Sep-Oct 2015 “ML essay” published Dec 17, 2015 ”Suntola’s ALE essay” published Oct 15, 2014 & FinALD40 release 10.1002/cvde.201502013/abstract
  22. 22. Puurunen, Teaching demonstration, 11.12.2014, Aalto UniversityPuurunen et al. Baltic ALD 2016, 2016-10-03, St. Petersburg 24 Times cited: 0 “ML essay” published Dec 17, 2015 1973 ML group LTI by Lensovet 1977 Drozd’s reactor 1982 column flow unit ALE-4 Linz 1996: George, Suntola, Drozd, Niinistö, Leskelä 2004 conf. St Petersburg Aleskovskii, Malygin 10.1002/cvde.201502013/abstract
  23. 23. Puurunen, Teaching demonstration, 11.12.2014, Aalto UniversityPuurunen et al. Baltic ALD 2016, 2016-10-03, St. Petersburg 25 LinkedIn question May 6, 2013 Publication Plan October 18, 2013 (updated Jan 13, 2014 & April 5, 2015) VPHA opened July 25, 2013 + ALD 2013 San Diego Puurunen visit to St. Petersburg November 2013 Baltic ALD 2014 Helsinki: VPHA poster + FinALD40 exhibition ALD 2014 Kyoto: history tutorial + two posters ALD Russia Moscow + Baltic ALD Tartu Sep-Oct 2015 “ML essay” published Dec 17, 2015 ALD 2016 Dublin: Malygin invited talk + VPHA poster ”Suntola’s ALE essay” published Oct 15, 2014 & FinALD40 release Malygin Parsons http://vph-ald.com/UploadedPublications/Malygin-ALD2016-25July.pdf http://vph-ald.com/VPHApublications/VPHA-poster_July2016_FINAL_2016-07-19.pdf http://aldhistory.blogspot. fi/2016/07/ald-2016- travel-notes.html
  24. 24. Puurunen, Teaching demonstration, 11.12.2014, Aalto UniversityPuurunen et al. Baltic ALD 2016, 2016-10-03, St. Petersburg 26 LinkedIn question May 6, 2013 Publication Plan October 18, 2013 (updated Jan 13, 2014 & April 5, 2015) VPHA opened July 25, 2013 + ALD 2013 San Diego Puurunen visit to St. Petersburg November 2013 Baltic ALD 2014 Helsinki: VPHA poster + FinALD40 exhibition ALD 2014 Kyoto: history tutorial + two posters ALD Russia Moscow + Baltic ALD Tartu Sep-Oct 2015 “ML essay” published Dec 17, 2015 ALD 2016 Dublin: Malygin invited talk + VPHA poster VPHA manuscript + Baltic ALD 2016 St. Petersburg ”Suntola’s ALE essay” published Oct 15, 2014 & FinALD40 release 62 authors, submitted Oct 30, 2016 http://aldhistory.blogspot.fi/search/label/JVSTA Darker grey  more VPHA contributors
  25. 25. 6 Puurunen, HERALD COST action event Riika, May 22, 2017 22/05/2017 6 VPHA article published in the special ALD issue  Journal of Vacuum Science & Technology A: Vacuum, Surfaces, and Films 35, 010801 (2017); doi: http://dx.doi.org/10.1116/1.4971389  62 authors (alphabetical order)  Was featured and most read for several months (now 2nd)  VPHA reading is still open & we are collecting info on ALD theses, reviews & conferences worldwide. Contact: info@vph-ald.com  Add info through http://vph-ald.com/VPHAopenfiles.html
  26. 26. 7 Puurunen, HERALD COST action event Riika, May 22, 2017 22/05/2017 7 ALD conformality testing with microscopic lateral structures Lateral structures being developed at VTT  http://pillarhall.com  Twitter: #TestedWithPillarHall 2
  27. 27. 8 Puurunen, HERALD COST action event Riika, May 22, 2017 22/05/2017 8
  28. 28. 9 Puurunen, HERALD COST action event Riika, May 22, 2017 22/05/2017 9
  29. 29. 10 Puurunen, HERALD COST action event Riika, May 22, 2017 22/05/2017 10 VTT’s approach: all-silicon microscopic lateral high-aspect-ratio structures – PillarHall® Proto3 15 mm 20mm l Si (side view) l g = Gao et al., J. Vac. Sci. Technol. A 33 (2015) 010601; Mattinen et al., Langmuir 32 (2016) 10559; Puurunen, Gao, IEEE Xplore, http://ieeexplore.ieee.org/document/7886526/ . Opening w AR 2 : 1 … 10 000 : 1 (small to ”infinite”) = 1 to 5000 µm 200 to 1000 nm PillarHall(R)
  30. 30. 11 Puurunen, HERALD COST action event Riika, May 22, 2017 22/05/2017 11 PillarHall®: Multitude of analysis possibilities Penetration depth under membrane ~70 µm AR ~140:1 Cross-section, SEM (50 nm by ALD) For scientific publications, see DOI 10.1116/1.4903941; DOI acs.langmuir.6b03007 More info to come in conference talks: Puurunen et al., EuroCVD 2017 & ALD 2017 Top-view microscopy (50 nm by ALD) Quick semiquantitative (nondestructive) analysis Traditional electron microscopy cross-sections Uniform coating all around the feature, AR ~40:1, gap height 500 nm
  31. 31. 12 Puurunen, HERALD COST action event Riika, May 22, 2017 22/05/2017 12 PillarHall®: Remove top membrane to access detailed, reproducible information of film on Si Photo: Riikka Puurunen, VTT Distance from LHAR opening (µm) Reflectometry Al2O3 ALD For scientific publications, see: DOI 10.1116/1.4903941; DOI acs.langmuir.6b03007 More info to come in conference talks: Puurunen et al., EuroCVD 2017 & ALD 2017
  32. 32. 13 Puurunen, HERALD COST action event Riika, May 22, 2017 22/05/2017 13 distance, aspect ratio thickness • Optimise reaction times/doses (tA, tB, pA, pB) • Extract kinetic parameters • Optimise purge times (tA2, tB2) • Understand reaction mechanisms PillarHall® line scans: route to understanding and optimising process fundamentals
  33. 33. 14 Puurunen, HERALD COST action event Riika, May 22, 2017 22/05/2017 14 Modelling outcome example (not published, not final) made by Markku Ylilammi/VTT • Sticking coefficient 0.0108 • Equilibrium constant 51.3 Pa-1 • TMA partial pressure at inlet 93.4 Pa (Manuscript preparation on-going)
  34. 34. 15 Puurunen, HERALD COST action event Riika, May 22, 2017 22/05/2017 15 Imagine what all can be done with the chips!  How uniform are the films actually inside the 3D structure?  Composition?  Morphology?  Electrical properties?  …  What is the highest aspect ratio one can coat?  What methods can be used for non-destructive analysis?  What methods can be used for line scans & extracting kinetic information?  How will our understanding of ALD reactions evolve through exposing a new parameter space for investigation? ”?!
  35. 35. 16 Puurunen, HERALD COST action event Riika, May 22, 2017 22/05/2017 16 Imagine what all can be done with the chips!  How uniform are the films actually inside the 3D structure?  Composition?  Morphology?  Electrical properties?  …  What is the highest aspect ratio one can coat?  What methods can be used for non-destructive analysis?  What methods can be used for line scans & extracting kinetic information?  How will our understanding of ALD reactions evolve through exposing a new parameter space for investigation? ”?!
  36. 36. 17 Puurunen, HERALD COST action event Riika, May 22, 2017 22/05/2017 17 More test users for PillarHall chips welcome - prototype development ongoing  Academic partners welcome: goal is joint publications  Conditions in Materials Transfer Agreement (MTA)  To get an idea, grab a prototype brochure  Or: have a look at the PillarHall demo – it is always with me!  Email: pillarhall@vtt.fi  Website: http://pillarhall.com
  37. 37. 18 Puurunen, HERALD COST action event Riika, May 22, 2017 22/05/2017 18 Part 2: conformality analysis (with lateral structures) 3 Link * Full version in SlideShare
  38. 38. VTT TECHNICAL RESEARCH CENTRE OF FINLAND LTD Comparison of interpretations on the surface chemistry of the Me3Al-H2O ALD process ALD 2016 Ireland, July 2016 Riikka L. Puurunen VTT Technical Reseach Centre of Finland, Ltd.
  39. 39. 2R. L. Puurunen, ALD 2016, July 26, 2016 From: Puurunen, EuroCVD 2007 (in SlideShare)
  40. 40. 3R. L. Puurunen, ALD 2016, July 26, 2016 Me3Al/H2O – has evolved to The Model System  Puurunen, 2005, J. Appl. Phys. Me3Al/H2O surface chemistry critically reviewed & discussed  George, 2010, Chem. Rev. ” The ALD of Al2O3 has developed as a model ALD system. An earlier extensive review by Puurunen … [Puurunen2005]”  Knapas & Ritala, 2013, Crit. Rev. Solid State Mater. Sci. ”The AlMe3 (TMA) – H2O process … the most studied ALD system, and has also been adopted as a model system for ALD [George2010].”  Weckman & Laasonen, 2015, Phys. Chem. Chem. Phys. ” … the TMA/H2O system is considered as a model process for ALD [George2010, Puurunen2005]” 995 1287 26 Cited WoS 20.7.2016 2
  41. 41. 4R. L. Puurunen, ALD 2016, July 26, 2016  Puurunen, 2005, J. Appl. Phys. Me3Al/H2O surface chemistry critically reviewed & discussed  George, 2010: Chem. Rev. ” The ALD of Al2O3 has developed as a model ALD system. An earlier extensive review by Puurunen … [Puurunen2005]”  Knapas & Ritala, 2013, Crit. Rev. Solid State Mater. Sci. ”The AlMe3 (TMA) – H2O process … the most studied ALD system, and has also been adopted as a model system for ALD [George2010].”  Weckman & Laasonen, 2015, Phys. Chem. Chem. Phys. ” … the TMA/H2O system is considered as a model process for ALD [George2010, Puurunen2005]” Me3Al/H2O – The Model System Let us treat the Me3Al/H2O process with the critical eye that the model system deserves
  42. 42. 5R. L. Puurunen, ALD 2016, July 26, 2016 Some fundamental questions related to ALD  How does the GPC vary with temperature?  What is the ALD window of a given process?  What defines the Growth Per Cycle (GPC)?   What is the limiting factor that causes saturation?  Which surface reaction mechanisms take place?  How fast are they? Postulate: different works explain the variation in GPC in significantly different ways [Puurunen2005] [George2010] [Knapas2013]
  43. 43. 7R. L. Puurunen, ALD 2016, July 26, 2016 [Puurunen2005]  Puurunen et al., J. Phys. Chem. B 104 (2000) 6599  Puurunen et al., Phys. Chem. Chem. Phys., 3 (2001) 1093 From: Puurunen, EuroCVD 2007 (in SlideShare) [Me] Ccontent Alcontent
  44. 44. 8R. L. Puurunen, ALD 2016, July 26, 2016 [Puurunen2005] Fitting reference: Puurunen, Appl. Surf. Sci. 245 (2005) 6-10  Quantitative explanation of GPC vs temperature via loss of [OH] and ~constant [Me] From: Puurunen, EuroCVD 2007 (in SlideShare)
  45. 45. 13R. L. Puurunen, ALD 2016, July 26, 2016 Conclusion, The Model System Source Puurunen, 2005 George, 2010 Knapas & Ritala, 2013 Explaination of less-than- monolayer GPC & temp. trend Quantitative Qualitative - Description of GPC change with temperature Decreases with * decreasing [OH], * [Me] ~constant Decreases with * decreasing [OH], * decreasing [Me] (* n/z about constant at 1.5) Background data, Change of surface [Me] vs temperature [Me] [Me] [Me]
  46. 46. 14R. L. Puurunen, ALD 2016, July 26, 2016 Conclusion Source Puurunen, 2005 George, 2010 Knapas & Ritala, 2013 Explaination of less-than- monolayer GPC & temp. trend Quantitative Qualitative - Description of GPC change with temperature Decreases with * decreasing [OH], * [Me] ~constant Decreases with * decreasing [OH], * decreasing [Me] * n/z about constant at 1.5 Change of surface [Me] vs temperature in ”background data” [Me] [Me] [Me] • Significant differences, which have remained unnoticed so far? • Me3Al/H2O is model system  scientific discussion & agreement on the basic trends needed • New research activity welcome!
  47. 47. 19 Puurunen, HERALD COST action event Riika, May 22, 2017 22/05/2017 19 Conclusion --- by Riikka, in Riika  (1/2) The view on ALD’s history is changing  Facts need to be right. Virtual Project on the History of ALD still welcomes new volunteers  info@vph-ald.com  No single full balanced historical review of ALD exists currently. Good combination: (1) ALE and (3) ML essays together, topped up with (3) the JVSTA 2017 review. PillarHall conformality test structure development  Interested in scientific/industrial POC studies?  Please contact us (pillarhall@vtt.fi) Room for scientific studies on surface chemistry of ALD  Many ALD processes are used in industry, without understanding the fundamental surface reaction chemistry
  48. 48. 20 Puurunen, HERALD COST action event Riika, May 22, 2017 22/05/2017 20 Conclusion (1/2)  Could ALD and Tuomo Suntola get the Millennium Technology Prize 2018?  Let us propose it! DL end Jul  Riikka) will write proposal & get CV  Support letters from all over the world are welcome and needed!  Those wishing to support: please send your letter either to riikka.puurunen (at) aalto.fi, or  Directly to Technology Academy Finland (TAF) Example support letter:
  49. 49. 21 Puurunen, HERALD COST action event Riika, May 22, 2017 22/05/2017 21 Thank you, questions? Atomikerroskasvatus ‫השקעת‬ ‫אטומיות‬ ‫שכבות‬ εναπόθεση ατομικού στρώματος Atomlagenabscheidung Parmanu Parat Nishepan परमाणु परत निक्षेपण Deposizione a Strati Atomici 原子層堆積 원자층증착 आण्विक थर लेप Atomlagsdeponering атомно-слоевое осаждение Dépôt de Couches Atomiques Dépôt Chimique en Phase Vapeur à Flux Alternés Atomlagerdeponering Atomik Katman Biriktirme Oсадження атомних шарів Aatomkihtsadestus Depositación de Capas Atómicas Atomic Layer Deposition Atoomlaagdepositie 原子层沉积 Deposição por Camadas Atômicas ALD name collection in LinkedIn ALD – Atomic Layer Deposition Mолекулярное Hаслаивание
  50. 50. TECHNOLOGY FOR BUSINESS

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