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ALDhistory tutorial in Kyoto ALD 2014



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ALDhistory tutorial in Kyoto ALD 2014

  1. 1. History of Atomic Layer Deposition Tutorial at 14th International Conference on Atomic Layer Deposition (AVS-ALD 2014, Kyoto, Japan) Dr. Riikka Puurunen VTT Technical Research Centre of Finland
  2. 2. 2Puurunen, ALD 2014 Kyoto, June 15, 2014, tutorial session Two historical routes to film growth in alternating, saturating gas-solid reactions Atomic Layer Epitaxy Molecular Layering
  3. 3. 3Puurunen, ALD 2014 Kyoto, June 15, 2014, tutorial session Atomic Layer Epitaxy Finland
  4. 4. 4Puurunen, ALD 2014 Kyoto, June 15, 2014, tutorial session Background of the invention of Atomic Layer Epitaxy (ALE)  Humidity sensor by Suntola/VTT to Vaisala  Demonstrator 1973  40 years HUMICAP® in 2013  Company Instrumentarium looking for new products  Suntola invited to ”suggest and find out something”  Suntola with small humidity team moved to Instrumentarium 1974 Suntola on Vaisala’s Youtube video
  5. 5. 5Puurunen, ALD 2014 Kyoto, June 15, 2014, tutorial session Early 1974: market need/technology mapping study  Sensor technologies diversified into small unities, difficult to build a technology platform on such basis  However: a display, preferably small, is needed in most instruments Suntola’s proposed to work on:  ion-selective sensors  flat panel displays “I am still confusedbut at a higher level.” Let’s go ahead! Let’s develop an electroluminescent flat panel display …nobody has done it yet
  6. 6. 6Puurunen, ALD 2014 Kyoto, June 15, 2014, tutorial session ZnS: quality of existing thin films insufficient  Electroluminescence requires controlled crystallinity  Deposition () not sufficient  Growth () needed  Atomic Layer Epitaxy  Epitaxy from Greek: Epi taxis, on-arrangement
  7. 7. 7Puurunen, ALD 2014 Kyoto, June 15, 2014, tutorial session First ALE experiments with elemental Zn and S First ALE patent applied November 29, 1974 Images by Suntola
  8. 8. 8Puurunen, ALD 2014 Kyoto, June 15, 2014, tutorial session ALE patent granted in 26 countries  In prior art study, closest found a German patent from mid-50s  saturation was missing from this patent  Hearings related to the patent were organized in several countries, including The United States, Japan, and The Soviet Union
  9. 9. 9Puurunen, ALD 2014 Kyoto, June 15, 2014, tutorial session Switch to flow reactor & compound reactants, EL demo  High-vacuum-system would not be production worthy  towards flow apparatus and exchange reactions  Zn + Sx  Successful  ZnCl2 + Sx  No success  ZnCl2 + Sx + H2  No success  ZnCl2 + H2S ”That’s it”! (by Pakkala) ALE-EL development sold to Lohja Oy in 1978 2nd ALE patent, Feb 28, 1979Sven Lindfors and a flow-reactor
  10. 10. 10Puurunen, ALD 2014 Kyoto, June 15, 2014, tutorial session SID conference 1980: first publication & demo Society for Information Display (SID), San Diego, California, April 29 to May 1, 1980  Revolutionary EL display  3000-4000 product requests Suntola, 2014:  “we had neither the production line constructed nor the product developed”  “What a tragedy, wasted marketing”  demand for flat panel displays confirmed 1980 SID Outstanding Paper Award for the EL work – Suntola, Antson, Lindfors, Pakkala, given in SID 1981.
  11. 11. 11Puurunen, ALD 2014 Kyoto, June 15, 2014, tutorial session International Conference on Vapor Growth and Epitaxy, 5 in San Diego, California  Suntola invited talk on Atomic Layer Epitaxy  Little scientific information available on the ALE grown material  Use of the term “epitaxy” for non-single-crystal thin films was criticized  Prof Jun-ichi Nishizawa from Japan was among the participants, realized the significance of ALE  initiation of GaAs research in Japan (“Molecular Layer Epitaxy”)  Nishizawa, MLE-GaAs in the 16th, (1984 International) Conference on Solid State Devices and Materials, in Kobe, Japan, 1984
  12. 12. 12Puurunen, ALD 2014 Kyoto, June 15, 2014, tutorial session ALE-EL pilot production in Lohja, Kunnarla  First real test: Helsinki- Vantaa airport information flight display boards, 1983  Al2O3-TiO2 nanolaminate (”ATO”) chosen as the dielectric  15 years in continuous use, without a single character module replaced Dr. Ralf Graeffe & display board test assembly, Helsinki-Vantaa airport underground cave, 1983.
  13. 13. 13Puurunen, ALD 2014 Kyoto, June 15, 2014, tutorial session Production facilities built in Espoo 1983-1984  Production started gradually in 1985. Bought by Planar in 1990.  EL-production continues, operated by Beneq Oy since 2012 Photo: Tuomo Suntola ALE-EL licenced to France, in 1983, 500 x 500 mm2 substrates
  14. 14. 14Puurunen, ALD 2014 Kyoto, June 15, 2014, tutorial session Microchemistry Ltd. in 1987 Founded by Suntola as a subsidiary of Neste Corporation  ALE-based solar panels  ALE to heterogeneous catalyst • F-120 reactor developed for own use became the 1st commercial ALD reactor • “Catalyst work brought highly desired chemistry expertise into Microchemistry”
  15. 15. 15Puurunen, ALD 2014 Kyoto, June 15, 2014, tutorial session ALE-1 conference, Prof. Niinistö, Espoo/Helsinki The first International Symposium on Atomic Layer Epitaxy, June 11-13, 1990 Ms. Erja Nykänen, Helsinki University of Technology (HUT); Prof. Konagai, Tokyo Institute of Technology; Dr. Tuomo Suntola, Microchemistry Ltd.; Prof. Niinistö, HUT; Prof. Nishizawa, Semiconductor Laboratory, Sendai; Prof. Bedair, North Carolina University.
  16. 16. 16Puurunen, ALD 2014 Kyoto, June 15, 2014, tutorial session MRS 1994 Annual Meeting in Boston First-ever exhibition booth of ALE  Suntola invited talk: ALE for Semiconductor Applications   interest in ALE from semiconductor industry and equipment manufacturers
  17. 17. 17Puurunen, ALD 2014 Kyoto, June 15, 2014, tutorial session  1998, Suntola left behind the active role in ALE (ALD)  2004 The European SEMI Award “Honoring the Pioneer in Atomic Layer Deposition Techniques ... that paved the way for the development of nanoscale semiconductor devices“  2014: Suntola continues as a board member of Picosun Oy, the chairman of the Physics Foundations Society and a board member and a frequent lecturer in the Finnish Society for Natural Philosophy.
  18. 18. 18Puurunen, ALD 2014 Kyoto, June 15, 2014, tutorial session Molecular Layering Mолекулярное Hаслаивание USSR/Russia Professor Valentin Borisovich Aleskovskii ∗ 03.06.1912 † 29.01.2006 Professor Stanislav Ivanovich Koltsov ∗ 30.08.1931 † 26.05.2003 Rector x 2 Corresponding member of the USSR Academy of Sciences (now the Russian Academy of Sciences)
  19. 19. 19Puurunen, ALD 2014 Kyoto, June 15, 2014, tutorial session Aleskovskii 1952: Thesis for habilitation degree (doktor nauk, ”2nd thesis”)  ”Matrix hypothesis and way of synthesis of some active solid compounds”,  Leningrad Lensoviet Institute of Technology  The matrix hypothesis (or skeleton hypothesis) enabled two basic ways of transforming a solid to another: (1) substituting atoms in the skeleton and (2) reactions of functional groups.  Later, further work on (1) led to Destruction-Epitaxial Transformations method (A.P. Dushina) and on (2) to Molecular Layering (S. I. Koltsov, 1971)
  20. 20. 20Puurunen, ALD 2014 Kyoto, June 15, 2014, tutorial session Scientific and Technical Conference, Leningrad abstract books available, Publisher: Gozkhimiizdat 1963: Koltsov: Synthesis of multilayered inorganic polymers April 1965: Aleskovskii, Koltsov: Some characteristics of molecular layering reactions
  21. 21. 21Puurunen, ALD 2014 Kyoto, June 15, 2014, tutorial session 2nd USSR conference on high temperature chemistry of oxides, November 26-29, 1965, Leningrad, USSR  Shevjakov, A. M.; Kuznetsova, G. N. and Aleskovskii, V. B.: Interaction of titanium and germanium tetrachlorides with hydrated silica.  10 cycles TiCl4/H2O  Later, Koltsov: Preparation and investigation of the products of interaction between titanium tetrachloride and silica gel. J. Appl. Chem. USSR. 42, 975-979 1969
  22. 22. 22Puurunen, ALD 2014 Kyoto, June 15, 2014, tutorial session ML thin films on planar substrates: TiO2 and SiO2 on Si published in 1970 Sveshnikova, G. S., Kol'tsov, S. I. & Aleskovskii, V. B. Interaction of titanium tetrachloride with hydroxylated silicon surfaces J. Appl. Chem. USSR., 43, 432- 434, 1970 [in English and in Russian] Sveshnikova, G. V.; Kol'tsov, S. I. & Aleskovskii, V. B. Formation of a silicon oxide layer of predetermined thickness on silicon by the molecular layering method. J. Appl. Chem. USSR, 43, 1155-1157, 1970 [in English and Russian]
  23. 23. 23Puurunen, ALD 2014 Kyoto, June 15, 2014, tutorial session Koltsov 1971: ”The ML Thesis”  Kol’tsov, S. I. Synthesis of solids by the Molecular Layering Method, Doktor nauk thesis, Lensovet Leningrad Technological Institute, 1971, 383 p. [In Russian]  Secrecy requirements relaxed in 2013
  24. 24. 24Puurunen, ALD 2014 Kyoto, June 15, 2014, tutorial session Author’s certificates in 1972, catalyst preparation  A.N. Volkova, A.A. Malygin, S.I. Kol’tsov, V.B. Aleskovskii: The method of synthesis of Cr(III) and P(V) oxide layers on the silicagel surface (for catalytic dehydrogenation, dehydrocyclization and other reactions)  sposob-polucheniya-okisnogo-crill- i-pv-sloya-na-poverkhnosti- kremnezela.html
  25. 25. 25Puurunen, ALD 2014 Kyoto, June 15, 2014, tutorial session Drozd thesis 1978 – ”kandidat nauk” / PhD  Vacuum thin film reactor with programmable unit  Diodes with ML dielectrics, electrical characterization Cr2O3 V2O5 TiO2 HfO2 ZrO2 Ta2O5 WO3 Nb2O5 MoO2 Oxide layer composition Layer thickness Barrier height Barrier height Si-Me
  26. 26. 26Puurunen, ALD 2014 Kyoto, June 15, 2014, tutorial session Some other ML papers (there are many, many more  see the Kyoto VPHA posters #3, #4)  Aleskovskii, V. B., Chemistry and technology of solids. J. Appl. Chem. USSR., 47, 2207-2217, 1974. [in English and in Russian] (review)  Yakovlev, S. V.; Malygin, A. A.; Kol'tsov, S. I.; Aleskovskii, V. B.; Chesnokov, Yu. G. & Protod'yakonov, I. O. Mathematical model of molecular layering with the aid of a fluidizided bed, J. Appl. Chem. USSR, 52, 959-963, 1979. [in English and in Russian]  Tolmachev, V. A. Possibility of the use of a gravimetric method for studying the process of molecular layering in disperse silica samples. J. Appl. Chem. USSR., 55(6), 1298-1299, 1982. [in English and in Russian] (in situ)  V. D. Ivin, R. M. Levit, A. A. Malkov, E. P. Smirnov. Interaction of methane with the chlorinated surface of carbon fibers. J. Appl. Chem. USSR. 1985, V. 58, № 3, P. 592-595. [in English and in Russian] (growth of carbon)
  27. 27. 27Puurunen, ALD 2014 Kyoto, June 15, 2014, tutorial session Examples of applications using ML (more info poster #3) Adsorbents to stabilize the device’s internal environment during storage and operation Ceramics for X-ray tubes, ML to decrease sintering temperature Source: Prof Malygin’s Aleskovskii 100-year presentation
  28. 28. 28Puurunen, ALD 2014 Kyoto, June 15, 2014, tutorial session ALE-1 conference, June 11-13, 1990 The first International Symposium on Atomic Layer Epitaxy, Espoo/Helsinki  Dr. Drozd attended  Proceedings: Aleskovskii, V. B. & Drozd, V. E. Acta Polytech. Scand., Chem. Technol. Ser., 1990, 195, 155-161
  29. 29. 29Puurunen, ALD 2014 Kyoto, June 15, 2014, tutorial session Ritala, M., Leskelä, M. Nalwa, H. S. (Ed.) Atomic Layer Deposition Handbook of Thin Film Materials, Academic Press, 2002, 1, 103-159
  30. 30. 30Puurunen, ALD 2014 Kyoto, June 15, 2014, tutorial session Puurunen, J. Appl. Phys 97(2005) 121301 Riikka’s ALD history activities as postdoc at IMEC ”.. Most of the publications referred to in Table I have been published in Soviet– Russian journals, which have been translated into English. The overview of Table I is meant to be introductory, and it can by no means be expected to be complete.”
  31. 31. 31Puurunen, ALD 2014 Kyoto, June 15, 2014, tutorial session Virtual Project on the History of ALD (VPHA)  VPHA set up to clarify open questions on the history of ALD  Carried out in atmosphere of Openness, Respect, Trust  Collect & read ALD literature until 1986.  Common literature list collected in the publicly accessible ALD- history-evolving-file  VPHA open since: July 25, 2013, announced at ALD 2013  First publication: poster at Baltic ALD, May 12-13, Helsinki  At this AVS-ALD 2014 conference in Kyoto: two posters (#3, #4) Work on-going Everyone welcome to join!
  32. 32. 32Puurunen, ALD 2014 Kyoto, June 15, 2014, tutorial session Conclusion: two independent roots of ALD (Riikka’s own current personal view) Atomic Layer Epitaxy (ALE)  Initiated in industry,  originally for EL displays,  by people with semiconductor physics background  Directed to industrial use of the ALD  Very secret in the beginning, only patent publications  Commercial reactors triggered worldwide ALD activity in 1990s Molecular Layering (ML)  Initiated in academia,  for broad goals,  by people with chemistry background  Key: understanding ways of modifying solids  Partly secret in the beginning, broad variety of publications  Rich history in ALD, details being unraveled in VPHA
  33. 33. 33Puurunen, ALD 2014 Kyoto, June 15, 2014, tutorial session Acknowledgements  Finnish history: Dr. Tuomo Suntola  USSR/Russian history: Prof. Anatoly Malygin & Prof. Victor Drozd  VPHA co-leadership: Dr. Jonas Sundqvist  VPHA: Jaan Aarik, Andrew R. Akbashev, Mikhael Bechelany, Maria Berdova, David Cameron, Nikolai Chekurov, Victor E. Drozd, Simon D. Elliott, Gloria Gottardi, Kestutis Grigoras, Marcel Junige, Tanja Kallio, Jaana Kanervo, Yury Koshtyal, Marja-Leena Kääriäinen, Tommi Kääriäinen, Luca Lamagna, Anatoly Malkov, Anatoly Malygin, Jyrki Molarius, Cagla Ozgit-Akgun, Henrik Pedersen, Alexander Pyymäki Perros, Robin H. A. Ras, Fred Roozeboom, Timo Sajavaara, Hele Savin, Thomas E. Seidel, Pia Sundberg, Jonas Sundqvist, Massimo Tallarida, J. Ruud van Ommen, Thomas Wächtler, Claudia Wiemer, Oili M. E. Ylivaara. Aziz Abdulagatov, Annina Titoff  Partly funded by the Academy of Finland’s Finnish Centre of Excellence in Atomic Layer Deposition
  34. 34. 34Puurunen, ALD 2014 Kyoto, June 15, 2014, tutorial session Links and sources  Website of Virtual Project on the History of ALD (VPHA)  Being built at  Contains (/will contain) links to all relevant VPHA material  2005 review with notions on ALD history:  J. Appl. Phys 97(2005) 121301   Suntola ALD webpage:  Contains e.g. links to presentations  LinkedIn ALD History group:  Exhibition: 40 Years of ALD in Finland – Photos, Stories  In Espoo/Helsinki, traveled to ALD 2014 in Kyoto  “Tuomo Suntola’s Atomic Layer Epitaxy in Short” by Riikka Puurunen, submitted (May 12, 2014) to Chem. Vap. Deposition
  35. 35. 35Puurunen, ALD 2014 Kyoto, June 15, 2014, tutorial session Thank You! 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