Post on 26-Oct-2020
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 Puurunen, 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 Puurunen, ALD 2014 Kyoto, June 15, 2014, tutorial session
Atomic Layer Epitaxy Finland
4 Puurunen, 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 products Suntola invited to ”suggest and find out something” Suntola & small humidity team moved to Instrumentarium 1974
Suntola on Vaisala’s Youtube video
5 Puurunen, ALD 2014 Kyoto, June 15, 2014, tutorial session
Early 1974: market need/technology mapping study Sensor technologies diversified into small unities, which makes it
difficult to build a technology platform on such a 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!
6 Puurunen, ALD 2014 Kyoto, June 15, 2014, tutorial session
ZnS: quality of existing thin films insufficient
Electroluminescence requires controlled crystallinity Deposition (↓) not sufficient Growth (↑) needed
Epitaxy from Greek:
Epi taxis, on-arrangement
7 Puurunen, ALD 2014 Kyoto, June 15, 2014, tutorial session
First ALE experiments with elemental Zn and S
First ALE patent applied November 29, 1974
8 Puurunen, 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 Puurunen, 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 + S
Successful ZnCl2 + S
No success ZnCl2 + S + H2
No success ZnCl2 + H2S
”that’s it”!
ALE-EL development sold to Lohja Oy in 1978
2nd ALE patent, Feb 28, 1979
Sven Lindfors and a flow-reactor
10 Puurunen, 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 Puurunen, ALD 2014 Kyoto, June 15, 2014, tutorial session
International Conference on Vapor Growth and Epitaxy, 5 in San Diego, California
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 Puurunen, 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. Graeffe & display modules,
Helsinki-Vantaa airport underground cave, 1983.
13 Puurunen, 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
EL display image
14 Puurunen, ALD 2014 Kyoto, June 15, 2014, tutorial session
Microchemistry Ltd. in 1987
Founded by Suntola as a subsidiary of Neste 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 Puurunen, 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
Dr. 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.
Erja Nykänen Dr.?
16 Puurunen, 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 Puurunen, 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 Puurunen, ALD 2014 Kyoto, June 15, 2014, tutorial session
Molecular Layering Mолекулярное Hаслаивание USSR/Russia
Left: Corresponding member of the USSR Academy of Sciences (now the Russian Academy of Sciences) Professor Valentin Borisovich Aleskovskii ∗ 03.06.1912 † 29.01.2006 Right: Professor Stanislav Ivanovich Koltsov ∗ 30.08.1931 † 26.05.2003
19 Puurunen, ALD 2014 Kyoto, June 15, 2014, tutorial session
Aleskovskii 1952: Thesis for habilitation degree (doktor nauk) ”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 Puurunen, 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 Puurunen, 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 Puurunen, ALD 2014 Kyoto, June 15, 2014, tutorial session
ML thin films on planar substrates: TiO2, SiO2 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 Puurunen, 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] Secret thesis; secrecy requirements relaxed in 2013
24 Puurunen, 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) http://patentdb.su/2-422446-
sposob-polucheniya-okisnogo-crill-i-pv-sloya-na-poverkhnosti-kremnezela.html
25 Puurunen, ALD 2014 Kyoto, June 15, 2014, tutorial session
Drozd thesis 1978 – ”kandidat nauk” / PhD
Vacuum thin film reactor with programmable unit Capacitors 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 Puurunen, ALD 2014 Kyoto, June 15, 2014, tutorial session
Some other ML papers (there are many, many more)
Aleskovskii, V. B., Chemistry and technology of solids. J. Appl. Chem. USSR., 47, 2207-2217, 1974. Review. [in English and in Russian] 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 Puurunen, ALD 2014 Kyoto, June 15, 2014, tutorial session
Examples of applications using ML
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 Puurunen, 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 learned of ALE-1 in a Tallinn conference from Prof. Markus Pessa Prof. Niinistö helped Dr. Drozd in organizing the travelling
Proceedings: Aleskovskii, V. B. & Drozd, V. E. Acta Polytech.
Scand., Chem. Technol. Ser., 1990, 195, 155-161
29 Puurunen, 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
Get a better copy of the table
30 Puurunen, ALD 2014 Kyoto, June 15, 2014, tutorial session
Puurunen, J. Appl. Phys 97(2005) 121301 Summarizes Riikka’s ALD history activities as a 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 Puurunen, 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 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
Work on-going Everyone welcome to join!
32 Puurunen, ALD 2014 Kyoto, June 15, 2014, tutorial session
Conclusion: two independent roots of ALD
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 possible
ways of transformations in solids Partly secret in the beginning,
broad variety of publications Rich history in ALD, details
being unraveled in VPHA
33 Puurunen, 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, Riikka L. Puurunen, 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
Funding: Finnish Centre of Excellence in Atomic Layer Deposition
34 Puurunen, ALD 2014 Kyoto, June 15, 2014, tutorial session
Thank You!
Atomikerroskasvatus
שכבות אטומיות השקעתεναπόθεση ατομικού στρώματος
Atomlagenabscheidung
Parmanu Parat Nishepan
परमाणु परत �न�ेपण
Deposizione a Strati Atomici
原子層堆積
원자층증착
आिण्व 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
35 Puurunen, ALD 2014 Kyoto, June 15, 2014, tutorial session
Links
2005 review: J. Appl. Phys 97(2005) 121301 http://www.vtt.fi/inf/julkaisut/muut/2010/Puurunen.pdf Suntola ALD webpage: http://www.sci.fi/~suntola/ald.html Aldpulse.com: http://www.aldpulse.com/node/189 and
http://www.aldpulse.com/node/248: VPHA Open Introduction: http://www.slideshare.net/RiikkaPuurunen/ald-
historyproject-openintroductioncurrent VPHA poster abstract, Baltic ALD:
http://www.slideshare.net/RiikkaPuurunen/vpha-bald2014-finalsubmitted140202b LinkedIn ALD History group: https://www.linkedin.com/groups/ALD-History-
5072051/about “Tuomo Suntola’s Atomic Layer Epitaxy in Short” by Riikka Puurunen,
submitted (May 12) to Chem. Vap. Deposition
TECHNOLOGY FOR BUSINESS