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

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Two historical routes to film growth in alternating, saturating gas-solid reactions Atomic Layer Epitaxy Molecular Layering

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Atomic Layer Epitaxy Finland

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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

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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!

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ZnS: quality of existing thin films insufficient

Electroluminescence requires controlled crystallinity Deposition (↓) not sufficient Growth (↑) needed

Epitaxy from Greek:

Epi taxis, on-arrangement

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First ALE experiments with elemental Zn and S

First ALE patent applied November 29, 1974

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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.

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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

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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.

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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.

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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.

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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

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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”

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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.?

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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

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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.

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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

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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)

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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

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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

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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]

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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

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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

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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

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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)

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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

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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

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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

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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.”

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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!

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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

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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

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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

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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

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