ALDhistory tutorial in Kyoto ALD 2014

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

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

Atomic Layer Epitaxy
Finland

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

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

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

First ALE experiments with elemental Zn and S
First ALE patent applied November 29, 1974
Images by Suntola

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

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

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.

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

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.

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

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”

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.

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

 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.

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)

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)

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

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

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]

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

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

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

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)

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

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

Ritala, M.,
Leskelä, M.
Nalwa, H. S. (Ed.)
Atomic Layer
Deposition
Handbook of Thin
Film Materials,
Academic Press,
2002, 1, 103-159

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.”

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!

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

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

Links and sources
 Website of Virtual Project on the History of ALD (VPHA)
 Being built at http://baldengineering.com/vpha.html
 Contains (/will contain) links to all relevant VPHA material
 2005 review with notions on ALD history:
 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
 Contains e.g. links to presentations
 LinkedIn ALD History group:
https://www.linkedin.com/groups/ALD-History-5072051/about
 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

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

ALDhistory tutorial in Kyoto ALD 2014

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