ALDhistory tutorial in Kyoyo 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

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



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

http://www.vaisala.com/en/corporate/cases/Pages/humicapcelebratesits40years.aspx

http://www.youtube.com/watch?v=OuMZ8eisH64






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

confusedbut 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


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, 1979 Sven 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

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!

https://docs.google.com/document/d/1AlJg29dJM2if4SGzMJSSmwZskCNaAMQMO9LU6UYPios/








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

http://baldengineering.com/vpha.html



http://dx.doi.org/10.1063/1.1940727

http://dx.doi.org/10.1063/1.1940727

http://dx.doi.org/10.1063/1.1940727

http://dx.doi.org/10.1063/1.1940727

http://dx.doi.org/10.1063/1.1940727

http://dx.doi.org/10.1063/1.1940727




http://www.sci.fi/~suntola/ald.html

http://www.sci.fi/~suntola/ald.html









Thank You!

Atomikerroskasvatus

שכבות אטומיות השקעת

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

https://www.linkedin.com/groupItem?view=&gid=1885076&type=member&item=5843740056048644097&qid=43314a3d-3593-49b9-bf7b-06bce4c5ec50&trk=groups_most_popular-0-b-ttl&goback=.gna_1885076.gmr_1885076.gmp_1885076








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