Invited seminar talk by R. L. Puurunen, November 15, 2013, Beneq and ETU (LETI) joint ALD laboratory opening seminar, St. Petersburg, Russia, title: History of ALD: from lab research to industrial applications

1. History of ALD: from lab research to industrial applications
Beneq and ETU joint ALD laboratory opening seminar 15.11.2013 Riikka Puurunen (Dr.), Senior Scientist VTT Technical Research Centre of Finland

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Riikka Puurunen, VTT, 15.11.2013
Outline
1.
Very briefly about ALD (-ML)
2.
Suntola’s invention: from lab to production and beyond
3.
Aleskovskii, Kol’tsov and the Virtual project on the history of ALD
4.
Conclusion

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Riikka Puurunen, VTT, 15.11.2013
ALD: a chemical gas-phase technique for growing conformal (inorganic) material layers on solid substrates
ALD cycle Substratebefore ALDStep 2 /4purgeStep 4 /4purgeStep 1 /4 Reactant AStep 3 /4Reactant B Reactant AReactant BBy-product
From: Aarik et al., Thin Solid Films 340 (1999) 110, adapted with permission
saturating, irreversible chemisorption reactions

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Riikka Puurunen, VTT, 15.11.2013
ALD, atomic layer deposition АСО, атомно-слоевое осаждение ≡ ML, molecular layering, МН, молекулярное наслаивание

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Riikka Puurunen, VTT, 15.11.2013
Many classes of materials have been studied by ALD: oxides, nitrides, sulfides, metals, …
Source: review by Miikkulainen, Leskelä, Ritala, Puurunen, J. Appl. Phys. 113, 021301 (2013); http://dx.doi.org/10.1063/1.4757907 with >2000 references

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Riikka Puurunen, VTT, 15.11.2013
Many classes of materials have been studied by ALD: oxides, nitrides, sulfides, metals, …
Source: review by Miikkulainen, Leskelä, Ritala, Puurunen, J. Appl. Phys. 113, 021301 (2013); http://dx.doi.org/10.1063/1.4757907 with >2000 references
!
Drozd

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Riikka Puurunen, VTT, 15.11.2013
TFEL displays - start
Used with permission from Tuomo Suntola
0.4 μm grown in 30 min from elements Zn and S

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Riikka Puurunen, VTT, 15.11.2013
FIN 52359, US 4 058 430, …M ethod for producing compound thin fims
ALE Patent

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Riikka Puurunen, VTT, 15.11.2013
TFEL displays - structure
 Production since ~1985
Used with permission from Tuomo Suntola
ZnS(Mn) from ZnCl2, H2S (MnCl2)
ATO from AlCl3, TiCl4, H2O

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Riikka Puurunen, VTT, 15.11.2013
Used with permission from Jonas Sundqvist
Metal-oxide-semiconductor field effect transistors (MOSFET) Dynamic random access memories (DRAM)
DRAM 2004
MOSFET
2007

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Riikka Puurunen, VTT, 15.11.2013
Thin film ALD reactor technology: key to industrial success
Solved for the TFEL production:

Fast pulsing to grow thick films (>>100 nm) productively
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High-temperature valving with inert gas
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Large batch reactors

…
Finnish ALD equipment manufacturers have their roots in the TFEL display manufacturing  Fast, productive reactors

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Riikka Puurunen, VTT, 15.11.2013
TFEL displays - structure
Used with permission from Tuomo Suntola

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Riikka Puurunen, VTT, 15.11.2013
Used with permission from Tuomo Suntola
???

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Riikka Puurunen, VTT, 15.11.2013
Limit: year 1986

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Riikka Puurunen, VTT, 15.11.2013
Please join! Open until Dec 31
Authors to be confirmed by Nov 20

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Riikka Puurunen, VTT, 15.11.2013
Many questions looking for answers

What is the first public record of the invention of ALD in Russia?

What is the Matrix hypothesis and how is it related to ALD?
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What kinds of thin film studies?

Are there microelectronic applications?
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What kinds of reactors?
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Powders

Thin films

… other?

What kind of catalysts?

What kinds of sorbents?
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What other applications?
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How was it to do research with Aleskovskii & Koltsov?
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Is there ALD reactant development in Russia?

ALD in industrial scale in Russia?

Products?

How and when did Russian scientists get to know of other ALD groups?

Current ALD activities in Russia?

...

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Riikka Puurunen, VTT, 15.11.2013
Conference: November 26-29, 1965, Leningrad
TiCl4/H2O at 180C on silica
ALD cycles since 1965

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Riikka Puurunen, VTT, 15.11.2013
Thin film studies since 1969
Vacuum thin film ALD reactors
SPbU
Films, nanolaminates, alloys… Prof. Aleskovskii in 1974 predicted future microelectronics devise shrinkage and important role of ALD

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Riikka Puurunen, VTT, 15.11.2013
Particle coating knowhow & products
From Hilovo 2012 presentation by Prof Malygin, used with permission
Adsorbents to stabilize the device’s internal environment during storage and operation: P2O5 & VO3 POCl3/H2O, VOCl3/H2O
Ceramics for X-ray tubes, ML to decrease sintering temperature: TiO2 & V2O5 from TiCl4/H2O, VOCl3/H2O
Particle ML: Indicators, sorbents, catalysts, composite fillers, …
SPb Technological Institute

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Riikka Puurunen, VTT, 15.11.2013
To conclude:

Finnish ALD (ALE)

Industry-initiated in 1974

Production of TFEL displays already in mid-1980’s

Tool manufacturers

Russia has a rich history of ALD, however the details have been largely unknown to many

Please participate in the Virtual project on the history of ALD:

Help us to generate an overview of the Russian works to help us learn from them

Participate in the poster and at Baltic ALD 2014 (Dec 31)

”Open authorship” for the review article (Nov 20)

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Riikka Puurunen, VTT, 15.11.2013
Acknowledgements

Dr. Tuomo Suntola (Espoo, Finland)

Prof. Anatoly Malygin (St Peterburg State Technological Institute, Russia)

Prof. Victor Drozd (St Petersburg State University, Russia)

Dr. Yury Koshtyal (Ioffe institute, Russia)

Dr. Aziz Abdulagatov (National Institute of Standards and Technology, USA)

Dr. Jonas Sundqvist (Fraunhofer IPMS- CNT, Germany)

… and all others who have helped in the Virtual Project on the History of ALD
Thank you for your attention
СПАСИБО ЗА ВНИМАНИЕ!
ВОПРОСЫ?

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Riikka Puurunen, VTT, 15.11.2013
VTT creates business from technology