ALD Fundamentals and Applications
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The document is a presentation on atomic layer deposition (ALD) given by Riikka Puurunen at the IUPAC|CHAINS2023 World Chemistry Congress. The presentation provides an introduction to ALD, including its history dating back to 1974 with its independent inventions in Finland and Russia. It discusses the fundamentals and typical process conditions of ALD as well as examples of its applications. The presentation emphasizes ALD's ability to conformally coat substrates and provides examples of Puurunen's own research on ALD catalyst synthesis and modeling ALD growth. It concludes by discussing opportunities for future ALD research and the importance of open science practices.
![Puurunen, IUPAC|Chains2023 World Chemistry Congress, The Hague, Aug 20-25, 2023
Atomic layer
deposition (ALD):
Introduction and
progress examples
Riikka Puurunen
IUPAC|CHAINS2023 August 20-25, 2023.
‘Connecting Chemical Worlds’
3
Invited talk in parallel session 62:
Advanced Thin Film Technology
of Energy and Smart Materials
The Sower
Vincent van Gogh (1853 - 1890), Arles,
November 1888
oil on canvas, 32.5 cm x 40.3 cm
Credits: Van Gogh Museum,
Amsterdam (Vincent van Gogh
Foundation)
[vangoghmuseum-s0029V1962-800.jpg; brightness adjusted]](https://image.slidesharecdn.com/puuruneniupacchains2023final2023-08-24with-audio-230825133312-a463208f/85/puurunen-invited-talk-at-iupacchains2023-the-hague-netherlands-aug-2025-2023-1-320.jpg)
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ALD Fundamentals and Applications
- 1. Puurunen, IUPAC|Chains2023 World Chemistry Congress, The Hague, Aug 20-25, 2023 Atomic layer deposition (ALD): Introduction and progress examples Riikka Puurunen IUPAC|CHAINS2023 August 20-25, 2023. ‘Connecting Chemical Worlds’ 3 Invited talk in parallel session 62: Advanced Thin Film Technology of Energy and Smart Materials The Sower Vincent van Gogh (1853 - 1890), Arles, November 1888 oil on canvas, 32.5 cm x 40.3 cm Credits: Van Gogh Museum, Amsterdam (Vincent van Gogh Foundation) [vangoghmuseum-s0029V1962-800.jpg; brightness adjusted]
- 2. Puurunen, IUPAC|Chains2023 World Chemistry Congress, The Hague, Aug 20-25, 2023 What is ALD? Van Ommen, Goulas, Puurunen, “Atomic layer deposition” in Kirk-Othmer Encyclopedia of Chemical Technology, 2021, https://doi.org/10.1002/0471238961.koe00 059 CC BY 4.0 Wikimedia Commons Growth per cycle (GPC) Thin films based on repeated self- terminating gas-solid reactions
- 3. Puurunen, IUPAC|Chains2023 World Chemistry Congress, The Hague, Aug 20-25, 2023 Where is ALD? Van Ommen, Goulas, Puurunen, “Atomic layer deposition” in Kirk-Othmer Encyclopedia of Chemical Technology, 2021, https://doi.org/10.1002/0471238961.koe00 059 CC BY 4.0 Wikimedia Commons Moore’s law’s enabler in your pocket, etc.
- 4. Puurunen, IUPAC|Chains2023 World Chemistry Congress, The Hague, Aug 20-25, 2023 Who am I to talk about ALD? • 25 years of ALD • Same alma mater (and workplaces!*) as the inventor • Catalysts • CMOS • MEMS • Mechanisms • Terminology • Modelling • Reviews • History Krause Suntola Puurunen Photo, Millennium Technology Prize organization, 2018 * Microchemistry, Neste, VTT Semiconductor lab
- 5. Puurunen, IUPAC|Chains2023 World Chemistry Congress, The Hague, Aug 20-25, 2023 Outline • (General intro on ALD – done) • Some words on fundamentals of ALD • How ALD started – some words on history (and integrity) • Conformality: core characteristic of ALD • Own research examples • On “Sustainable Open Science” • Conclusion
- 6. Puurunen, IUPAC|Chains2023 World Chemistry Congress, The Hague, Aug 20-25, 2023 Ideal ALD: saturating & irreversible Van Ommen, Goulas, Puurunen, “Atomic layer deposition” in Kirk-Othmer Encyclopedia of Chemical Technology, 2021, https://doi.org/10.1002/0471238961.koe00059 CC BY 4.0 Wikimedia Commons Time Amount adsorbed
- 7. Puurunen, IUPAC|Chains2023 World Chemistry Congress, The Hague, Aug 20-25, 2023 Growth per cycle (GPC), with cycles Van Ommen, Goulas, Puurunen, “Atomic layer deposition” in Kirk-Othmer Encyclopedia of Chemical Technology, 2021, https://doi.org/10.1002/0471238961.koe00059 CC BY 4.0 Wikimedia Commons & Wikimedia Commons Growth mode?
- 8. Puurunen, IUPAC|Chains2023 World Chemistry Congress, The Hague, Aug 20-25, 2023 Typical ALD process conditions? Temperature • 102 C Pressure • 102 Pa Growth per cycle (GPC) • < 5 metal atoms per nm2 * • 10-1 nm (i.e., Ångström range) • [fraction of a solid bulk monolayer] Growth rate** (average) • 100 nm/min Substrate type • Flat solid 8 Cycle time • 100 s * Blomberg, ECS Trans. 58 (10) (2013) 3; https://doi.org/10.1149/05810.0003ecst **Note: Also in ALD literature: growth rate in units of nm/cycle ALD reactor type • Temporal Time
- 9. Puurunen, IUPAC|Chains2023 World Chemistry Congress, The Hague, Aug 20-25, 2023 Invention: Atomic Layer Epitaxy, 1974 Puurunen & Suntola 2014, Wikimedia Commons CC BY-SA 4.0 Essay on ALE: Puurunen, Chem. Vap. Deposition 20 (2014) 332-344; https://doi.org/10.1002/cvde.201402012 https://en.wikipedia.org/wiki/Tuomo_Suntola Helsinki-Vantaa (HEL) airport, 1983 Dr. Suntola’s 1st experiment
- 10. Puurunen, IUPAC|Chains2023 World Chemistry Congress, The Hague, Aug 20-25, 2023 Invention: Molecular Layering, 1960s Prof. Valentin Borisovich Aleskovskii Prof. Stanislav Ivanovich Koltsov Essay on ML: Malygin et al., Chem. Vap. Deposition 21 (2015) 216-240, DOI: 10.1002/cvde.201502013 https://en.wikipedia.org/wiki/Valentin_Aleskovsky Malygin & particle ML-ALD reactor 1982 10 “Framework hypothesis” Virtual Project on the History of ALD vph-ald.com Worldwide collaborative effort, in an atmosphere of openness, respect and trust
- 11. Puurunen, IUPAC|Chains2023 World Chemistry Congress, The Hague, Aug 20-25, 2023 11 EuroCVD 22 - Baltic ALD 16, in Luxembourg, June 24-28, 2019. Virtual Project on the History of ALD (VPHA). Abstract Poster http://vph-ald.com aldhistory.blogspot.fi Review Article: Recommended reading list of early publications on atomic layer deposition—Outcome of the “Virtual Project on the History of ALD” Journal of Vacuum Science & Technology A 35, 010801 (2017). https://doi.org/10.1116/1.4971389
- 12. Puurunen, IUPAC|Chains2023 World Chemistry Congress, The Hague, Aug 20-25, 2023 Same ALD principles, many practices Van Ommen, Goulas, Puurunen, “Atomic layer deposition” in Kirk-Othmer Encyclopedia of Chemical Technology, 2021, https://doi.org/10.1002/0471238961.koe00 059 CC BY 4.0 Wikimedia Commons
- 13. Puurunen, IUPAC|Chains2023 World Chemistry Congress, The Hague, Aug 20-25, 2023 Conformality: core ALD characteristic Arts et al., Chem. Mater. 33 (2021) 5002–5009. https://doi.org/10.1021/acs.chemmater.1c00781 13 Puurunen, Kattelus, Suntola, Atomic Layer Deposition in MEMS technology, Handbook of Silicon-based MEMS materials and Technologies, 2010, https://doi.org/10.1016/C2009-0-19030-X Van Ommen, Goulas, Puurunen, “Atomic layer deposition” in Kirk-Othmer Encyclopedia of Chemical Technology, 2021, https://doi.org/10.1002/0471238961.koe00059 CC BY 4.0 Wikimedia Commons
- 14. Puurunen, IUPAC|Chains2023 World Chemistry Congress, The Hague, Aug 20-25, 2023 Conformality test structures PillarHallTM Ylilammi et al. J. Appl. Phys. 123, 205301 (2018). https://doi.org/10.106 3/1.5028178 Miikkulainen et al., J. Appl. Phys. 113 (2013) 021301. https://doi.org/10.1 063/1.4757907. Continued at: https://www.atomiclimit s.com/alddatabase/
- 15. Puurunen, IUPAC|Chains2023 World Chemistry Congress, The Hague, Aug 20-25, 2023 Conformality analysis & modelling Yim, Verkama et al. Phys. Chem. Chem. Phys. 24 (2022) 8645-8660. https://doi.org/10.1039/D1CP04758B Yim, Ylivaara et al., Phys. Chem. Chem. Phys. 22 (2020) 23107-23120. https://doi.org/10.1039/D0CP03358H
- 16. Puurunen, IUPAC|Chains2023 World Chemistry Congress, The Hague, Aug 20-25, 2023 Fundamental progress enabled by PillarHallTM Arts et al., J. Vac. Sci. Tech. A 37, 030908 (2019) https://doi.org/10.1116/1.5093620 θ x ~ 16 Method to extract kinetics for thermal ALD (Kn >> 1) Method to extract plasma recombination probability for plasma- enhanced ALD Arts et al., J. Phys. Chem. C 2021, 125, 15, 8244–8252; https://doi.org/10.1021/acs.jpcc.1c01505 https://en.wikipedia.org/wik i/The_Red_Vineyard#/med ia/File:Red_vineyards.jpg
- 17. Puurunen, IUPAC|Chains2023 World Chemistry Congress, The Hague, Aug 20-25, 2023 Case: CO2 hydrogenation to methanol Effect of Zn promoter location (ALD) Support - ZrO2 Cu/ZnO/Zr ZnO/Cu/Zr ZnO/Zr Cu/Zr ZnO/Cu/ZnO/Zr ZnO (by ALD) Cu (by impregnation) Arandia et al., Appl. Catal. B 321 (2023) 122046, https://doi.org/10.1016/j.apcatb.2022.122046 0 2 4 6 8 10 12 1 2 3 CO 2 conversion, % a Zr Zn/Zr Cu/Zr Zn/Cu/Zr Cu/Zn/Zr Zn/Cu/Zn/Zr 450 K 500 K 550 K No measured activity STY methanol 0 100 200 300 425 450 475 500 525 550 575 c 0 1 2 3 4 425 450 475 500 525 550 575 b b 450 K 500 K 550 K STY methanol mmolCH3OH gCu -1h-1 mmolCH3OH gcat -1h-1 Conditions: 30 bar, H2/CO2/N2 (71/23/6, v/v/v); GHSV = 7500 h-1 0 100 200 300 425 450 475 500 525 550 575 c 0 1 2 3 4 425 450 475 500 525 550 575 b b 450 K 500 K 550 K STY methanol mmolCH3OH gCu -1h-1 mmolCH3OH gcat -1h-1 Space time yield
- 18. Puurunen, IUPAC|Chains2023 World Chemistry Congress, The Hague, Aug 20-25, 2023 Future • Own powder ALD reactor being built • EuropaCat 2023, several presentations
- 19. Puurunen, IUPAC|Chains2023 World Chemistry Congress, The Hague, Aug 20-25, 2023 “Sustainable Open Science” Wikimedia Commons Category: Atomic Layer Deposition (K-O images pre-published with CC) #ALDep #IUPACchains2023 (Question!) ALD saturation profile - open data https://github.com/ Aalto-Puurunen Puurunen, CC BY-SA 4.0 openlearning.aalto.fi ALD
- 20. Puurunen, IUPAC|Chains2023 World Chemistry Congress, The Hague, Aug 20-25, 2023 Conclusion • Two independent inventions of ALD • ALD: multitool for industrial applications and academic research (Van Gogh, The Sower) • ALD is fantastic, but not full monolayer per cycle • Many practices for different substrate types • “Sustainable Open Science” • Thought: IUPAC terminology work -- ALD, too? 0 2 4 6 8 10 12 1 2 3 CO 2 conversion, % a Zr Zn/Zr Cu/Zr Zn/Cu/Zr Cu/Zn/Zr Zn/Cu/Zn/Zr 450 K 500 K 550 K No measured activity STY methanol
- 21. Puurunen, IUPAC|Chains2023 World Chemistry Congress, The Hague, Aug 20-25, 2023 Acknowledgements • Prof. Ruud Van Ommen, TU Delft • Prof. Erwin Kessels group (K. Arts), TU Eindhoven Aalto Catalysis group (Summer day 2023) (Research Council of Finland)
- 22. Puurunen, IUPAC|Chains2023 World Chemistry Congress, The Hague, Aug 20-25, 2023 The Sower Vincent van Gogh (1853 - 1890), Arles, November 1888 oil on canvas, 32.5 cm x 40.3 cm Credits: Van Gogh Museum, Amsterdam (Vincent van Gogh Foundation) [vangoghmuseum-s0029V1962- 800.jpg; brightness adjusted]
Editor's Notes
- DescriptionEnglish: Schematics of some of the main commercial applications of atomic layer deposition (ALD): (a) Thin Film Electroluminescent Display; (b) 3-D Dynamic Random Access Memory; (c) metal-oxide-semiconductor field-effect transistor; (d) write and read head of a hard disk; (e) silver coin; (f) passivated emitter and reactor contact cell (photovoltaic cell).More background info in: M. Ritala and M. Leskelä, “Chapter 2 - Atomic layer deposition,” in Handbook of Thin Films, H. Singh Nalwa, Ed. Burlington: Academic Press, 2002, pp. 103–159. S. K. Kim, S. W. Lee, J. H. Han, B. Lee, S. Han, and C. S. Hwang, “Capacitors with an Equivalent Oxide Thickness of <0.5 nm for Nanoscale Electronic Semiconductor Memory,” Adv. Funct. Mater., vol. 20, no. 18, pp. 2989–3003, 2010. K. E. Williams, “Hard disk-drive technology revolutionizes processing,” Solid State Technol., vol. 47, no. 9, pp. S21–S21, 2004. S. Maat and A. C. Marley, “Physics and Design of Hard Disk Drive Magnetic Recording Read Heads,” in Handbook of Spintronics, Y. Xu, D. D. Awschalom, and J. Nitta, Eds. Dordrecht: Springer Netherlands, 2016, pp. 977–1028. B. Macco, B. W. van de Loo, and W. M. Kessels, “Atomic layer deposition for high efficiency crystalline silicon solar cells,” in Atomic Layer Deposition in Energy Conversion Applications, Wiley, 2017, pp. 41–99. Date25 March 2021SourceOwn workAuthorJ. Ruud van Ommen, Fenne B.M. van Ommen, Riikka L. Puurunen
- I happen to have shared the university (TKK) and three work places (Microchemistry/Neste, VTT Semiconductor lab) with the Finnish inventor
- The American Academy of Dermatology says that hair grows about 1/2 inch per month on average. That's a grand total of about 6 inches per year for the hair on your head. 1 cm per month for hair 230 nm/min for hair Discussion on this slide in: Discussion: https://twitter.com/rlpuu/status/1330129040720732161?s=20
- Valentin Borisovich Aleskovskii Stanislav Ivanovich Kol'tsov
- Fundamental info on ALD processes missing. Growth per cycle, growth kinetics. Saturation profile in well-defined high-aspect-ratio structures
- https://joint-research-centre.ec.europa.eu/what-open-education_en