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Introduction to atomic layer deposition (ALD): principles, applications, future

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Introductory lecture on Atomic Layer Deposition (ALD) by Prof. Riikka Puurunen, given at Aalto University School of Chemical Engineering on November 8, 2018. Lecture contents: Principles and concepts of ALD; Some history; Applications of ALD; Words on future. In addition to the core lecture contents, discusses where we have ALD layers in our smart mobile phones; mentions (some) faces of ALD in Finland; STG podcasts; Virtual Project on the History of ALD.
Corresponding lecture capture by Panopto available at: https://aalto.cloud.panopto.eu/Panopto/Pages/Viewer.aspx?id=bd0aee67-7ca5-4973-8216-a99200e888b1

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Introduction to atomic layer deposition (ALD): principles, applications, future

  1. 1. Puurunen, Aalto University CHEM-E5205, November 8, 2018 Introduction to atomic layer deposition (ALD) principles, applications, future Prof. Riikka Puurunen CHEM-E5205 Advanced Functional Materials 8.11.2018
  2. 2. Puurunen, Aalto University CHEM-E5205, November 8, 2018 Lecture contents 1. Principles and concepts of ALD 2. Some history 3. Applications of ALD 4. Words on future
  3. 3. Puurunen, Aalto University CHEM-E5205, November 8, 2018 Before we start, discussion: • What do you already know of Atomic Layer Deposition (ALD)? • Where can one find ALD films in practice?
  4. 4. Puurunen, Aalto University CHEM-E5205, November 8, 2018 Connections between lectures Where ALD? ? ? ? ? ? yes
  5. 5. Puurunen, Aalto University CHEM-E5205, November 8, 2018 2018 Millennium Technology Prize (MTP) to Dr. Tuomo Suntola for ALD • MTP is Finland's tribute to innovations for a better life. • The Prize is worth one million euros and it is awarded every second year. • Dr. Suntola thanks the community for support and shares honor for the prize. Photo: Technology Academy Finland 2018 President Sauli Niinistö, Dr. Tuomo Suntola More: www.taf.fi http://aldhistory.blogspot.com/search/label/MTP2018 https://issuu.com/aaltouniversity/docs/aum_23_en_pdf-150dpi/24
  6. 6. Puurunen, Aalto University CHEM-E5205, November 8, 2018 Expected learning outcomes After this lecture, you should… 1. be able to describe the principles of ALD 2. be aware of the history of ALD including the two independent discoveries 3. be able to name some applications where ALD is used
  7. 7. Puurunen, Aalto University CHEM-E5205, November 8, 2018 ALD: Principles and concepts
  8. 8. Puurunen, Aalto University CHEM-E5205, November 8, 2018 The 2005 review by Puurunen J. Appl. Phys. 97 (2005) 121301. DOI: 10.1063/1.1940727 • Times cited: 1327 (as of 8.11.2018, WoS) • Section III written to explain the surface chemistry concepts • Section V written to discuss problematic assumptions • Review used for teaching ALD
  9. 9. Puurunen, Aalto University CHEM-E5205, November 8, 2018 How is ALD defined? ” ALD can be defined as a film deposition technique that is based on the sequential use of self- terminating gas–solid reactions” Review: Puurunen JAP 97 (2005) 121301 ALD cycle Reactant A Reactant B By-product Substrate before ALD Step 2 /4 purge Step 4 /4 purge Step 1 /4 Reactant A Step 3 /4 Reactant B Reactant A Reactant B By-product Puurunen, J. Appl. Phys. 97 (2005) 121301. DOI: 10.1063/1.1940727 Open Access: https://www.vtt.fi/inf/julkaisut/muut/2010/Puurunen.pdf
  10. 10. Puurunen, Aalto University CHEM-E5205, November 8, 2018 Self-terminating  Saturating & irreversible desorptionnon-saturation unsaturation amount adsorbed saturates amount adsorbed stays NO: pulse purge Puurunen, J. Appl. Phys. 97 (2005) 121301. https://doi.org/10.1063/1.1940727 open access pdf sequential use of self-terminating gas–solid reactions
  11. 11. Puurunen, Aalto University CHEM-E5205, November 8, 2018 Gas-solid reactions  Chemical adsorption Physisorption • non-specific • minimal electronic interaction • chemical nature of the adsorbate not altered • adsorption energy similar to the energy of condensation (exothermic) • non-activated • equilibrium is established • multilayers may form Chemisorption • chemical specificity • changes in electronic state • reversible/irreversible • chemisorption energy as for a chemical reaction (exothermic/endothermic) • often involves an activation energy • for “large” activation energies (“activated adsorption”), true equilibrium may be achieved slowly • monolayer adsorption http://old.iupac.org/reports/2001/colloid_2001/manual_of_s_and_t/node16.html sequential use of self-terminating gas–solid reactions
  12. 12. Puurunen, Aalto University CHEM-E5205, November 8, 2018 Chemisorption mechanisms typical in ALD Puurunen, J. Appl. Phys. 97 (2005) 121301. https://doi.org/10.1063/1.1940727 open access pdf
  13. 13. Puurunen, Aalto University CHEM-E5205, November 8, 2018 Growth per cycle (GPC) • ALD is characterized by a GPC, which depends typically on: • reactants • temperature • substrate • In ALD, there is no ”growth rate” in the sense as e.g. in chemical vapor deposition Puurunen, J. Appl. Phys. 97 (2005) 121301. https://doi.org/10.1063/1.1940727 open access pdf sequential use of self-terminating gas–solid reactions
  14. 14. Puurunen, Aalto University CHEM-E5205, November 8, 2018 Note: typically less than monolayer growth per cycle • ”Monolayer” has many definitions and can be confucing Puurunen, J. Appl. Phys. 97 (2005) 121301. https://doi.org/10.1063/1.1940727 open access pdf (a) a chemisorbed monolayer (the substrate before chemisorption indicated above, with reactive sites shown), (b) a physisorbed monolayer, and (c) a monolayer of the ALD-grown material. GPC rarely >50% of a monolayer
  15. 15. Puurunen, Aalto University CHEM-E5205, November 8, 2018 Concept of ”ALD window” (original by Suntola) Suntola 1981, re-shared in: http://aldhistory.blogspot.com/2016/01/ald-terminology-discussion-ald- window-2.html
  16. 16. Puurunen, Aalto University CHEM-E5205, November 8, 2018 Concept of ”ALD window” (original by Suntola) Suntola, ”Atomic layer epitaxy” Mater. Sci. Rep. 4 (1989) 261-312. DOI: 10.1016/S0920-2307(89)80006-4 Explanations (shortened by RLP) L1: condensation to be prevented L2: activation energy to exceed H1: decomposition H2: re-evaporation How GPC can vary within an ALD window? Puurunen, J. Appl. Phys. 97 (2005) 121301. https://doi.org/10.1063/1.1940727 open access pdf
  17. 17. Puurunen, Aalto University CHEM-E5205, November 8, 2018 Typical reactant/precursor classes H2O NH3 H2S Non-metal precursors, “thermal” ALD plasma-enhanced ALD (not for catalysts) O2 N2 H2 Metal precursor type Elements Halides Alkyls Cyclopentadienyls Alkoxides b-diketonates Alkylamides and silylamides Amidinates InorganicMetal-organic Organo- metallic Class N NM N M O M O O M M M M Cl M etc etc Puurunen, J. Appl. Phys. 97 (2005) 121301. https://doi.org/10.1063/1.1940727 open access pdf
  18. 18. Puurunen, Aalto University CHEM-E5205, November 8, 2018 Status of two-reactant ALD process research >700 processes tested Miikkulainen, Leskelä, Ritala, Puurunen (review), J. Appl. Phys. 113 (2013) 021301. http://dx.doi.org/10.1063/1.4757907. open access pdf. >2000 references Would be good to update info
  19. 19. Puurunen, Aalto University CHEM-E5205, November 8, 2018 ”Model ALD process”: trimethylaluminium/water  Al2O3 Model status acknowledged/agreed e.g. in: • Puurunen 2005, review on the TMA/water process, DOI: 10.1063/1.1940727 • George 2010, DOI: 10.1021/cr900056b • Miikkulainen et al. 2013, DOI: 10.1063/1.4757907 • Knapas & Ritala 2013, DOI: 10.1080/10408436.2012.693460 • Weckman & Laasonen 2018, DOI: 10.1039/C5CP01912E • Van Bui et al. 2017, DOI: 10.1039/c6cc05568k Van Bui, Grillo, Van Ommen, Chem. Commun. 53 (2017) 45. DOI: 10.1039/c6cc05568k
  20. 20. Puurunen, Aalto University CHEM-E5205, November 8, 2018 Conformality: ALD’s core benefit Sneh et al., Thin Solid Films 402 (2002) 248.
  21. 21. Puurunen, Aalto University CHEM-E5205, November 8, 2018 Why use ALD? ALD is not perfect! • ALD overall slow (reactions non-continuous) • Special equipment and chemicals needed  can be expensive • Sometimes, toxic chemicals • ”Research grade” layers often have impurities and other non-idealities ALD has many benefits • Scalable to large substrates & batch processing • Reproducible, even from equipment to equipment ( nature controlled) • Excellent nucleation control (first few monolayers of growth) • High (optimized) layer quality • Unmatched conformality
  22. 22. Puurunen, Aalto University CHEM-E5205, November 8, 2018 Where ALD? Aalto University Magazine October 2018, https://issuu.com/aaltouniversity/docs/aum_23_en_pdf-150dpi/24
  23. 23. Puurunen, Aalto University CHEM-E5205, November 8, 2018 Some history
  24. 24. Puurunen, Aalto University CHEM-E5205, November 8, 2018 Discovered independently twice • Atomic layer epitaxy (ALE) • 1974  Molecular Layering (ML) ? 1965  Dr. Tuomo S. Suntola Photo:RiikkaPuurunen,Wikimedia Prof. Valentin B. Aleskovskii Prof. Stanislav I. Koltsov Suntola T, Antson J (1974). Patent FIN 52359 (29 November 1974); corresponds to U.S. patent 4 058 430 (25 November 1975). Aleskovskii VB, Koltsov SI (1965). Some characteristics of molecular layering reactions. In Abstract of Scientific and Technical Conference of the Leningrad Technological Institute by Lensovet (Goskhimizdat, Leningrad, 1965), pp. 67–67 (in Russian). Puurunen, J. Appl. Phys. 97 (2005) 121301. DOI: 10.1063/1.1940727
  25. 25. Puurunen, Aalto University CHEM-E5205, November 8, 2018 • Launched in 2013 to make the early days of ALD more transparent • Volunteer based • Currently, >70 contributors from >20 countries • Voluntary coordinator: Puurunen • Colours: shades of gray • In atmosphere of openness, respect, and trust http://vph-ald.com, http://aldhistory.blogspot.fi
  26. 26. Puurunen, Aalto University CHEM-E5205, November 8, 2018 VPHA started from a question 9.11.2018 26 May 6, 2013, Riikka Puurunen LinkedIn ”ALD - Atomic Layer Deposition” group https://www.linkedin.com/groups/1885076/1885076-238399494
  27. 27. Puurunen, Aalto University CHEM-E5205, November 8, 2018 Atomic layer epitaxy (ALE) Puurunen, Chem. Vap. Deposition 20 (2014) 332-344. DOI: 10.1002/cvde.201402012 • “A Short History of Atomic Layer Deposition: Tuomo Suntola's Atomic Layer Epitaxy” • ALE-ALD in 1974, patent, ZnS FinALD40 exhibition – 40 years from filing the first patent in Nov 1974 ImagebyRiikkaPuurunen VPHA article 1
  28. 28. Puurunen, Aalto University CHEM-E5205, November 8, 2018 Learnings on the history of ALD, atomic layer epitaxy (1/2) • Spatial ALD concepts already in the early ALE patents • 1st conference presentation in 1980 with ALE-EL demo: 1000s of product inquiries • 2nd conference presentation by Suntola in 1981 laid seeds for ALE development in Japan 9.11.2018 28 R. L. Puurunen, ECS Transactions 86 (6) (2018) 3-17. DOI: 10.1149/08606.0003ecst R. L. Puurunen, Chem. Vap. Deposition 20 (2014) 332-344. DOI: 10.1002/cvde.201402012 Sven Lindfors and the flow ALE-ALD reactor in 1978
  29. 29. Puurunen, Aalto University CHEM-E5205, November 8, 2018 Learnings on the history of ALD, atomic layer epitaxy (2/2) • ALE-EL airport display demonstrator 15 years in continuous use • ALE-EL licensed to France to CGE ( Alcatel) in early 1980s • Early ALD research in Finland was fully related to EL displays • ALD was used for CdTe photovoltaic applications in 1990s 9.11.2018 29 R. L. Puurunen, ECS Transactions 86 (6) (2018) 3-17. DOI: 10.1149/08606.0003ecst R. L. Puurunen, Chem. Vap. Deposition 20 (2014) 332-344. DOI: 10.1002/cvde.201402012 Ralf Graeffe in 1983
  30. 30. Puurunen, Aalto University CHEM-E5205, November 8, 2018 Molecular layering (ML) 9.11.2018 30 Malygin, Drozd, Malkov, Smirnov, Chem. Vap. Deposition 21 (2015) 216-240. DOI: 10.1002/cvde.201502013 • From V. B. Aleskovskii's “Framework” Hypothesis to the Method of Molecular Layering/Atomic Layer Deposition VPHA article 2 Aleskovskii, 1952, matrix hypothesis
  31. 31. Puurunen, Aalto University CHEM-E5205, November 8, 2018 PhotobyRiikkaPuurunen Learnings on the history of ALD, molecular layering side (1/2) • Oldest confirmed written ML-ALD record: abstract from 1965 • Atmospheric pressure used in many early ML studies • The first USSR patents on ALD for catalysis date from 1972 • ML thin film growth in mid-1970s • Early catalysis ALD works in Bulgaria 9.11.2018 31 Drozd’s thin film reactor, 1977 Drozd Baltic ALD 2014 R. L. Puurunen, ECS Transactions 86 (6) (2018) 3-17. DOI: 10.1149/08606.0003ecst A. Malygin, V. E. Drozd, A. A. Malkov, V. M. Smirnov, Chem. Vap. Deposition 21 (2015) 216-240. DOI: 10.1002/cvde.201502013
  32. 32. Puurunen, Aalto University CHEM-E5205, November 8, 2018 Learnings on the history of ALD, molecular layering side (2/2) • Amine-catalysed SiO2 process • In situ gravimetry during ML • Small-scale production by ML-ALD • Fluidized bed for particle coating • Massive list of PhD theses • Aleskovskii’s central academic role • Central role of Koltsov’s ML thesis 9.11.2018 32 Malygin & particle ML-ALD reactor 1982 R. L. Puurunen, ECS Transactions 86 (6) (2018) 3-17. DOI: 10.1149/08606.0003ecst A. Malygin, V. E. Drozd, A. A. Malkov, V. M. Smirnov, Chem. Vap. Deposition 21 (2015) 216-240. DOI: 10.1002/cvde.201502013
  33. 33. Puurunen, Aalto University CHEM-E5205, November 8, 2018 Full slide set shared openly through ECSarXiv, DOI: 10.1149/osf.io/u6vw7 Related article, Puurunen, ECS Transactions 86 (6) (2018) 3-17. DOI: 10.1149/08606.0003ecst, open access preprint https://ecsarxiv.org/exyv3/
  34. 34. Puurunen, Aalto University CHEM-E5205, November 8, 2018 Scientific articles on the history of ALD Puurunen, J. Appl. Phys. 97 (2005) 121301. DOI: 10.1063/1.1940727 1. Puurunen, ”A Short History of Atomic Layer Deposition: Tuomo Suntola's Atomic Layer Epitaxy,” Chem. Vap. Deposition 20 (2014) 332-344. DOI: 10.1002/cvde.201402012 2. Malygin, Drozd, Malkov, Smirnov, ”From V. B. Aleskovskii's “Framework” Hypothesis to the Method of Molecular Layering/Atomic Layer Deposition,” Chem. Vap. Deposition 21 (2015) 216-240. DOI: 10.1002/cvde.201502013 3. Ahvenniemi et al. (62 coauthors), ”Review Article: Recommended reading list of early publications on atomic layer deposition—Outcome of the “Virtual Project on the History of ALD”,” J. Vac. Sci. Technol. A 31 (2017) 010801. DOI: 10.1116/1.4971389 4. Puurunen, “Learnings from an Open Science Effort: Virtual Project on the History of ALD,” ECS Transactions 86 (6) (2018) 3-17. DOI: 10.1149/08606.0003ecst (open access preprint: https://ecsarxiv.org/exyv3/)
  35. 35. Puurunen, Aalto University CHEM-E5205, November 8, 2018 ALD theses (VPHA) • VPHA-generated formally unpublished summary of ALD theses worldwide • Image status: 07/2017 • Access and propose to add info through: http://vph- ald.com/VPHAopenfile s.html
  36. 36. Puurunen, Aalto University CHEM-E5205, November 8, 2018 ALD timeline – RLP’s initial draft, to be improved (in VPHA) 1965, 1st record of ML 1980s 1990s1970s1960s 2000s 2010s 1974, 1979, Patents, ALE 1971, Koltsov thesis 1972 Catalysis authors’s inventions ALE-EL display factory Fluidized bed activity 1987 Microchemistry Ltd, Finland 1st catalysis thesis, Finland DRAM production ALD high-k in CMOS Photovoltaics 2005 review TMA-water 2013 VPHA started 2018 Millennium Technology Prize Formally unpublished ALD timeline draft presented in Puurunen’s invited presentations in 2018 at EMRS fall meeting Warsaw and ECS-AiMES symposium in Cancun Mexico
  37. 37. Puurunen, Aalto University CHEM-E5205, November 8, 2018 ALD in industrial applications
  38. 38. Puurunen, Aalto University CHEM-E5205, November 8, 2018 ”Strategic decisions to keep the use of ALD as a trade secret … concerns on patent issues ... ” • Ritala, Niinistö, “Industrial Applications of Atomic Layer Deposition”, ECS Transactions 25 (2009) 641-652, http://dx.doi.org/10.1149/1.3207651 ” jos joku puolijohdevalmistaja ottaisi tällaisen passivointimenetelmän käyttöönsä, ei se siitä kertoisi” • https://lehti.tek.fi/bosund, accessed 31.10.2018 Photo by Riikka Puurunen / Taneli Ras
  39. 39. Puurunen, Aalto University CHEM-E5205, November 8, 2018 ALD in numbers • The yearly size of the ALD equipment market is estimated as USD 1.4-1.5 Billion • source: Gartner 2016 Wafer Equipment report, VLSI Research (CMC 2017) and Sundqvist / BALD Engineering • Forecast: ” Atomic Layer Deposition (ALD) Market Size Worth $3.01 Billion By 2025” • https://www.grandviewresearch.com/press-release/global-atomic-layer-deposition-market
  40. 40. Puurunen, Aalto University CHEM-E5205, November 8, 2018 Companies selling ALD reactors (RLP’s incomplete list from July 2018) 1. Aixtron (www.aixtron.com, USA), 2. ALD Nanosolutions (www.aldnanosolutions.com, USA), 3. Applied Materials (www.appliedmaterials.com, USA), 4. Arradiance (www.arradiance.com, USA), 5. ASM (www.asm.com, Netherlands), 6. Beneq (www.beneq.com, Finland), 7. CN1 (www.cn-1.co.kr/about-us/news, Korea), 8. Delft IMP (http://delft-imp.nl/, The Netherlands), 9. Encapsulix (www.encapsulix.com, France), 10. Eugene Technology (www.eugenetechnology.com, Korea), 11. Ferri Watt (www.magnetron.ru, Russia), 12. Holst Centre (www.holstcentre.com, The Netherlands), 13. Forge Nano (www.forgenano.com, USA), 14. Jusung Engineering (http://www.jseng.com/eng/, Korea), 15. Kobus (http://kobus-tech.com/, France) 16. Kurt J. Lesker (http://www.lesker.com/, USA), 17. LAM Research Corporation (www.lamresearch.com, USA), 18. Levitech (www.levitech.nl, The Netherlands), 19. Modularflow (www.modularflow.com, Germany), 20. Nano-Master (http://www.nanomaster.com/ald.html, USA), 21. NCD (http://www.ncdtech.co.kr/, Korea), 22. Oxford Instruments Plasma Technology (www.oxford- instruments.com/plasma, UK), 23. Picosun (www.picosun.com, Finland), 24. Samco (www.samcointl.com, Japan), 25. Sentech (www.sentech.com, Germany), 26. SolayTech (http://www.solaytec.com/, The Netherlands), 27. Suga (http://www.suga.ne.jp/, Japan), 28. Sundew (http://www.sundewtech.com/, USA), 29. SVT Associates (www.svta.com, USA), 30. Tokyo Electron (www.tel.com, Japan), 31. Veeco CNT (www.veeco.com, http://www.cambridgenanotechald.com/, USA), 32. Wonik IPS (http://www.ips.co.kr/eng_main/sub1_1.php, Korea).
  41. 41. Puurunen, Aalto University CHEM-E5205, November 8, 2018 Blog post: https://beneq.com/en/beneq/blog/playing-with-the-big-guys Also: http://fortune.com/global500/
  42. 42. Puurunen, Aalto University CHEM-E5205, November 8, 2018 Achievable functional properties, for example • Electrical: isolation, controlled leakage, conduction; high dielectric constant • Optical: transparency, high refractive index, low refractive index, luminescence, … • Chemical: resistance to given surrounding; controlled release; hard mask in lithographic etching • Morphological: controlled surface roughness
  43. 43. Puurunen, Aalto University CHEM-E5205, November 8, 2018 Conformality as core benefit Gutsche, Future Fab Intl. Issue 14; George, plenary talk, AVS-ALD 2013 Ni/zirconia, submitted, preprint DOI: 10.26434/chemrxiv.7204847.v1 Source: Applied Materials post
  44. 44. Puurunen, Aalto University CHEM-E5205, November 8, 2018 Electroluminescent (EL) flat panel displays 1985  (Espoo, Finland) Ritala, Niinistö, ECS Transactions 25 (2009) 641-652. http://dx.doi.org/10.1149/1.3207651 Puurunen, Chem. Vap. Deposition 20 (2014) 332-344. DOI: 10.1002/cvde.201402012 Beneq blog 12.10.2018, accessed 31.10.2018 https://beneq.com/en/displays/blog/transparent-lumineq-matrix- displays-just-got-lot-bigger Luminescent: ZnS:Mg Insulating: ~200 nm Al2O3, AlxTiyO
  45. 45. Puurunen, Aalto University CHEM-E5205, November 8, 2018 EL display in harsh environments e.g. in Airbus A350 • Lumineq 5.7” TFEL display • Service control display for water management Blog links: • https://beneq.com/en/displays/applications/airbus-water-management-system • https://beneq.com/displays/blog/lumineq-flying-high
  46. 46. Puurunen, Aalto University CHEM-E5205, November 8, 2018 Newer: transparent TFEL displays • Thanks to Beneq Oy for TASEL the demo for teaching! • https://beneq.com/en/displays/pr oducts/tasel/elt-15s • E.g., in 2019: Valtra tractors • https://beneq.com/en/displays/bl og/proven-in-field • https://beneq.com/en/videos/lumi neq-tour-in-agritechnica-valtra- smartglass-windshield
  47. 47. Puurunen, Aalto University CHEM-E5205, November 8, 2018 Thin film structure of TASEL display * A low atomic number capping layer has been used to protect the upper surface of the sample during the ion beam thinning preparation of the section Electron microscopy image courtesy of Beneq Oy
  48. 48. Puurunen, Aalto University CHEM-E5205, November 8, 2018 Scheme courtesy of Beneq Oy
  49. 49. Puurunen, Aalto University CHEM-E5205, November 8, 2018 Where ALD? https://issuu.com/aaltouniversity/docs/aum_23_en_pdf-150dpi/24 Where is ALD in the smartphone? • Memory chip, logics chip, sacrificial layer in lithography steps • Where else? • (One would need to know the technology used in smart phones to be able to tell in detail) • A bit related: ”Puhelin palasina” (in Finnish), https://www.hs.fi/teknologia/art-2000005867359.html, accessed 31.10.2018 My solution  Ask Twitter!
  50. 50. Puurunen, Aalto University CHEM-E5205, November 8, 2018 ”Twitter knows first” • https://twitter.com/rlpuu/status/1057620486136442880
  51. 51. Puurunen, Aalto University CHEM-E5205, November 8, 2018 CMOS transistors: • ”High-k metal gate technology”
  52. 52. Puurunen, Aalto University CHEM-E5205, November 8, 2018 Multiple patterning in lithography ” ALD for Self-Aligned Multiple Patterning (SAxP) – How litho has become patterning and requires ALD”, March 13, 2017, link • In ”Atomic limits” blog by Prof Kessels & coworkers, TU Eindhoven https://www.atomiclimits.com/2017/03/13/ald-for-self-aligned- multiple-patterning-saxp-how-litho-has-become-patterning-and- requires-ald/ http://www.blog.baldengineering.com/2014/04/video -understanding-new-finfet.html
  53. 53. Puurunen, Aalto University CHEM-E5205, November 8, 2018 http://www.eenewsanalog.com//news/iedm-samsung-makes-3nm-gate-all-around-cmos
  54. 54. Puurunen, Aalto University CHEM-E5205, November 8, 2018 ALD keep the Moore’s law going • IEEE Spectrum, Oct 1, 2017 • https://spectrum.ie ee.org/semiconduc tors/design/the- highk-solution
  55. 55. Puurunen, Aalto University CHEM-E5205, November 8, 2018 Logic chips: 2007 
  56. 56. Puurunen, Aalto University CHEM-E5205, November 8, 2018 Memory chips: 2004  Sundqvist, Story of ZyALD, http://www.aldcoe.fi/events/finald40.pdf, accessed 31.10.2018 Shim et al., J. Mater. Chem. C, 2017, 5, 8000- 8013, DOI: 10.1039/C6TC05158H
  57. 57. Puurunen, Aalto University CHEM-E5205, November 8, 2018 Microelectromechanical systems (MEMS)
  58. 58. Puurunen, Aalto University CHEM-E5205, November 8, 2018 Still from Twitter… Answer to https://twitter.com /rlpuu/status/1057 620486136442880
  59. 59. Puurunen, Aalto University CHEM-E5205, November 8, 2018 Protection against dark(ening) forces, 2006  M. Ritala, J. Niinistö, “Industrial Applications of Atomic Layer Deposition”, ECS Transactions 25 (2009) 641-652, http://dx.doi.org/10.1149/1.3207651. https://beneq.com/en/thin-films/blog/may-coating-be-you, accessed 31.10.2018 Barrier against sulfur from air: ~10 nm Al2O3 protects Ag (alloys) from tarnishing
  60. 60. Puurunen, Aalto University CHEM-E5205, November 8, 2018 ALD in the watchmaking industry • Picosun press release • Probably reliable • No application details http://www.watchpro.com/picosun-group-solidifies-position-watchmaking-market/ accessed 31.10.2018
  61. 61. Puurunen, Aalto University CHEM-E5205, November 8, 2018 ALD in space
  62. 62. Puurunen, Aalto University CHEM-E5205, November 8, 2018 Words on the future • ”Playing the Wizard”… • https://en.wikipedia.org/wiki/The_Wonderful_Wizard_of_Oz
  63. 63. Puurunen, Aalto University CHEM-E5205, November 8, 2018 Microelectronics scaling continues • Microelectronics will remain the driving force for ALD development • Counterpart developing rapidly, too: atomic layer etching • Kanarik et al., Journal of Vacuum Science & Technology A 33, 020802 (2015); https://doi.org/10.1116/1.4913379
  64. 64. Puurunen, Aalto University CHEM-E5205, November 8, 2018 Catalysis • Third forthcoming, now worldwide • Earlier: Soviet Union & Bulgaria; Finland • Separate lecture, CHEM-E1130 Catalysis course • Next course, MyCourses site: https://mycourses.aalto.fi/course/view.php?id=20383
  65. 65. Puurunen, Aalto University CHEM-E5205, November 8, 2018 Pharmaceuticals & medical applications • Controlled release of medicine • Affecting the flow of powders • Protective biocompatible layers • Startups in Sweden, Finland/USA
  66. 66. Puurunen, Aalto University CHEM-E5205, November 8, 2018 Saturation profile as ”the ALD observable”? name by Yanguas-Gil, 2017 Distance l (µm, mm, …) Relative dimensionless distance l / g [r.d.u.] Amount grown (nm, # of atoms, …) (per cycle) 50%-thickness- penetration-depth (PD50%) Slope at PD50% GPC just inside + initial slope Knee GPC just outside x1. 2. 3. 4. 5. 6. Gap entrance (relative distance units) Ylilammi, Ylivaara, Puurunen, J. Appl. Phys. 2018, DOI: 10.1063/1.5028178 Watch out for conformality review to be published, Cremers, Puurunen, Dendooven
  67. 67. Puurunen, Aalto University CHEM-E5205, November 8, 2018 Debate on the surface chemistry details of the ”model ALD process”? • Slides by Puurunen at the Ireland ALD 2016 conference, oral presentation slides in SlideShare • See also: Vandalon & Kessels 2017, DOI https://doi.org/10.1116/1.4993597; Winter 2018, DOI: 10.1149/osf.io/b6kzv
  68. 68. Puurunen, Aalto University CHEM-E5205, November 8, 2018 More / better citing of original references? • E.g., Suntola review from 1989 surprisingly little cited • DOI: 10.1016/S0920- 2307(89)80006-4 • Times cited: 426 (Elsevier statistics) From: Puurunen, “Learnings from an Open Science Effort: Virtual Project on the History of ALD,” ECS Transactions 86 (6) (2018) 3-17. DOI: 10.1149/08606.0003ecst (open access preprint: https://ecsarxiv.org/exyv3/ )
  69. 69. Puurunen, Aalto University CHEM-E5205, November 8, 2018 To conclude
  70. 70. Puurunen, Aalto University CHEM-E5205, November 8, 2018 ALD: growing & transitioning field • ALD: a multitool of nanotechnology • ”The latest major breakthrough in the field of CVD” Pedersen & Elliott 2014, DOI: 10.1007/s00214-014-1476-7 • 2018 Millennium Technology Prize • https://finland.fi/business-innovation/finnish-physicist-tuomo-suntola-wins- millennium-technology-prize/ • ALD invented independently twice • 1st industrial application: flat panel displays 1980s , enabler of Moore’s law 2000s  • Yearly ALD equipment market size >USD 1B
  71. 71. Puurunen, Aalto University CHEM-E5205, November 8, 2018 (Some) faces of ALD of Finland Mr. Sven Lindfors Dr. Tuomo Suntola Prof. Markku Leskelä University of Helsinki Prof. Hele Savin Aalto University Prof. Maarit Karppinen Aalto University Prof. Riikka Puurunen Aalto University Prof. Mikko Ritala University of Helsinki + Dr. Jonas Sundqvist BALD Engineering + Prof. Sean Barry Carleton University Companies: ASM, Beneq, Picosun, + 100’s of other faces Photo: TAF Source: DOI: 10.1002/cvde.201402012 Photo:Puurunen,2014 Photo:Puurunen,2015 Photo:Puurunen,2014 Photo:HY,link Photo:AaltoUniversity Photo:AaltoUniversity Photo:AaltoUniversity
  72. 72. Puurunen, Aalto University CHEM-E5205, November 8, 2018 Additional information
  73. 73. Puurunen, Aalto University CHEM-E5205, November 8, 2018 Aalto University Magazine October 2018 https://issuu.com/aal touniversity/docs/au m_23_en_pdf- 150dpi/24
  74. 74. Puurunen, Aalto University CHEM-E5205, November 8, 2018 Puurunen’s latest Publication (submitted) Puurunen, Riikka; Voigt, Pauline; Haimi, Eero; Lahtinen, Jouko; Cheah, You Wayne; Mäkelä, Eveliina; et al. (2018): Nickel Supported on Mesoporous Zirconium Oxide by Atomic Layer Deposition: Initial Fixed-Bed Reactor Study. ChemRxiv. Preprint. Doi: 10.26434/chemrxiv.7204847.v1
  75. 75. Puurunen, Aalto University CHEM-E5205, November 8, 2018 STG podcasts – Aalto students, with ALD
  76. 76. Puurunen, Aalto University CHEM-E5205, November 8, 2018 More info on the VPHA Virtual Project on the History of ALD
  77. 77. Puurunen, Aalto University CHEM-E5205, November 8, 2018 VPHA started from a question 9.11.2018 77 May 6, 2013, Riikka Puurunen LinkedIn ”ALD - Atomic Layer Deposition” group https://www.linkedin.com/groups/1885076/1885076-238399494
  78. 78. Puurunen, Aalto University CHEM-E5205, November 8, 2018 How does VPHA work? *Voluntary *Open Science • We collect together info on early ALD publications up to 1986 • We collect individual summaries (”comments”) on those publications (goal: ≥3 comments/publication) in the ALD-history-evolving-file, openly shared (Google Docs) • Everyone who shares at least one comment, becomes contributor (now: 76, from >20 countries in 4 continents)  coauthor • Website: http://vph-ald.com • http://vph-ald.com/Publication%20Plan.html • Blog: http://aldhistory.blogspot.fi 9.11.2018 78
  79. 79. Puurunen, Aalto University CHEM-E5205, November 8, 2018 9.11.2018 79 • Openness, • Respect, and • Trust Colours: shades of gray
  80. 80. Puurunen, Aalto University CHEM-E5205, November 8, 2018 VPHA outcomes • 4 scientific articles (reviews): 2 CVD, 1 JVSTA, 1 ECST • Conference presentations: ~4 ALD, ~2 BALD • Exhibition: 40 Years of ALD in Finland – Photos, Stories • Wikipedia updates • Contributing to 2018 Millennium Technolology Prize nomination 9.11.2018 80 2013 Malygin laboratory, 2013 https://twitter.com/rlpuu/status/509792544373620736 ALD 2014 2014
  81. 81. Puurunen, Aalto University CHEM-E5205, November 8, 2018 VPHA article 3 JVSTA 2017, DOI: 10.1116/1.4971389 Joint article, 62 co-authors Review Article: Recommended reading list of early publications on atomic layer deposition—Outcome of the “Virtual Project on the History of ALD” • List of 22 significant publications • Created by voting among VPHA contributors 9.11.2018 81
  82. 82. Puurunen, Aalto University CHEM-E5205, November 8, 2018 Ib 9.11.2018 82 DOI: 10.1149/08606.0003 ecst ECSarXiv, open acecss: 10.1149/osf.io/exyv3 ECST #Aimes2018 VPHA article 4
  83. 83. Puurunen, Aalto University CHEM-E5205, November 8, 2018 VPHA continues, final review to be written • More contributors  co-authors welcome! Tentative contents: • ALD history timeline – make by voting within VPHA? • Cite each early ALD publication (confirm first they are ALD) • List of doctoral theses on ALD, up to end of 2018 • List of ALD conferences, up to end of 2018? • List of ALD reviews, up to end of 2018? • Other contents? • Interested? Contact Riikka Puurunen or: info @ vph-ald.com 9.11.2018 83
  84. 84. Puurunen, Aalto University CHEM-E5205, November 8, 2018 aalto.fi Contact: firstname.lastname@aalto.fi Twitter: @rlpuu Aalto: aalto.fi/cmet/catalysis Prof. Riikka Puurunen Aalto University Photo:AaltoUniversity

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