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ALD for Industry 2019: Slides of invited tutorial by Prof. Riikka Puurunen

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Invited tutorial given by Prof. Riikka Puurunen at the ALD for Industry event, Berlin, 19.3.2019.

Video record taken with Panopto, (to be) shared in Youtube, you find the links e.g. through the blog post: https://blogs.aalto.fi/catprofopen/2019/03/19/prof-puurunen-invited-tutorial-at-ald-for-industry-berlin/

Title: ALD Technology – Introduction, History & Principles
Abstract: This tutorial keynote will introduce atomic layer deposition (ALD) – a variant of chemical vapor deposition - and fundamental principles and concepts related it from a generic viewpoint applicable to any ALD process and reactor. The early history and current usage of ALD are briefly overviewed: who made the first experiments, when, and why? How has the view on the history of ALD evolved? Where is ALD now used, by whom, and why? ALD relies on repeated chemical adsorption steps from gas phase to surface. The status of understanding the adsorption steps of ALD films will be presented and discussed using mainly the archetype trimethylaluminium-water ALD process as example and 3D conformality modelling as additional vehicle. Plenty of links to further sources of information will be included in this keynote presentation.

A related SlideShare: placeholder, where I meant to update the slides afterwards, but this did not succeed as the reupload function has been removed: https://www.slideshare.net/RiikkaPuurunen/ald-for-industry-2019-invited-tutorial-by-prof-riikka-puurunen/RiikkaPuurunen/ald-for-industry-2019-invited-tutorial-by-prof-riikka-puurunen. The update was waiting for the publication of the following review article, which was still in press when giving the presentation: Cremers, Puurunen, Dendooven, Appl. Phys. Rev. (2019), https://doi.org/10.1063/1.5060967. Article published 4.4.2019: Applied Physics Reviews 6, 021302 (2019)

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ALD for Industry 2019: Slides of invited tutorial by Prof. Riikka Puurunen

  1. 1. Puurunen, Tutorial, ALD for Industry, Berlin, 19.3.2019 Invited tutorial ALD Technology – Introduction, History & Principles Prof. Riikka Puurunen, Aalto University School of Chemical Engineering ALD for Industry, Berlin, March 19-20, 2019
  2. 2. Puurunen, Tutorial, ALD for Industry, Berlin, 19.3.2019 Atomic layer deposition (ALD) 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 (scheme: Puurunen) George, Chem. Rev. 110 (2010) 111–131. DOI: 10.1021/cr900056b  Time 
  3. 3. Puurunen, Tutorial, ALD for Industry, Berlin, 19.3.2019 20.3.2019 3 Associate professor, Catalysis Sci. & Tech., Aalto University 1999-2002, Catalysis, D. Sc. (Tech.) HUT 1998, M.Sc., HUT 2003-2004, postdoc, microelectronics, IMEC, Belgium 2004-2017, MEMS (Senior) researcher, project manager, VTT, Finland 2017  (ALD) career overview, Riikka Puurunen 2013 , Virtual Project on the History of ALD publications: 57, H-index 24 2005, review in J. App. Phys., >1300 citations 2015 , ALD film conformality test concept ? times cited: 3502
  4. 4. Puurunen, Tutorial, ALD for Industry, Berlin, 19.3.2019 Outline • (Very brief introduction of topic and speaker) 1. On the history of ALD: who, when, why, what? 2. Surface chemistry of ALD – Terminology, mechanisms, conformality analysis 3. Surface chemistry of ALD – Some progress notes 4. Where ALD used? 5. Conclusion • (Additional material) #ALDep Panopto
  5. 5. Puurunen, Tutorial, ALD for Industry, Berlin, 19.3.2019 On the history of ALD: Who, when, why, what?
  6. 6. Puurunen, Tutorial, ALD for Industry, Berlin, 19.3.2019 ALD discovered independently twice Atomic layer epitaxy (ALE) 1974  Molecular Layering (ML) ? ~1965  Dr. Tuomo S. Suntola Espoo, Finland Photo:RiikkaPuurunen,27.7.2017 Prof. Valentin B. Aleskovskii Prof. Stanislav I. Koltsov St. Petersburg, USSR / Russia https://en.wikipedia.org/wiki/Tuomo_Suntola, https://en.wikipedia.org/wiki/Valentin_Aleskovsky
  7. 7. Puurunen, Tutorial, ALD for Industry, Berlin, 19.3.2019 TechnologyAcademyFinland2019
  8. 8. Puurunen, Tutorial, ALD for Industry, Berlin, 19.3.2019 Essay: Puurunen, Chem. Vap. Deposition 20 (2014) 332-344. https://doi.org/10.1002/cvde.201402012 1974 Electroluminescent displays
  9. 9. Puurunen, Tutorial, ALD for Industry, Berlin, 19.3.2019 1987 Suntola: Microchemistry F-120 Small research reactors, solar panels (CdTe), catalysts (powder ALD),   microelectronics MRS 1994 Essay: Puurunen, Chem. Vap. Deposition 20 (2014) 332-344. https://doi.org/10.1002/cvde.201402012 Review: Parsons et al. J. Vac. Sci. Technol. A 31 (2013) 050818. https://doi.org/10.1116/1.4816548
  10. 10. Puurunen, Tutorial, ALD for Industry, Berlin, 19.3.2019 Prof.MarkkuLeskelä’sretirementlecture,6.3.2019 UniversityofHelsinki, PhotobyRiikkaPuurunen • Helsinki University of Technology (Espoo)  Prof. Niinistö, Leskelä • (Part of) research moved to Univ. of Helsinki (Helsinki) with professorship of Leskelä • Three-colour displays made by filtering from ZnS:Mn yellow (not new new chemistry) • Colour development brought significant expertise in ALD process development Essay: Puurunen, Chem. Vap. Deposition 20 (2014) 332-344. https://doi.org/10.1002/cvde.201402012 (Full) colour ALE-EL display? ? 
  11. 11. Puurunen, Tutorial, ALD for Industry, Berlin, 19.3.2019 Suntola, Mater. Sci. Reports 4 (1989) 261–312. https://doi.org/10.1016/S0920-2307(89)80006-4 1989 1. Finland 2. Japan 3. USA 4. …
  12. 12. Puurunen, Tutorial, ALD for Industry, Berlin, 19.3.2019 Essays in Chem. Vap. Deposition On Atomic Layer Epitaxy, by Puurunen On Molecular Layering, by Malygin et al. Puurunen, Chem. Vap. Deposition 20 (2014) 332-344. https://doi.org/10.1002/cvde.201402012 Malygin et al., Chem. Vap. Deposition 21 (2015) 216-240. https://doi.org/10.1002/cvde.201502013 2015 2004, European SEMI Award at the Munich Electronics Show 2004, In the winter garden of the St. Petersburg State University … conference “Chemistry of highly organized substances and fundamental scientific basics of nanotechnology“ 2014
  13. 13. Puurunen, Tutorial, ALD for Industry, Berlin, 19.3.2019 (review article) V. B. Aleskovskii, “ Chemistry and technology of solids,” Zh. Prikl. Khim. 47, 2145 (1974) V. B. Aleskovskii [J. Appl. Chem. USSR 47, 2207 (1974)]. 1974
  14. 14. Puurunen, Tutorial, ALD for Industry, Berlin, 19.3.2019 • (10.1149/08606.0003ecst, Ref. 32) V. B. Aleskovskii and S. I. Koltsov, “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, English title translated in the VPHA. Original title in Russian: “Некоторые закономерности реакций молекулярного наслаивания”). • Discussed in Section III.B.1 in: Ahvenniemi et al. (62 authors), J. Vac. Sci. Technol. A 35 (2017) art. 010801; https://doi.org/10.1116/1.4971389. [Included as Ref. 51: V. B. Aleskovskii and S. I. Koltsov, “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).] 1965 First written record of ”Molecular Layering” (?)
  15. 15. Puurunen, Tutorial, ALD for Industry, Berlin, 19.3.2019 Applications of Molecular Layering - ALD? https://commons.wikimedia.org/wiki/File:Russian-Matroshka_no_bg.jpg It’s like…
  16. 16. Puurunen, Tutorial, ALD for Industry, Berlin, 19.3.2019 Visions of Aleskovskii, 1974 Entry #9 in https://doi.org/10.1116/1.4971389 (VPHA): ” The review reflects the vision of the Aleskovskii group(s), reviewing advances made by 1974 and predicting what could be achieved by molecular layering. Aleskovskii presents an early suggestion of surface-selective deposition: “if necessary, part of its <i.e., support's> surface is shielded by flat (monolayer) or relief coating in the form of specified pattern.” He also notices the possibility of using templates for growth “at the end of the synthesis, the support is removed, if necessary, by chemical or mechanical methods.” He notices the possibility of fine regulation of pore size in sorbents and concludes that ML works in a similar manner on single crystals (e.g., silicon, germanium), porous materials (e.g., silica gel, carbon), and fine powders (e.g., talc, kaolin, aerosil). He notices, using several examples, that four to six “monolayers” (the name he used for ML cycles) are needed for the material to reach the properties that the solid material would have. He describes the deposition of ternary materials (TiO2 and POx combined as a mixed oxide) where the sequence of depositions in total of four ALD cycles (14 possible combinations of cycles, all synthesized) influences the catalytic activity of the system. Striking is Aleskovskii's comment on the potential applications of ML in the down-scaling of semiconductor technology: “The route to further miniaturization of microelectronic devices and to molecular electronics is evident.”” V. B. Aleskovskii, “ Chemistry and technology of solids,” Zh. Prikl. Khim. 47, 2145 (1974) [J. Appl. Chem. USSR 47, 2207 (1974)]. Ahvenniemi et al. (62 authors, alphabetical order), 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 35 (2017) art. 010801; https://doi.org/10.1116/1.4971389
  17. 17. Puurunen, Tutorial, ALD for Industry, Berlin, 19.3.2019 Malygin et al., Chem. Vap. Deposition 21 (2015) 216-240. https://doi.org/10.1002/cvde.201502013 http://vph-ald.com/UploadedPublications/Malygin-ALD2016-25July.pdf ALD reactor cell with in situ ellipsometry 1975 Reactors, in-situ analysis, sorbents, catalysts, coatings to lower sintering temperature, humidity indicators, semiconductor-related tests,… Thin film reactor 1977 Powder processing 1987 Malygin: >600 papers, >70 patent certificates, … (ALD 2016 info)
  18. 18. Puurunen, Tutorial, ALD for Industry, Berlin, 19.3.2019 (Abstract) This paper … presents a recommended reading list of early ALD publications, created collectively by the VPHA participants through voting. The list contains 22 publications from Finland, Japan, Soviet Union, United Kingdom, and United States. Up to now, a balanced overview regarding the early history of ALD has been missing; the current list is an attempt to remedy this deficiency. J. Vac. Sci. Technol. A 35 (2017) art. 010801; https://doi.org/10.1116/1.4971389 2017, 62 authors
  19. 19. Puurunen, Tutorial, ALD for Industry, Berlin, 19.3.2019 Time to write another review? VPHA collaboration planned, Open Science; more volunteers welcome vph-ald.com
  20. 20. Puurunen, Tutorial, ALD for Industry, Berlin, 19.3.2019 Surface chemistry of ALD – Terminology, mechanisms, conformality analysis
  21. 21. Puurunen, Tutorial, ALD for Industry, Berlin, 19.3.2019 Definition of ALD – is there one? ” ALD can be defined as a film deposition technique that is based on the sequential use of self- terminating gas–solid reactions” Puurunen, 2005 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
  22. 22. Puurunen, Tutorial, ALD for Industry, Berlin, 19.3.2019 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
  23. 23. Puurunen, Tutorial, ALD for Industry, Berlin, 19.3.2019 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
  24. 24. Puurunen, Tutorial, ALD for Industry, Berlin, 19.3.2019 ALD: (simplified) variant of CVD Image: Pedersen, H. & Elliott, S.D. Theor Chem Acc 133 (2014) 1476. https://doi.org/10.1007/s00214-014-1476-7 x in ALD: gas phase reactions excluded, (ideally) irreversible reactions CVD: continuous flow ALD: separate pulsing of reactant vapors xadsorption x
  25. 25. Puurunen, Tutorial, ALD for Industry, Berlin, 19.3.2019 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 CVD 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
  26. 26. Puurunen, Tutorial, ALD for Industry, Berlin, 19.3.2019 >700 ALD reactant - co-reactant pairs 26 H2O NH3 H2S Non-metal co-reactants, “thermal” ALD Energy-enhanced ALD 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, Appl. Phys. 97 (2005) 121301. https://doi.org/10.1063/1.1940727 Miikkulainen, Leskelä, Ritala, Puurunen, J. Appl. Phys. 113 (2013) 021301. http://dx.doi.org/10.1063/1.4757907. O3 … Metal reactant type
  27. 27. Puurunen, Tutorial, ALD for Industry, Berlin, 19.3.2019 Chemisorption mechanisms typical in ALD Fig. 11, Puurunen, J. Appl. Phys. 97 (2005) 121301. https://doi.org/10.1063/1.19 40727 open access pdf Dissociation L Reaction: MLn + surface L/M < n L/M = n L/M = n
  28. 28. Puurunen, Tutorial, ALD for Industry, Berlin, 19.3.2019 Chemisorption mechanisms - 2 Barry, Teplyakov, Zaera, Acc. Chem. Res. 51 (2018) 800–809. DOI: 10.1021/acs.accounts.8b00012 (graphical summary; solution-related parts removed) Note mechanistic difference of dissociation compared with J. Appl. Phys. 97 (2005) 121301. https://doi.org/10.10 63/1.1940727 L L
  29. 29. Puurunen, Tutorial, ALD for Industry, Berlin, 19.3.2019 Monolayer – three different Puurunen, J. Appl. Phys. 97 (2005) 121301. https://doi.org/10.1063/1.1940727 open access pdf Chemisorbed monolayer Physisorbed monolayer Monolayer of ALD-grown material GPC typically <50% of a monolayer
  30. 30. Puurunen, Tutorial, ALD for Industry, Berlin, 19.3.2019 ALD window Suntola, ”Atomic layer epitaxy” Mater. Sci. Rep. 4 (1989) 261-312. DOI: 10.1016/S0920-2307(89)80006-4 Explanations (shortened) L1: condensation to be prevented L2: activation energy to exceed H1: decomposition H2: re-evaporation GPC variations within an ALD window Puurunen, J. Appl. Phys. 97 (2005) 121301. https://doi.org/10.1063/1.1940727 open access pdf For Suntola’s newer views, see: http://aldhistory.blogspot.com/2019/03/mtp2018-suntola-photos-from-May23-2018.html, accessed 16.3.2019 #ALDepWindow
  31. 31. Puurunen, Tutorial, ALD for Industry, Berlin, 19.3.2019 Conformality Cremers, Puurunen, Dendooven, Appl. Phys. Rev. (2019) in press, DOI: 10.1063/1.5060967 in atomic layer deposition: Current status overview of analysis and modelling To analyse: ”Infinite” lateral high-aspect ratio test structures (LHAR) In press Not conformal Conformal
  32. 32. Puurunen, Tutorial, ALD for Industry, Berlin, 19.3.2019 (Hole-)equivalent aspect ratio (EAR) Cremers, Puurunen, Dendooven, Appl. Phys. Rev. 2019, DOI:10.1063/1.5060967 Ylilammi, Ylivaara, Puurunen, J. Appl. Phys. 123, 205301 (2018); DOI: 10.1063/1.5028178 50% pene- tration depth (PD50%) 0.5 In press
  33. 33. Puurunen, Tutorial, ALD for Industry, Berlin, 19.3.2019 EAR Cremers, Puurunen, Dendooven, Appl. Phys. Rev. 2019, DOI:10.1063/1.5060967 [Comparison before EAR: Mattinen et al., Langmuir 32 (2016) 10559–10569, doi:10.1021/acs.langmuir.6b03007] In press PD50%
  34. 34. Puurunen, Tutorial, ALD for Industry, Berlin, 19.3.2019 Saturation profile  ALD observable? Yanguas-Gil, 2017 Thickness(nm) Unpublished data, PillarHall LHAR3  Should the thickness be normalized?
  35. 35. Puurunen, Tutorial, ALD for Industry, Berlin, 19.3.2019 Surface chemistry of ALD – Some progress notes
  36. 36. Puurunen, Tutorial, ALD for Industry, Berlin, 19.3.2019 Some surface chemistry questions 1. Which material is grown? 2. Is the growth self-terminating  is it ALD? 3. What is the temperature range where ALD growth occurs? ( ALD window?) 4. How much material is grown in an ALD cycle; what is the GPC? 5. Which gaseous byproducts form and when? 6. (Do byproducts re-adsorb on the surface?) 7. Which surface species are formed? How much of them? 8. Through which mechanisms does (reactive) adsorption take place? What defines GPC? 9. How does the GPC vary within in the ALD window, and why? 10.Are there impurities in the film & (how) do they affect the film growth? 11.How fast are the surface reactions; kinetics of growth? Can you think of more questions? https://www.atomiclimits.com/2019/02/12/atomic-layer-deposition-process-development-10-steps-to- successfully-develop-optimize-and-characterize-ald-recipes/  recommended post on process development
  37. 37. Puurunen, Tutorial, ALD for Industry, Berlin, 19.3.2019 Prototype ALD process: trimethylaluminium/water  Al2O3 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 #TMAwater
  38. 38. Puurunen, Tutorial, ALD for Industry, Berlin, 19.3.2019 ALD window: r.t. up to ~300°C (wide!) 38 300°C 327°C 350°C 250°C200°C150°C80°C Puurunen et al., Phys. Chem. Chem. Phys. 3 (2001) 1093. http://dx.doi.org/10.1039/B007249O Review: Puurunen, J. Appl. Phys. 97 (2005) 121301; https://doi.org/10.1063/1.1940727 & references therein Surface saturates with reaction products No saturation: Reactant decomposes AlMe3 reaction temperature (K) on alumina Carbonatoms(nm-2)
  39. 39. Puurunen, Tutorial, ALD for Industry, Berlin, 19.3.2019 GPC? • GPC ~0.1 nm • GPC ~30% of monolayer • GPC decreases with temperature Review: Puurunen, J. Appl. Phys. 97 (2005) 121301; https://doi.org/10.1063/1.1940727 & references therein
  40. 40. Puurunen, Tutorial, ALD for Industry, Berlin, 19.3.2019 “Correlation between the growth-per-cycle and the surface hydroxyl group concentration in the atomic layer deposition of aluminum oxide from trimethylaluminum and water” Puurunen, Appl. Surf. Sci. 245 (2005) 6-10. DOI:10.1016/j.apsusc.2004.10 .003 • ~All OH groups react & release a ligand (CH4) • Reaction stops because of steric hindrance L/M Ligand exchange Dissociation/ association
  41. 41. Puurunen, Tutorial, ALD for Industry, Berlin, 19.3.2019 Kinetics? Sticking probability? Slope of the leading edge of saturation profile related to reaction kinetics Knoops et al., J. Electrochem. Soc. 157 (2010) G241-G249. DOI: 10.1149/1.3491381 Cremers, Puurunen, Dendooven, Appl. Phys. Rev. (2019) in press, DOI: 10.1063/1.5060967
  42. 42. Puurunen, Tutorial, ALD for Industry, Berlin, 19.3.2019 Kinetics? Sticking probability? Cremers, Puurunen, Dendooven, Appl. Phys. Rev. (2019) in press, DOI: 10.1063/1.5060967 In press
  43. 43. Puurunen, Tutorial, ALD for Industry, Berlin, 19.3.2019 Langmuir adsorption model in sticking probability derivation 20.3.2019 43 https://en.wikipedia.org/wiki/Langmuir_adsorption_ model#/media/File:Langmuir_Adsorption_Model.jpg Ylilammi, Ylivaara, Puurunen, J. Appl. Phys. 123, 205301 (2018); DOI: 10.1063/1.5028178 https://en.wikipedia.org/wiki/Langmuir_adsorption_model, accessed 13.9.2018 • Flat surface & isothermal conditions • Surface sites are equal • Adsorbed species do not interact • Adsorption & desorption are elementary processes Cremers, Puurunen, Dendooven, Appl. Phys. Rev. (2019) in press, DOI: 10.1063/1.5060967 Association
  44. 44. Puurunen, Tutorial, ALD for Industry, Berlin, 19.3.2019 Real ALD is more complex 20.3.201944 Langmuir adsorption reality Association Ligand exchange Dissociation Association No adsorbate-adsorbate interactions Adsorbate-adsorbate interactions
  45. 45. Puurunen, Tutorial, ALD for Industry, Berlin, 19.3.2019 Where ALD used?
  46. 46. Puurunen, Tutorial, ALD for Industry, Berlin, 19.3.2019 VPHA poster submission ALD 2019 On the list collection of doctoral theses on ALD worldwide http://aldhistory.blogspot.com/2019/02/vpha-communication-ald2019-abstract-submitted.html https://twitter.com/rlpuu/status/1096385902971113472 • Japan? Australia? • Germany (more)? • …?
  47. 47. Puurunen, Tutorial, ALD for Industry, Berlin, 19.3.2019 Conclusion
  48. 48. Puurunen, Tutorial, ALD for Industry, Berlin, 19.3.2019 Conclusion • ALD discovered twice; history (still) not in general well presented in books / review articles • 1974, Initially industrial; electroluminescent displays • 1960s, Academic; wide scope • Basics of ALD ~well understood; views & terminology evolving • Recent progress in conformality measurement & analysis • Opportunities to create fundamental understanding on ALD
  49. 49. Puurunen, Tutorial, ALD for Industry, Berlin, 19.3.2019 Additional materials and links • JAP 2005 review as teaching material & Do not mix up … • Some interview links • Reviews on surface chemistry of ALD • ALD-related blogs • About this tutorial presentation and the author • Links to Panopto lecture capture & Catalysis Professor’s Open blog
  50. 50. Puurunen, Tutorial, ALD for Industry, Berlin, 19.3.2019 JAP 2005 review as teaching material & Do not mix up …
  51. 51. Puurunen, Tutorial, ALD for Industry, Berlin, 19.3.2019 The 2005 review by Puurunen as teaching material 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 in several groups
  52. 52. Puurunen, Tutorial, ALD for Industry, Berlin, 19.3.2019 Do not mix up: Molecular Layering and Molecular Layer Deposition • Molecular Layering: old Russian name for ALD • Molecular Layer Deposition: variant of ALD where the reactants are organic compounds instead of metal compunds
  53. 53. Puurunen, Tutorial, ALD for Industry, Berlin, 19.3.2019 Do not mix up: Growth rate (e.g. nm/cyc) & Growth rate (e.g. nm/min) • Growth rate (nm/cyc) in ALD publications: same as GPC (nm) • Growth rate (nm/min) in CVD publications: kinetic quantity
  54. 54. Puurunen, Tutorial, ALD for Industry, Berlin, 19.3.2019 Some interview links
  55. 55. Puurunen, Tutorial, ALD for Industry, Berlin, 19.3.2019 Where ALD? Aalto University Magazine October 2018, https://issuu.com/aaltouniversity/docs/aum_23_en_pdf-150dpi/24
  56. 56. Puurunen, Tutorial, ALD for Industry, Berlin, 19.3.2019 Interviews of Suntola https://twitter.com/icallan/status/1087754240871809024 http://peoplebehindthescience.libsyn.com/461-atomic- layer-deposition-developer-fundamental-physicist-and- scientific-philosopher-dr-tuomo-suntola
  57. 57. Puurunen, Tutorial, ALD for Industry, Berlin, 19.3.2019 Interviews of Suntola – in Finnish • https://twitter.com/rlpuu/status/11 02506280973942784 • https://areena.yle.fi/1-4452599 Tiedeykkönen Millennium-palkinto 2018: Tuomo Suntolan nerokas ALD mahdollisti nykyiset mikroprosessorit
  58. 58. Puurunen, Tutorial, ALD for Industry, Berlin, 19.3.2019 Reviews on surface chemistry of ALD
  59. 59. Puurunen, Tutorial, ALD for Industry, Berlin, 19.3.2019 Reviews on surface chemistry of ALD From: http://vph-ald.com/VPHAopenfiles.html ( list of ~200 reviews) Suntola, Appl. Surf. Sci. 100/101 (1996) 391–398. http://doi.org/10.1016/0169-4332(96)00306-6 • Surface chemistry of materials deposition at atomic layer level George et al., J. Phys. Chem. 100 (1996) 13121–13131. http://doi.org/10.1016/0169-4332(96)00306-6 • Surface chemistry for atomic layer growth Puurunen, J. Appl. Phys. 97 (2005) 121301 (Appl. Phys. Rev.). https://doi.org/10.1063/1.1940727 • Surface chemistry of atomic layer deposition: a case study for the trimethylaluminum/water process Zaera, J. Mater. Chem. 18 (2008) 3521–3526. http://dx.doi.org/10.1039/B803832E • The surface chemistry of thin film atomic layer deposition (ALD) processes for electronic device manufacturing Zaera, J. Phys. Chem. Lett. 3 (2012) 1301–1309. http://doi.org/10.1021/jz300125f • The surface chemistry of atomic layer depositions of solid thin films Probably there are more… e.g. Knapas & Ritala, Crit. Rev. Solid State Mater. Sci. 38 (2013) 167-202. http://doi.org/10.1080/10408436.2012.693460 In Situ Studies on Reaction Mechanisms in Atomic Layer Deposition
  60. 60. Puurunen, Tutorial, ALD for Industry, Berlin, 19.3.2019 ALD-related blogs
  61. 61. Puurunen, Tutorial, ALD for Industry, Berlin, 19.3.2019 BALD Engineering Blog http://www.blog.baldengineering.com/, accessed 16.3.2019 By Dr. Jonas Sundqvist
  62. 62. Puurunen, Tutorial, ALD for Industry, Berlin, 19.3.2019 Atomic Limits Blog By Prof. Erwin Kessels and coworkers https://www.atomiclimits.com/, accessed 16.3.2019 @atomiclimits
  63. 63. Puurunen, Tutorial, ALD for Industry, Berlin, 19.3.2019 ALD History Blog http://aldhistory.blogspot.com/, accessed 16.3.2019 By Prof. Riikka Puurunen @aldhistoryblog
  64. 64. Puurunen, Tutorial, ALD for Industry, Berlin, 19.3.2019 About this tutorial presentation and the author
  65. 65. Puurunen, Tutorial, ALD for Industry, Berlin, 19.3.2019 Abstract, Prof Puurunen Keynote: ALD Technology – Introduction, History & Principles ALD for Industry, Berlin, 19.-20.3.2019 This tutorial keynote will introduce atomic layer deposition (ALD) – a variant of chemical vapor deposition - and fundamental principles and concepts related it from a generic viewpoint applicable to any ALD process and reactor. The early history and current usage of ALD are briefly overviewed: who made the first experiments, when, and why? How has the view on the history of ALD evolved? Where is ALD now used, by whom, and why? ALD relies on repeated chemical adsorption steps from gas phase to surface. The status of understanding the adsorption steps of ALD films will be presented and discussed using mainly the archetype trimethylaluminium-water ALD process as example and 3D conformality modelling as additional vehicle. Plenty of links to further sources of information will be included in this keynote presentation.
  66. 66. Puurunen, Tutorial, ALD for Industry, Berlin, 19.3.2019 Description: Riikka Puurunen, Associate professor, Catalysis Science and Technology, Aalto University School of Chemical Engineering Prof. Riikka Puurunen has worked with ALD since 1998 at different locations (Microchemistry, HUT, IMEC, VTT, Aalto Univ) and with various applications (catalysis, microelectronics and MEMS). Prof. Puurunen has written several high-impact review articles, which have among other things contributed to the acceptance of the trimethylaluminium-water process as “model” or “archetype” ALD process; that a “periodic table of ALD materials” has been created; and that the view on the history of ALD has been renewed with another independent discovery. Prof. Puurunen has also envisioned and realized new types of lateral microscopic conformality test structures that enable exploration of ALD fundamentals new ways.
  67. 67. Puurunen, Tutorial, ALD for Industry, Berlin, 19.3.2019 Tutorial programme 19.3.2019
  68. 68. Puurunen, Tutorial, ALD for Industry, Berlin, 19.3.2019 aalto.fi Panopto lecture capture: https://aalto.cloud.panopto.eu/Panopto/Pages/Viewer.aspx?id=e05d5cde- 6e6c-4893-807d-aa150110c0e3 Related blog post in Catalysis Professor’s Open: https://blogs.aalto.fi/catprofopen/2019/03/19/prof-puurunen-invited-tutorial- at-ald-for-industry-berlin/

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