T. Suntola: 30 years of ALD ALD 2004, Aug , 2004, University of Helsinki, Finland. 30 years of ALD Tuomo Suntola

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1 30 years of ALD Tuomo Suntola

2 Key tool for finding the ALE in 1974

3 Key tool for finding the ALE in 1974

4 Tool for the demonstration of ALE in 1974

5 ALE growth of ZnS in Aug/Sept 1974

6 ALE growth of ZnS in Aug/Sept 1974 Zn S

7 ALE growth of ZnS in Aug/Sept 1974 Zn S

8 ALE growth of ZnS in Aug/Sept 1974 Zn S

9 ALE growth of ZnS in Aug/Sept Hexagonal ZnS: monolayer 3.13 Å n=2.36 μm 320 C 0.4 4x10 5 torr 10 4 torr 2x10 2 torr 360 C Zn S 3x10 3 torr 100 C minutes 2 c/s

10 ALE growth of ZnS in Aug/Sept Hexagonal ZnS: monolayer 3.13 Å n=2.36 μm 320 C 0.4 4x10 5 torr 10 4 torr 2x10 2 torr 360 C Zn S 3x10 3 torr 100 C minutes 2 c/s

11 ALE growth of ZnS in Aug/Sept Hexagonal ZnS: monolayer 3.13 Å n=2.36 μm 1/3 x monolayer 320 C 0.4 4x10 5 torr 10 4 torr 2x10 2 torr 360 C Zn S 3x10 3 torr 100 C minutes 2 c/s

12 Milestones in ALE-ALD development Instrumentarium demonstration of ALE for ZnS (Instrumentarium)

13 Milestones in ALE-ALD development Instrumentarium Lohja demonstration of ALE for ZnS (Instrumentarium) travelling wave reactor (Lohja) exchange reactions for ZnS and oxides

14 T. Suntola: 30 years of ALD ALD 2004, Aug , 2004, University of Helsinki, Finland Milestones in ALE-ALD development Instrumentarium Lohja

15 Milestones in ALE-ALD development Instrumentarium Lohja substrate glass passivation layer (ion barrier) dielectric layers light emitting layer, ZnS(Mn) electrodes passivation layer black back layer Structure of thin film electroluminescent display EL- character module

16 Milestones in ALE-ALD development Instrumentarium Lohja demonstration of ALE for ZnS (Instrumentarium) travelling wave reactor (Lohja) exchange reactions for ZnS and oxides introduction of ALE-EL device performance

17 Milestones in ALE-ALD development Instrumentarium Lohja

18 Milestones in ALE-ALD development Instrumentarium Lohja Planar International Dr. Ralf Graeffe inspects the new large-area display in 1983

19 Milestones in ALE-ALD development Instrumentarium Lohja Planar International ALD superiority in EL: - very high dielectric strength of the dielectric layers (Al 2 O 3 + TiO 2 ) - pinhole free in large area - hexagonal ZnS; high efficiency, bright yellow color Evaporation, sputtering ALD

20 Milestones in ALE-ALD development Instrumentarium Lohja Planar International demonstration of ALE for ZnS (Instrumentarium) travelling wave reactor (Lohja) exchange reactions for ZnS and oxides introduction of ALE-EL device performance introduction of first ALE-EL product production line for flat-panel matrix displays P-250 >> P-400 reactors Commercial production of ALE-EL panels by Lohja > Planar

21 Milestones in ALE-ALD development Instrumentarium Lohja Planar International Ulf Stom and Tuomo Suntola look at a prototype of the new ELdisplay in 1984

22 Milestones in ALE-ALD development Instrumentarium Lohja Elcoteq Planar International demonstration of ALE for ZnS (Instrumentarium) travelling wave reactor (Lohja) exchange reactions for ZnS and oxides introduction of ALE-EL device performance introduction of first ALE-EL product production line for flat-panel matrix displays P-250 >> P-400 reactors Commercial production of ALE-EL panels by Lohja > Planar

23 Research activities in ALE-ALD Search for perfection in thin films for EL, ZnS & dielectrics ALE & precursor chemistry Search for perfection in III-V single crystals and supergrid structures Instumentarium, Lohja ALE and precursor chemistry, Helsinki University of Technology Helsinki University of Technology University & corporate groups in Japan University groups in the US

24 Research activities in ALE-ALD Superlattice by NEC, Japan

25 Research activities in ALE-ALD 2,0 Growth rate (ML/cycle) 1,5 (c) (a) (b) 1,0 0,5 (d) (e) Process temperature ( C) ALD Processing window for GaAS in different reactors

26 Research activities in ALE-ALD Visit to prof. Nishizawa s MLE-laboratory in Tohoku 1989

27 Research activities in ALE-ALD ALE conference in Helsinki 1990: From left: Prof. Konagai, Dr. Nykänen, Dr. Suntola, Prof. Niinistö, Prof. Nishizawa, Prof. & Mrs. Bedair

28 Milestones in ALE-ALD development Instrumentarium Lohja Elcoteq Planar International Microchemistry demonstration of ALE for ZnS (Instrumentarium) travelling wave reactor (Lohja) exchange reactions for ZnS and oxides introduction of ALE-EL device performance introduction of first ALE-EL product production line for flat-panel matrix displays P-250 >> P-400 reactors Commercial production of ALE-EL panels by Lohja > Planar F-120 reactors (Microchemistry) demonstration of ALE-CdTe solar cell performance introduction of ALE for catalytic surfaces

29 Research goals in ALE-ALD Search for perfection in thin films for EL, ZnS & dielectrics ALE & precursor chemistry Search for perfection in III-V single crystals and supergrid structures Heterogeneous catalysts, advanced surface chemistry Instumentarium, Lohja ALE and precursor chemistry, Helsinki University of Technology Helsinki University of Technology University & corporate groups in Japan University groups in the US Microchemistry, Helsinki University of Technology Colorado State University

30 Research goals in ALE-ALD Heterogeneous catalysts, advanced surface chemistry Microchemistry, Helsinki University of Technology (a) < 250 'C (b) > 300 'C Starting surface + TiCl4 + H2O HCl H H H H Cl Cl Cl Cl Cl O O Cl O O HCl + TiCl4 + H2O HCl HCl H O Si H H H H O O O O O Si Si Si Si Si Ti O O Si Si Ti O Si H H O O O Si Si Si Ti O O Si Si Ti O Si H H O O O Si Si Si Cl Si TiO2 H H H TiO2 nucl O O O O nucl Si Si Si Si Si Si Si Si H H O O Si Si O Si TiO 2 on silica by Suvi Haukka

31 Research goals in ALE-ALD Heterogeneous catalysts, advanced surface chemistry Microchemistry, Helsinki University of Technology precursor A precursor B surface spiecas/ support ZrCl 4 / SiO 2 WOCl 4 / Al 2 O 3 Ni(acac) 2 / Al 2 O 3 Cr(acac) 3 / SiO 2 Mg(thd) 2 / SiO 2 saturation density (atoms/nm 2 ) at top 1,44 0,04 1,44 at bottom 0,04 1,81 0,06 1,81 0,05 2,52 0,25 2,25 0,11 0,32 0,01 0,30 0,00 0,98 0,08 0,82 0,08 Uniformity of surface saturation in on porous catalyst carriers E-L. Lakomaa, M. Lindblad

32 Research goals in ALE-ALD Search for perfection in thin films for EL, ZnS & dielectrics ALE & precursor chemistry Search for perfection in III-V single crystals and supergrid structures Heterogeneous catalysts, advanced surface chemistry Instumentarium, Lohja ALE and precursor chemistry, Helsinki University of Technology Helsinki University of Technology University & corporate groups in Japan University groups in the US Microchemistry, Helsinki University of Technology Colorado State University Diffusion barriers and passivation layers enabling conformality in semiconductor devices Ultra-thin and high-k dielectrics for semiconductor devices Microchemistry, Helsinki University of Helsinki Semiconductor equipment manufacturers University groups Semiconductor manufacturers

33 Research goals in ALE-ALD Search for perfection in thin films for EL, ZnS & dielectrics ALE & precursor chemistry Search for perfection in III-V single crystals and supergrid structures Heterogeneous catalysts, advanced surface chemistry Instumentarium, Lohja ALE and precursor chemistry, Helsinki University of Technology Helsinki University of Technology University & corporate groups in Japan University groups in the US Microchemistry, Helsinki University of Technology Colorado State University Diffusion barriers and passivation layers enabling conformality in semiconductor devices Ultra-thin and high-k dielectrics for semiconductor devices Microchemistry, Helsinki University of Helsinki Semiconductor equipment manufacturers University groups Semiconductor manufacturers Molecular lay-up of oxide surfaces Prof. Aleskovski, St. Petersburg

34 Research goals in ALE-ALD 2500 A Al 2 O A Diffusion barriers and passivation layers enabling conformality in semiconductor devices Ultra-thin and high-k dielectrics for semiconductor devices Microchemistry, Helsinki University of Helsinki Semiconductor equipment manufacturers University groups Semiconductor manufacturers

35 Research goals in ALE-ALD Diffusion barriers and passivation layers enabling conformality in semiconductor devices Ultra-thin and high-k dielectrics for semiconductor devices Microchemistry, Helsinki University of Helsinki Semiconductor equipment manufacturers University groups Semiconductor manufacturers

36 Research goals in ALE-ALD SrTiO 3 Sr(C 5i Pr 3 H 2 ) 2 (THF) Diffusion barriers and passivation layers enabling conformality in semiconductor devices Ultra-thin and high-k dielectrics for semiconductor devices Microchemistry, Helsinki University of Helsinki Semiconductor equipment manufacturers University groups Semiconductor manufacturers

37 Milestones in ALE-ALD development Instrumentarium Lohja Elcoteq Planar International Microchemistry ASM Nanofin Picosun demonstration of ALE for ZnS (Instrumentarium) travelling wave reactor (Lohja) exchange reactions for ZnS and oxides introduction of ALE-EL device performance introduction of first ALE-EL product production line for flat-panel matrix displays P-250 >> P-400 reactors Commercial production of ALE-EL panels by Lohja > Planar F-120 reactors (Microchemistry) demonstration of ALE-CdTe solar cell performance introduction of ALE for catalytic surfaces F-450, F-850 reactors for large surfaces F-200 reactors for wafers Wafer cluster tool reactors (ASM) F-120 reactors (Nanofin) R-1 reactors (Picosun)

38 Development of ALD reactors F-120 reactors in Microchemistry in late 1980 s

39 Development of ALD reactors F-850 reactor, Microchemistry in 1998 Pulsar, ASM

40 Milestones in ALE-ALD development Instrumentarium Lohja Elcoteq Planar International Microchemistry ASM Nanofin Picosun demonstration of ALE for ZnS (Instrumentarium) travelling wave reactor (Lohja) exchange reactions for ZnS and oxides introduction of ALE-EL device performance introduction of first ALE-EL product production line for flat-panel matrix displays P-250 >> P-400 reactors Commercial production of ALE-EL panels by Lohja > Planar F-120 reactors (Microchemistry) demonstration of ALE-CdTe solar cell performance introduction of ALE for catalytic surfaces F-450, F-850 reactors for large surfaces F-200 reactors for wafers Wafer cluster tool reactors (ASM) F-120 reactors (Nanofin) R-1 reactors (Picosun)

41 Development of ALD reactors ALD R1 workstation by Picosun 2004

42 Moore s law for the complexity of IC s From 1960 to 1970, complexity is the number of components as initially described by Moore. After 1970, it was often cited as the number of bits in a DRAM or the number of transistors in a microprocessor. Source: Semiconductor International

43 Moore s law for the complexity of IC s Introduction of ALD From 1960 to 1970, complexity is the number of components as initially described by Moore. After 1970, it was often cited as the number of bits in a DRAM or the number of transistors in a microprocessor. Source: Semiconductor International

44 Moore s law for the complexity of IC s Introduction of ALD From 1960 to 1970, complexity is the number of components as initially described by Moore. After 1970, it was often cited as the number of bits in a DRAM or the number of transistors in a microprocessor. Source: Semiconductor International

45 Moore s law for the complexity of IC s Introduction of ALD ALD contribution to the learning curve From 1960 to 1970, complexity is the number of components as initially described by Moore. After 1970, it was often cited as the number of bits in a DRAM or the number of transistors in a microprocessor. Source: Semiconductor International

46 TUOMO SUNTOLA RECEIVES EUROPEAN SEMI AWARD FOR 2004 SEMI Honors Pioneer in Atomic Layer Deposition Techniques for Semiconductors paved the way for the development of nanoscale semiconductor devices Stanley Myers, President & CEO, SEMI. Walter Roessger, President, SEMI Europe, Tuomo Suntola, and Mart Graef, Chairman of the award committee

47 30 years of ALD Tuomo Suntola Thank you for your attention with wishes of inspiration, courage and success in your work on the ALD