ALD method and apparatus

• US 7,250,083 B2
• Filed: 03/07/2003
• Issued: 07/31/2007
• Est. Priority Date: 03/08/2002
• Status: Active Grant

• Current Assignee: Sundew Technologies LLC
• Original Assignee: Sundew Technologies LLC
• Inventors: Sneh, Ofer
• Primary Examiner(s): Gupta; Yogendra N.
• Assistant Examiner(s): SONG, MATTHEW J
• Application Number:
  US10/384,504
• Publication Number:
  US 20030168001A1
• Time in Patent Office: 1,607 Days
• Field of Search: 117/84, 117/88, 117/89, 117/91, 117/93, 117/99, 117/102, 117/105
• US Class Current: 117/84
• CPC Class Codes: C23C 16/02 Pretreatment of the material to be coated C23C16/04 takes precedence
• CPC Class Codes: C23C 16/14 Deposition of only one other metal element
• CPC Class Codes: C23C 16/306 AII BVI compounds, where A is Zn, Cd or Hg and B is S, Se or Te
• CPC Class Codes: C23C 16/34 Nitrides C23C16/303 takes precedence
• CPC Class Codes: C23C 16/40 Oxides
• CPC Class Codes: C23C 16/402 Silicon dioxide
• CPC Class Codes: C23C 16/403 of aluminium, magnesium or beryllium
• CPC Class Codes: C23C 16/405 of refractory metals or yttrium
• CPC Class Codes: C23C 16/45529 specially adapted for making a layer stack of alternating different compositions or gradient compositions
• CPC Class Codes: C23C 16/45534 Use of auxiliary reactants other than used for contributing to the composition of the main film, e.g. catalysts, activators or scavengers

Abstract

A method and an apparatus for executing efficient and cost-effective Atomic Layer Deposition (ALD) at low temperatures are presented. ALD films such as oxides and nitrides are produced at low temperatures under controllable and mild oxidizing conditions over substrates and devices that are moisture- and oxygen-sensitive. ALD films, such as oxides, nitrides, semiconductors and metals, are efficiently and cost-effectively deposited from conventional metal precursors and activated nonmetal sources. Additionally, substrate preparation methods for optimized ALD are disclosed.

Claims

1. An ALD method for depositing a layer on a surface of a substrate, comprising conducting a plurality of ALD cycles in a reaction chamber containing said substrate, wherein an ALD cycle comprises a saturating chemical dosage stage and a saturating CRISP stage, said saturating CRISP stage comprising;

introducing a plurality of CRISP reactants into said reaction chamber;

reacting said plurality of CRISP reactants in a continuous and non-saturating reaction which consumes said plurality of reactants and generates a volatile by product and an intermediate molecular fragment; and

reacting said intermediate molecular fragment with an intermediate ALD surface in a saturating fragment-surface reaction.

2. A method as in claim 1 wherein said plurality of reactants consists of two of said reactants.

3. A method as in claim 1, further comprising conducting a deactivation stage after said saturating fragment-surface reaction.

4. A method as in claim 1 wherein said intermediate ALD surface is a first intermediate ALD surface, and said fragment-surface reaction generates a second intermediate ALD surface, wherein said saturating chemical dosage stage comprises:

introducing a metal ALD precursor;

reacting said ALD precursor with said second intermediate ALD surface in a saturating metal precursor-surface reaction to generate an intermediate ALD surface.

5. A method as in claim 4 wherein said metal precursor-surface reaction generates a first intermediate ALD surface.

6. A method as in claim 4 wherein said metal precursor comprises an atom selected from the group consisting of Al, Si, Ti, Ni, Cu, Zn, Ga, Ge, Y, Zr, Nb, Mo, Ru, In, Sn, Hf, Ta, and W.

7. A method as in claim 4 for depositing a layer comprising TiN ALD films wherein:

said metal precursor in said saturating chemical dosage stage is TiCl₄;

a first CRISP reactant in said saturating CRISP stage is SiH₄; and

a second CRISP reactant in said saturating CRISP stage is NF₃.

8. A method as in claim 4 for depositing a layer comprising a ZrO₂ ALD film wherein:

said metal precursor in said saturating chemical dosage stage is selected from the group consisting of ZrCl₄ and Zr(O-t-C₄H₃)₄;

a first CRISP reactant in said saturating CRISP stage is selected from the group consisting of O, and B₂H₆; and

a second CRISP reactant in said saturating CRISP stage is selected from the group consisting of C₂H₄, C₈H₁₀, CH₃OH, C₂H₃OH, i-C₃H₇OH, t-C₄H₉OH, and F₂O.

9. A method as in claim 4 for depositing a layer comprising an HfO₂ ALD film wherein:

said metal precursor in said saturating chemical dosage stage is selected from the group consisting of HfCl₄ and Hf(O-t-C₄H₉)₄;

a first CRISP reactant in said saturating CRISP stage is selected from the group consisting of O₃ and B₂H₆; and

a second CRISP reactant in said saturating CRISP stage is selected from the group consisting of C₂H₄, C₈H₁₀, CH₃OH, C₂H₃OH, i-C₃H₇OH, t-C₄H₉OH , and F₂O.

10. A method as in claim 4 for depositing a layer comprising a SiO₂ ALD film wherein:

said metal precursor in said saturating chemical dosage stage is selected from the group consisting of Si(OC₂O₅)₄, SiCl₄, and SiH₂Cl₂;

a first CRISP reactant in said saturating CRISP stage is selected from the group consisting of O₃ and B₂H₆; and

a second CRISP reactant in said saturating CRISP stage is selected from the group consisting of C₂H₄, C₈H₁₀, CH₃OH, C₂H₃OH, i-C₃H₇OH, t-C₄H₉OH , and F₂O.

11. A method as in claim 4 for depositing a layer comprising a Ta₂O₅ ALD film wherein:

said metal precursor in said saturating chemical dosage stage is selected from the group consisting of Ta(OC₂O₅)₅ and TaCl₅;

a first CRISP reactant in said saturating CRISP stage is selected from the group consisting of O₃ and B₂H₆; and

a second CRISP reactant in said saturating CRISP stage is selected from the group consisting of C₂H₄, C₈H₁₀, CH₃OH, C₂H₅OH, i-C₃H₇OH, t-C₄H₉OH , and F₂O.

12. A method as in claim 4 for depositing a layer comprising a copper ALD film wherein:

said metal precursor in said saturating chemical dosage stage is selected from the group consisting of Cu(tfac)₂ and Cu(hfac)₂;

a first CRISP reactant in said situating CRISP stage is selected from the group consisting of SiH₄, SiH₂Cl₂, B₂H₆, Si₂H₆, C₈H₁₀, and CH₃OH; and

a second CRISP reactant in said saturating CRISP stage is selected from the group consisting of F₂, F₂O, NF₃, ClF₃, and O₃.

13. A method as in claim 4 for depositing a layer comprising a W ALD film wherein:

said metal precursor in said saturating chemical dosage stage is selected from the group consisting of WF₆ and WCl₆;

a first CRISP reactant in said saturating CRISP stage is selected from the group consisting of SiH₄, SiH₂Cl₂B₂H₆, Si₂H₆, C₈H₁₀, and CH₃OH; and

a second CRISP reactant in said saturating CRISP stage is selected from the group consisting of F₂, F₂O, NF₃, ClF₃, and O₃.

14. A method as in claim 4 for depositing a layer comprising a Mo ALD film wherein:

said metal precursor in said saturating chemical dosage stage is selected from the group consisting of MoCl₅;

a first CRISP reactant in said saturating CRISP stage is selected from the group consisting of SiH₄, SiH₂Cl₂, B₂H₆, C₈H₁₀, and CH₃OH; and

a second CRISP reactant in said saturating CRISP stage is selected from the group consisting of F₂, F₂O, NF₃, ClF₃, and O₃.

15. A method as in claim 4 for depositing a layer comprising a Si ALD film wherein:

said metal precursor in said saturating chemical dosage stage is selected from the group consisting of Si(OC₂H₅)₅, SiH₂Cl₂, SiCl₄, SiH₄, and SiHCl₃;

a first CRISP reactant in said saturating CRISP stage is selected from the group consisting of SiH₄, SiH₂Cl₂, B₂H₆, Si₂H₆, C₈H₁₀, and CH₃OH; and

a second CRISP reactant in said saturating CRISP stage is selected from the group consisting of F₂, F₂O, NF₃, ClF₃, and O₃.

16. A method as in claim 4 for depositing a layer comprising aluminum oxide (Al₂O₃) wherein:

a metal precursor in said saturating chemical dosage stage comprises trimethylaluminum;

a first CRISP reactant in said saturating CRISP stage comprises ozone (O3); and

a second CRISP reactant in said saturating CRISP stage comprises a hydrocarbon molecule selected from the group consisting of methane (CH₄), C₂H₆, C₂H₄, and C₈H₆.

17. A method as in claim 4 for depositing a layer comprising aluminum oxide (Al₂O₃) wherein:

a metal precursor in said saturating chemical dosage stage comprises trimethylaluminum;

a first CRISP reactant in said saturating CRISP stage comprises ozone (O₃); and

a second CRISP reactant in said saturating CRISP stage comprises an alcohol molecule.

18. A method as in claim 1, characterized in that said saturating CRISP stage further comprises:

varying a flow rate ratio of said CRISP reactants during said CRISP stage to effect a plurality of CRISP reactions in sequence;

wherein

each of said CRISP reactions is continuous and non-saturating;

each of said CRISP reactions generates a volatile by product and an intermediate reactive molecular fragment;

each intermediate reactive molecular fragment reacts with an intermediate ALD surface in a fragment-surface reaction in a cascade of fragment-surface reactions; and

each said fragment-surface reaction is saturating.

19. A method as in claim 18, characterized by varying said flow rate ratio so that a fragment-surface reaction substantially saturates before a succeeding fragment-surface reaction of said cascade of fragment-surface reactions begins.

20. A method as in claim 19 wherein

a first CRISP reaction generates a first intermediate reactive molecular fragment;

said first intermediate reactive molecular fragment reacts with a first intermediate ALD surface in a first saturating fragment-surface reaction; and

said first fragment-surface reaction generates a second intermediate ALD surface; and

wherein;

a second CRISP reaction generates a second intermediate reactive molecular fragment;

said second intermediate reactive molecular fragments reacts with said second intermediate ALD surface in a second saturating fragment-surface reaction; and

said second fragment-surface reaction generates a third intermediate ALD surface.

21. A method as in claim 19, characterized in that a final fragment-surface reaction of said cascade of fragment-surface reactions occurs at an intermediate ALD surface and generates a final intermediate ALD surface;

and further characterized in that said saturating chemical dosage stage comprises;

introducing a metal ALD precursor that reacts with said final intermediate ALD surface in a metal precursor-surface reaction;

said metal precursor-surface reaction is saturating; and

said metal precursor-surface reaction generates an intermediate ALD surface.

22. A method as in claim 1 wherein:

an ALD cycle comprises a saturating chemical dosage stage and a saturating CRISP stage; and

another ALD cycle comprises a saturating chemical dosage stage and a saturating surface restoration stage.

23. A method as in claim 1 wherein:

an ALD cycle comprises a first-type saturating chemical dosage stage and a corresponding first-type saturating CRISP stage; and

another ALD cycle comprises a second-type saturating chemical dosage stage and a corresponding second-type saturating CRISP stage.

24. A method as in claim 23, further characterized in that said first-type saturating chemical dosage stage comprises:

introducing a first metal ALD precursor that reacts with a first intermediate ALD surface in a first metal precursor-surface reaction;

said first metal precursor-surface reaction is saturating; and

said first metal precursor-surface reaction generates a first-metal intermediate ALD surface;

and further characterized in that said corresponding first-type saturating CRISP stage terminates said substrate surface with a second intermediate ALD surface;

and further characterized in that said second-type saturating chemical dosage stage comprises;

introducing a second metal ALD precursor that reacts with said second intermediate ALD surface in a second metal precursor-surface reaction;

said second metal precursor-surface reaction is saturating; and

said second metal precursor-surface reaction generates a second-metal intermediate ALD surface;

and further characterized in that said corresponding second-type saturating CRISP stage terminates said substrate surface with an intermediate ALD surface.

25. A method as in claim 24 wherein said second-type saturating CRISP stage terminates said substrate surface with said fist intermediate ALD surface.

26. A method as in claim 24 wherein said first intermediate ALD surface and said second intermediate ALD surface are terminated substantially similarly.

27. A method as in claim 24 wherein said first-type saturating CRISP stage and said second-type saturating CRISP stage are substantially similar.

28. A method as in claim 1 comprising techniques for synchronous modulation of flow and draw (SMFD), wherein an ALD cycle comprises, in the sequence set forth:

in a saturating chemical dosage stage, flowing a chemical precursor gas through said reaction chamber at a selected first-dosage flow rate and at an independently selected first-dosage pressure;

conducting a first purge stage by flowing a first purge gas through said reaction chamber at a selected first purge flow rate and at an independently selected first purge pressure; and

in a CRISP stag;

flowing said catalyzing reactants through said reaction chamber at selected second-dosage flow rates and at an independently selected second-dosage pressure.

29. A method as in claim 28, further comprising conducting a second purge stage after a saturating fragment-surface reaction of said CRISP stage by flowing a second purge gas through said reaction chamber at a selected second purge flow rate and at an independently selected second purge pressure.

30. A method as in claim 28, further comprising initiating said saturating chemical dosage stage by initially flowing said chemical precursor gas at a first transient flow rate, said first transient flow rate being initially substantially greater than said first-dosage flow rate.

31. A method as in claim 28, further comprising initiating said CRISP stage by initially flowing said second catalyzing reactants at second transient flow rates, said second transient flow rates being initially substantially greater than said second-dosage flow rates.

32. A method as in claim 28 wherein:

said flowing a chemical precursor gas through said reaction chamber comprises controlling a chemical-dosage pressure in said reaction chamber by controlling a draw-control pressure in a draw control chamber located downstream from said reaction chamber; and

said flowing CRISP reactants through said reaction chamber comprises controlling a CRISP-pressure in said reaction chamber by controlling a draw-control pressure in a draw control chamber located downstream from said reaction chamber.

33. A method as in claim 1 wherein said CRISP reaction generates a plurality of intermediate reactive molecular fragments and said intermediate reactive molecular fragments comprise a hydrogen atom and a molecular fragment selected from the group consisting of OH, NH, NH₂, SH, SeH, AsH, and AsH₂.

34. A method as in claim 33 further comprising controlling a flow rate ratio of said CRISP reactants into said reaction chamber to control relative surface concentrations of said hydrogen atoms and said molecular fragments.

35. A method as in claim 1 wherein said ALD is performed at a temperature not exceeding 200°

C.

36. A method as in claim 1 wherein said ALD is performed at a temperature not exceeding 100°

C.

37. A method as in claim 1 wherein:

said plurality of CRISP reactants comprises a first type of CRISP reactant and a second type of catalyzing CRISP reactant; and

said first type of CRISP reactant is selected from the group consisting of O₃, F₂, NF₃, ClF₃, HF, F₂O, FI, FNO, N₂F₂, F₂O₂, and F₄N₂; and

said second type of CRISP reactant is selected from the group consisting of CH₄, CN, C₂H₈N₂, CH₅N, CH₆N₂, C₂H₈, C₂H₃N, C₂H₄, C ₂H₄S, C₂H₅N, C₂H₆S, C₂H₆S₂, C₃H₆S, SiH₄, B₂H₆, Si₂H₆, SiH₂Cl₂, and PH₃.

38. A method as in claim 1 for depositing an oxide film characterized in that said saturating CRISP stage is conducted without using H₂O.

39. A method as in claim 1, further characterized by conducting at least one ALD cycle under mild oxidizing conditions, and by conducting at least one ALD cycle under strong oxidizing conditions.

40. A method as in claim 39, further comprising controlling a flow rare ratio of said CRISP reactants into said reaction chamber to control relative surface concentrations of hydrogen atoms and OH molecular fragments.

41. A method as in claim 1 wherein said intermediate reactive molecular fragment comprises atomic hydrogen.

42. A method as in claim 41 characterized by conducting an initial ALD cycle and further ALD cycles, wherein conducting said initial ALD cycle comprises:

introducing a metal ALD precursor that reacts with an initial ALD surface in an initial metal precursor-surface reaction to deposit a metal atom on said substrate;

said initial metal precursor-surface reaction is saturating; and

said metal precursor-surface reaction generates a first intermediate ALD surface;

said first intermediate ALD surface comprising a ligand of said metal ALD precursor, and

wherein conducting said initial ALD cycle further includes conducting an initial saturating CRISP stage in which an intermediate reactive molecular fragment comprising atomic hydrogen reacts with said first intermediate ALD surface in an initial saturating fragment-surface reaction;

said initial saturating fragment-surface reaction generating a volatile surface by-product containing a hydrated form of said metal precursor ligand, thereby removing said metal precursor ligand from said substrate;

said initial saturating fragment-surface reaction terminating said metal with hydrogen. thereby generating a second intermediate ALD surface; and

wherein conducting a further ALD cycle comprises;

introducing a metal ALD precursor that reacts with said hydrogen in said second intermediate ALD surface in a metal-surface reaction to deposit a metal atom on said substrate;

said metal-surface reaction is saturating; and

said metal-surface reaction generates said first intermediate ALD surface;

said first intermediate ALD surface comprising a ligand of said metal ALD precursor; and

wherein said conducting said further ALD cycle further includes conducting a CRISP stage in which an intermediate reactive molecular fragment comprising atomic hydrogen reacts with said first intermediate ALD surface in a saturating fragment-surface reaction;

said saturating fragment-surface reaction generating a volatile surface by-product containing a hydrated form of said metal precursor ligand, thereby removing said metal precursor ligand from said substrate;

said saturating fragment-surface reaction terminating said metal with hydrogen, thereby generating a second intermediate ALD surface.

43. A method as in claim 42 wherein said metal precursor comprises an atom selected from the group consisting of Al, Si, Ti, Ni, Cu, Zn, Ga, Ge, Y, Zr, Nb, Mo, Ru, In, Sn, Hf, Ta, and W.