ALD method and apparatus

• US 20030168001A1
• Filed: 03/07/2003
• Published: 09/11/2003
• Est. Priority Date: 03/08/2002
• Status: Active Grant

• Current Assignee: Sundew Technologies LLC
• Original Assignee: Sundew Technologies LLC
• Inventors: Sneh, Ofer
• Granted Patent: US 7,250,083 B2
• Time in Patent Office: Days
• US Class Current: 117/86
• 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.

2. A method as in claim 1 characterized in that said CRISP stage comprises:

introducing a first catalyzing reactant into said reaction chamber; and

introducing a second catalyzing reactant into said reaction chamber;

wherein said first catalyzing reactant and said second catalyzing reactant react in a catalyzing reaction;

said catalyzing reaction is continuous and non-saturating;

said catalyzing reaction generates a volatile by-product and an intermediate reactive molecular fragment;

said intermediate reactive molecular fragment reacts with (at) an intermediate ALD surface in a fragment-surface reaction; and

said fragment-surface reaction is saturating.

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

introducing a plurality of catalyzing reactants into said reaction chamber;

wherein said plurality of catalyzing reactants react in a catalyzing reaction;

said catalyzing reaction is continuous and non-saturating;

said catalyzing reaction generates a volatile by-product and an intermediate reactive molecular fragment;

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

said fragment-surface reaction is saturating.

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

5. A method as in claim 3 wherein said intermediate ALD surface is a first intermediate ALD surface, and said fragment-surface reaction generates a second intermediate ALD surface;

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

introducing a metal ALD precursor that reacts with said second 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.

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

7. A method as in claim 5 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.

8. A method as in claim 5 for depositing a layer comprising TiN ALD films wherein:

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

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

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

9. A method as in claim 5 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-C₄H₉)₄;

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

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

10. A method as in claim 5 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 catalyzing reactant in said saturating CRISP stage is selected from the group consisting of O₃ and B₂H₆; and

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

11. A method as in claim 5 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 catalyzing reactant in said saturating CRISP stage is selected from the group consisting of O₃ and B₂H₆; and

a second catalyzing 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 5 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 catalyzing reactant in said saturating CRISP stage is selected from the group consisting of O₃ and B₂H₆; and

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

13. A method as in claim 5 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 catalyzing reactant in said saturating CRISP stage is selected from the group consisting of SiH₄, SiH₂Cl₂, B₂H₆, Si₂H₆, C₈H₁₀, and CH₃OH; and

a second catalyzing 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 5 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 catalyzing reactant in said saturating CRISP stage is selected from the group consisting of SiH₄, SiH₂Cl₂, B₂H₆, Si₂H₆, C₈H₁₀, and CH₃OH; and

a second catalyzing 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 5 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 catalyzing reactant in said saturating CRISP stage is selected from the group consisting of SiH₄, SiH₂Cl₂, B₂H₆, Si₂H₆, C₈H₁₀, and CH₃OH; and

a second catalyzing 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 5 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 catalyzing reactant in said saturating CRISP stage is selected from the group consisting of SiH₄, SiH₂Cl₂, B₂H₆, Si₂H₆, C₈H₁₀, and CH₃OH; and

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

17. A method as in claim 5 for depositing a layer comprising aluminum oxide (Al₂O₃) wherein:

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

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

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

18. A method as in claim 5 for depositing a layer comprising aluminum oxide (Al₂O₃) wherein:

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

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

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

19. A method as in claim 3, characterized in that said saturating CRISP stage further comprises:

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

wherein

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

each of said catalyzing 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.

20. A method as in claim 19, 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.

21. A method as in claim 20 wherein:

a first catalyzing 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 catalyzing 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.

22. A method as in claim 20, 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.

23. A method as in claim 3 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.

24. A method as in claim 3 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.

25. A method as in claim 24, 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.

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

27. A method as in claim 25 wherein said first intermediate ALD surface and said second intermediate ALD surface are terminated substantially similarly.

28. A method as in claim 25 wherein said first-type saturating CRISP stage and said second-type saturating CRISP stage are substantially similar.

29. A method as in claim 3 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 stage, flowing said catalyzing reactants through said reaction chamber at selected second-dosage flow rates and at an independently selected second-dosage pressure.

30. A method as in claim 29, 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.

31. A method as in claim 29, 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.

32. A method as in claim 29, 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.

33. A method as in claim 29 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 catalyzing 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.

34. A method as in claim 3 wherein said catalyzing 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.

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

36. A method as in claim 3 wherein said ALD is performed at a temperature not exceeding 200°

C.

37. A method as in claim 3 wherein said ALD is performed at a temperature not exceeding 100°

C.

38. A method as in claim 3 wherein

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

and

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

said second type of catalyzing reactant is selected from the group consisting of CH₄, CN, C₂H₈N₂, CH₅N, CH₆N₂, C₂H₂, C₂H₃N, C₂H₄, C₂H₄S, C₂H₅N, C₂H₆S, C₂H₆S₂, C₃H₆S, SiH₄, B₂H₆, Si₂H₆, SiH₂Cl₂, and PH₃.

39. A method as in claim 3 for depositing an oxide film characterized in that said saturating CRISP stage is conducted without using H₂O.

40. A method as in claim 3, 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.

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

42. A method as in claim 3 wherein said intermediate reactive molecular fragment comprises atomic hydrogen.

43. A method as in claim 42 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.

44. A method as in claim 43 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.

45. A surface preparation method characterized by a saturating CRISP stage wherein said CRISP stage comprises:

introducing a plurality of catalyzing reactants into a reaction chamber containing a substrate with a surface;

wherein said catalyzing reactants react in a catalyzing reaction;

said catalyzing reaction is continuous and non-saturating;

said catalyzing reaction generates a volatile by-product and an intermediate reactive molecular fragment;

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

said fragment-surface reaction being substantially saturating.

46. A method as in claim 45 wherein said CRISP stage comprises:

introducing a first catalyzing reactant into said reaction chamber; and

introducing a second catalyzing reactant into said reaction chamber;

wherein said first catalyzing reactant and said second catalyzing reactant react in a catalyzing reaction; and

said catalyzing reaction is continuous and non-saturating.

47. A method as in claim 45 for cleaning a semiconductor surface comprising exposing said surface to a hydride/fluoride mixture of catalyzing reactants to generate hydrogen adsorbate on the surface to volatilize an atom selected from the group consisting of O, N, C, Sn, and Al from said surface.

48. A method as in claim 47 wherein said substrate comprises silicon or germanium and wherein a native oxide or nitride film is removed, and silicon or germanium from said oxide or nitride films is volatilized as SiH₄ or GeH₄, and said surface is thereby smoothed and becomes terminated with hydrogen.

49. A method as in claim 47 wherein said mixture of catalyzing reactants is selected from the group consisting of SiH₄/F₂, B₂H₆/F₂, Si₂H₆/F₂, SiH₂Cl₂/F₂, PH₃/F₂, SiH₄/ClF₃, B₂H₆/ClF₃, Si₂H₆/ClF₃, SiH₂Cl₂/ClF₃, PH₃/ClF₃, SiH₄/HF, B₂H₆/HF, Si₂H₆/HF, SiH₂Cl₂/HF, and PH₃/HF.

50. A method as in claim 45 wherein said substrate contains a contamination atom, and said fragment-surface reaction generates a volatile surface by-product molecule containing said contamination atom, thereby removing said contamination atom from said surface.

51. A method as in claim 50 wherein said substrate contains metallic contamination, and said fragment-surface reaction generates a volatile surface by-product molecule containing said metallic contamination, thereby removing said metallic contamination from said surface.

52. A method as in claim 50 wherein said intermediate reactive molecular fragment terminates said surface after said fragment-surface reaction.

53. A method as in claim 52 wherein said fragment-surface reaction saturates when said surface contains substantially no contamination atoms.

54. A method as in claim 52, further comprising initiating ALD growth by:

introducing a metal ALD precursor into said reaction chamber;

wherein said metal ALD precursor reacts with said surface terminated with said intermediate reactive molecular fragment.

55. A method as in claim 45 comprising:

introducing a first plurality of said catalyzing reactants;

said first plurality of catalyzing reactants reacting in a first catalyzing reaction under a first set of reaction conditions;

said first catalyzing reaction being continuous and non-saturating;

said first catalyzing reaction generating a first volatile by-product and a first intermediate reactive molecular fragment;

said first intermediate reactive molecular fragment reacting with said surface in a first fragment-surface reaction;

said first fragment-surface reaction generating a volatile surface by-product molecule containing a contamination atom, thereby removing said contamination atom from said surface; and

further comprising;

introducing a second plurality of said catalyzing reactants;

said second plurality of said catalyzing reactants reacting in a second catalyzing reaction under a second set of reaction conditions;

said second catalyzing reaction being continuous and non-saturating;

said second catalyzing reaction generating a second volatile by-product and a second intermediate reactive molecular fragment; and

said second intermediate reactive molecular fragment reacting with said surface in a second fragment-surface reaction, thereby terminating said surface.

56. A method as in claim 55 wherein said removing said contamination atom and said terminating said surface are conducted beyond saturation.

57. A method as in claim 55 wherein said contamination atom comprises an atom selected from the group consisting of Al, Si, O, N, S, Se, and Sn.

58. A method as in claim 55 wherein said substrate is terminated by an intermediate reactive molecular fragment selected from the group consisting of OH, NH, NH₂, SH, SeH, AsH, and AsH₂.

59. A method as in claim 45 wherein said intermediate reactive molecular fragment comprises atomic hydrogen.

60. A method as in claim 45 wherein said catalyzing reaction generates a plurality of intermediate reactive molecular fragments comprising a hydrogen atom and molecular fragments selected from the group consisting of OH, NH, NH₂, SH, SeH, AsH, and AsH₂.

61. A method as in claim 60, further comprising controlling a flow rate ratio of said catalyzing reactants into said reaction chamber to control relative surface concentrations of said hydrogen atoms and said molecular fragments.

62. A method as in claim 45 wherein said plurality of catalyzing reactants comprises a first type of catalyzing reactants and a second type of catalyzing reactants, and said catalyzing reactants comprise:

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

a second reactant type selected from the group consisting of CH₄, CN, C₂H₈N₂, CH₅N, CH₆N₂, C₂H₂, C₂H₃N, C₂H₄, C₂H₄S, C₂H₅N, C₂H₆S, C₂H₆S₂, C₃H₆S, SiH₄, B₂H₆, Si₂H₆, SiH₂Cl₂, and PH₃.

63. A CVD method for depositing a solid film on a surface of a substrate comprising:

introducing a CVD reactant into a reaction chamber containing said substrate;

introducing a plurality of catalyzing reactants into said reaction chamber, whereby said catalyzing reactants react in a catalyzing reaction;

said catalyzing reaction generating a volatile by-product molecule and an intermediate reactive molecular fragment at said surface;

said intermediate reactive molecular fragment reacting with said CVD reactant in a CVD reaction; and

said CVD reaction depositing said solid film on said surface.

64. A method as in claim 63 wherein said catalyzing reaction is more than 10 times faster than said CVD reaction.

65. A method as in claim 63 wherein said CVD reaction including said intermediate reactive molecular fragment and said CVD reactant is more than 10 times faster than a reaction including said catalyzing reactants and said CVD reactant.

66. A method as in claim 63 wherein said intermediate reactive molecular fragment comprises atomic hydrogen.

67. A method as in claim 66 wherein said CVD reactant comprises WF₆ and said solid film comprises W.

68. A method as in claim 66 wherein said CVD reactant comprises a copper (II) beta-diketonate complex and said solid film comprises copper.

69. A method as in claim 68 wherein said copper (II) beta-diketonate complex comprises Cu(tfac)₂.

70. A method as in claim 63 wherein said catalyzing 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.

71. A method of claim 70, further comprising controlling a flow ratio of said catalyzing reactants to control relative surface concentrations of said hydrogen atoms and said molecular fragments.

72. A method as in claim 70 wherein said CVD reactant comprises a copper (II) beta-diketonate complex, said solid film comprises copper, and said molecular fragments comprise OH.

73. A method as in claim 72 wherein said copper (II) beta-diketonate complex comprises Cu(hfac)₂.

74. A method as in claim 70 wherein said CVD reactant comprises tetraethoxysilane (TEOS) and said molecular fragment comprises OH.

75. A method as in claim 63 wherein said plurality of catalyzing reactants comprise a first type of catalyzing reactants and a second type of catalyzing reactants;

a first-type catalyzing reactant being selected from the group consisting of O₃, F₂, NF₃, ClF₃, HF, F₂O, FI, FNO, N₂F₂, F₂O₂, and F₄N₂; and

a second-type catalyzing reactant being selected from the group consisting of CH₄, CN, C₂H₈N₂, CH₅N, CH₆N₂, C₂H₂, C₂H₃N, C₂H₄, C₂H₄S, C₂H₅N, C₂H₆S, C₂H₆S₂, C₃H₆S, SiH₄, B₂H₆, Si₂H₆, SiH₂Cl₂, and PH₃.

76. A method as in claim 63 wherein:

said CVD reactant is introduced into an abatement reaction chamber from a chemical reaction chamber and said catalyzing reactants are introduced independently into said abatement reaction chamber; and

wherein said catalyzing reaction generates an intermediate reactive molecular fragment; and

said intermediate reactive molecular fragment react with said CVD reactant to facilitate abatement.

77. A method as in claim 76, further comprising conducting said abatement at a temperature not exceeding 150°

C.

78. A method as in claim 76 wherein said CVD reactant comprises TEOS.

79. A method as in claim 76 wherein said CVD reactant comprises WF₆.

80. A method as in claim 76 wherein said CVD reactant comprises a copper (II) beta-diketonate.

81. A method as in claim 76 wherein said CVD reactant comprises AlCl₃.

82. A dry etching method comprising:

introducing a plurality of catalyzing reactants into a reaction chamber containing a substrate;

wherein said plurality of catalyzing reactants react in a catalyzing reaction;

said catalyzing reaction is continuous and non-saturating;

said catalyzing reaction generates a volatile by-product and an intermediate reactive molecular fragment;

said intermediate reactive molecular fragment reacts with said substrate in a fragment-substrate reaction;

said fragment-substrate reaction generates a volatile molecular species, thereby etching said substrate; and

further comprising controlling substrate temperature to control said etching.

83. A method as in claim 82, further comprising applying an energy-containing beam to said substrate to facilitate anisotropic etching, said energy-containing beam selected from the group consisting of an ion beam and an atomic beam.

84. A method as in claim 82 wherein said intermediate reactive molecular fragment comprises atomic hydrogen.

85. A method as in claim 82 wherein said catalyzing reaction generates a plurality of intermediate reactive molecular fragments;

and

said intermediate reactive molecular fragments comprising hydrogen atoms and molecular fragments selected from the group consisting of Cl, Br, I, OH, NH, NH₂, SH, SeH, AsH, and AsH₂.

86. A method as in claim 85, further comprising controlling a flow rate ratio of said catalyzing reactants into said reaction chamber to control relative surface concentrations of said hydrogen atoms and said molecular fragments.

87. A method as in claim 82 wherein said plurality of catalyzing reactants comprise:

first catalyzing reactants selected from the group consisting of O₃, F₂, NF₃, ClF₃, HF, F₂O, FI, FNO, N₂F₂, F₂O₂, and F₄N₂; and

second catalyzing reactants selected from the group consisting of CH₄, CN, C₂H₈N₂, CH₅N, CH₆N₂, C₂H₂, C₂H₃N, C₂H₄, C₂H₄S, C₂H₅N, C₂H₆S, C₂H₆S₂, C₃H₆S, SiH₄, B₂H₆, Si₂H₆, SiH₂Cl₂, and PH₃.

88. A method as in claim 82 wherein said substrate comprises internal surfaces of a chemical processing apparatus.

89. A method as in claim 88 for in-situ cleaning of an ALD deposition chamber to remove a film deposit, comprising introducing a gas mixture of catalyzing reactants comprising a combination selected from the group consisting of hydride/fluoride, hydride/fluoride/ozone/hydrocarbons, PH₃/F₂, PH₃/F₂/O₃/C₂H₂, PH₃/FCl, and PH₃/FCl/O₃/C₂H₂.

90. A method as in claim 89 wherein said gas mixture comprises a combination selected from the group consisting of hydride/fluoride and hydride/ fluoride/ozone/hydrocarbons, and further comprises a source of chlorine selected from the group consisting of SCl₂, S₂Cl₂, ClF₃, ClF, ClI, and SiCl₄.

91. A method as in claim 82 wherein said substrate comprises a solid chemical source of a chemical process system.

92. A method as in claim 82 wherein:

said reaction chamber comprises a chemical source chamber upstream from an ALD deposition chamber; and

said substrate comprises a metallic target located in said source chamber.

93. A method as in claim 92, comprising varying a flow rate of at least one catalyzing reactant into said chemical source chamber so that said catalyzing reaction proceeds during a chemical delivery time, and said catalyzing reaction substantially ceases during a non-delivery time.

94. A method as in claim 93 wherein

said catalyzing reaction generates said intermediate reactive molecular fragment during said chemical delivery time;

and

said intermediate reactive molecular fragment reacts with said metallic target to generate said volatile molecular species during said chemical delivery time.

95. A method as in claim 94, further comprising controlling a temperature of said metallic target to effect fast volatilization of said volatile molecular species during said chemical delivery time, thereby generating pulse delivery of said volatile molecular species.

96. A method as in claim 94 wherein said volatile molecular species comprises a metal.

97. A method of treating a solid film on a substrate, comprising:

introducing a plurality of catalyzing reactants into a reaction chamber containing said solid film;

characterized in that said plurality of catalyzing reactants react in a catalyzing reaction;

said catalyzing reaction is continuous and non-saturating;

said catalyzing reaction generates a volatile by-product and an intermediate reactive molecular fragment;

said intermediate reactive molecular fragment reacts with said solid film in a fragment-film reaction; and

further comprising controlling a temperature of said chemical film to control said treating.

98. A method as in claim 97 wherein said intermediate reactive molecular fragment comprises hydrogen, and said hydrogen is incorporated into said chemical film during said fragment-film reaction.

99. A method as in claim 97 wherein said intermediate reactive molecular fragment comprises a hydrogen atom, and said hydrogen improves an interface between said solid film and said substrate.

100. A method as in claim 97 wherein said intermediate reactive molecular fragment comprises a hydrogen atom, and said hydrogen atom removes an in-film impurity.

101. A method as in claim 100 wherein said in-film impurity is selected from the group consisting of F, O, OH, Cl, and C.

102. A method as in claim 97 wherein said intermediate reactive molecular fragment comprises a dopant atom, and said dopant atom is incorporated into said chemical film during said fragment-film reaction.

103. A method as in claim 102 wherein said dopant atom is selected from the group consisting of B and P.

104. A method as in claim 97 wherein said treating comprises annealing said chemical film.

105. A method using CRISP for activating a surface of a substrate, comprising:

exposing said surface to a gas mixture comprising catalyzing reactants selected from the group of reactant combinations consisting of O₃/hydrocarbon, hydride/oxyfluoride, O₃/nitrogen-containing-hydrocarbon, hydride/amine-fluoride, and O₃/sulfur-containing-hydrocarbon.

106. A method as in claim 105 wherein said surface before said exposing comprises a surface termination selected from the group consisting of oxides, nitrides, and sulfides.

107. A method as in claim 105 wherein said exposing for activating said surface is conducted prior to deposition of an ALD layer comprising a material selected from the group consisting of oxides, nitrides, sulfides, metals, and semiconductor atoms.

108. A method as in claim 105 wherein said exposing comprises exposing said surface to a gas mixture comprising catalyzing reactants selected from the group of reactant combinations consisting of O₃/hydrocarbon and hydride/ oxyfluoride to effect surface hydroxylation.

109. A method as in claim 108 wherein said mixture of catalyzing reactants is selected from the group consisting of O₃/CH₄, O₃/C₂H₂, O₃/C₂H₄, SiH₄/F₂O, B₂H₆/F₂O, Si₂H₆/F₂O, SiH₂Cl₂/F₂O, PH₃/F₂O, SiH₄/F₂O₂, B₂H₆/F₂O₂, Si₂H6/F₂O₂, SiH₂Cl₂/F₂O₂, and PH₃/F₂O₂.

110. An atomic layer deposition (ALD) apparatus for synchronous modulation of flow and draw (SMFD), comprising:

a first gas distribution chamber;

a second gas distribution chamber;

a reaction chamber disposed downstream from said first and second gas distribution chambers;

a first gas-distribution flow restriction element (FRE), providing fluidic communication between said first gas distribution chamber and said reaction chamber;

a second gas-distribution flow restriction element (FRE), providing fluidic communication between said second gas distribution chamber and said reaction chamber;

a draw control chamber disposed downstream from said reaction chamber;

a reaction-chamber FRE in fluidic communication between said reaction chamber and said draw control chamber;

a draw exhaust line in serial fluidic communication with said draw control chamber; and

a draw-control FRE in serial fluidic communication between said draw control chamber and said draw exhaust line.

111. An apparatus as in claim 110, further comprising:

a first catalyzing reactant source in fluid communication with, and disposed upstream from, said first gas distribution chamber; and

a second catalyzing reactant source in fluid communication with, and disposed upstream from, said second gas distribution chamber.

112. An apparatus as in claim 110, further comprising:

a draw-source shut-off valve to control a flow of draw-gas through said draw control chamber; and

a draw-source-FRE in serial fluidic communication with said draw-source shut-off valve and said draw control chamber.

113. An apparatus as in claim 110, further comprising:

a DGIC, said DGIC being in serial fluidic communication between said reaction chamber and said draw control chamber;

a draw-source shut-off valve to control a flow of draw gas into said DGIC;

a draw-source-FRE in serial fluidic communication with said draw-source shut-off valve and said draw control chamber; and

a DGIC-FRE located between said DGIC and said draw control chamber;

wherein said reaction-chamber FRE is located between said process chamber and said DGIC.

114. An apparatus as in claim 110, further comprising an inert gas source in fluidic communication with a gas distribution chamber.

115. An apparatus as in claim 110 having a plurality of draw-control FREs and a plurality of after-draw control chambers, comprising:

a first after-draw control chamber located downstream from said draw control chamber;

a first draw-control FRE disposed between said draw control chamber and said first after-draw control chamber;

a first after-draw FRE in serial fluidic communication between said first after-control chamber and said exhaust line;

a second after-draw control chamber located downstream from said draw control chamber;

a second draw-control FRE disposed between said draw control chamber and said second after-draw control chamber; and

a second after-draw FRE in serial fluidic communication between said second after-control chamber and said exhaust line.

116. An apparatus as in claim 115, further comprising:

an after-draw gas inlet in said first after-draw control chamber; and

a first after-draw gas source for providing after-draw control gas to said first after-draw control chamber to control a first after-draw pressure in said first after-draw control chamber and thereby to control gas flow out of said draw control chamber.

117. An apparatus as in claim 116, further comprising an abatement element disposed in an after-draw control chamber.