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Supercritical fluid-assisted deposition of materials on substrates, such as semiconductor substrates for integrated circuit device manufacture. The deposition is effected using a supercritical fluid-based composition containing the precursor(s) of the material to be deposited on the substrate surfac

Supercritical fluid-assisted deposition of materials on substrates, such as semiconductor substrates for integrated circuit device manufacture. The deposition is effected using a supercritical fluid-based composition containing the precursor(s) of the material to be deposited on the substrate surface. Such approach permits use of precursors that otherwise would be wholly unsuitable for deposition applications, as lacking requisite volatility and transport characteristics for vapor phase deposition processes.

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What is claimed is: 1. A method of forming a material on a substrate, comprising depositing the material on the substrate from a deposition composition comprising (a) a precursor of said material, (b) at least one surfactant, and (c) a supercritical fluid. 2. The method of claim 1, wherein the su

What is claimed is: 1. A method of forming a material on a substrate, comprising depositing the material on the substrate from a deposition composition comprising (a) a precursor of said material, (b) at least one surfactant, and (c) a supercritical fluid. 2. The method of claim 1, wherein the supercritical fluid comprises a fluid selected from the group consisting of: carbon dioxide, oxygen, argon, krypton, xenon, ammonia, methane, ethane, methanol, ethanol, isopropanol, dimethyl ketone, sulfur hexafluoride, carbon monoxide, dinitrogen oxide, forming gas, hydrogen, and mixtures thereof. 3. The method of claim 1, wherein the supercritical fluid comprises carbon dioxide. 4. The, method of claim 1, wherein said composition furthercomprises a co-solvent. 5. The method of claim 4, wherein said co-solvent comprises a solvent selected from the group consisting of: methanol, ethanol, isopropyl alcohol, N-methylpyrrolidone, N-octylpyrrolidone, N-phenylpyrrolidone, dimethylsulfoxide, sulfolane, catechol, ethyl lactate, acetone, butyl carbitol, monoethanolamine, butyrol lactone, diglycol amine, γ-butyrolactone, butylene carbonate, ethylene carbonate, and propylene carbonate. 6. The method of claim 1, wherein the deposition composition consists essentially of said supercritical fluid, said precursor, and said surfactant. 7. The method of claim 1, wherein the deposition composition consists of said supercritical fluid, said precursor, and said surfactant. 8. The method of claim 1, wherein said material comprises a semiconductor manufacturing material. 9. The method of claim 8, wherein said semiconductor manufacturing material comprises a material selected from the group consisting of semiconductor materials, dielectric materials, barrier layer materials, interconnect materials and metallization materials. 10. The method of claim 1, wherein said material comprises a semiconductor material. 11. The method of claim 1, wherein said material comprises a dielectric material. 12. The method of claim 1, wherein said material comprises a low k material. 13. The method of claim 1, wherein said material comprises a high k material. 14. The method of claim 1, wherein said material comprises a barrier layer material. 15. The method of claim 14 wherein said barrier layer material comprises a material selected from the group consisting of TiN, TaN, NbN, WN, and corresponding silicides thereof. 16. The method of claim 1, wherein said material comprises an interconnect material. 17. The method of claim 16, wherein said interconnect material comprises a material selected from the group consisting of metals and metal alloys. 18. The method of claim 17, wherein said material comprises a metal selected from the group consisting of copper and aluminum. 19. The method of claim 1, wherein said material comprises a metallization material. 20. The method of claim 19, wherein said metallization material comprises a material selected from the group consisting of metals and metal alloys. 21. The method of claim 20, wherein said material comprises a metal selected from the group consisting of copper and aluminum. 22. The method of claim 1, wherein the deposition composition further comprises at least one component selected from the group consisting of co-solvents, co-reactants, diluents, and depostion-enhancing agents. 23. The method of claim 22, wherein said at least one component comprises at least one co-solvent or co-reactant, wherein said at least one co-solvent or co-reactant is selected from the group consisting of alcohols, N-alkyl pyrrolidones, N-aryl pyrrolidones, dimethylsulfoxide, sulfolane, catechol, ethyl lactate, acetone, butyl carbitol, monoethanolamine, butyrol lactone, diglycol amine, y-butyrolactone, butylene carbonate, ethylene carbonate, and propylene carbonate. 24. The method of claim 1, wherein said at least one surfactant comprises a species selected from the group consisting of an anionic surfactant, a neutral surfactant, a cationic surfactant, and a zwitterionic surfactant. 25. The method of claim 1, wherein said at least one surfactant comprises a surfactant selected from the group consisting of acetylenic alcohols, acetylenic diols, long alkyl chain secondary and tertiary amines, and fluorinated derivatives of the foregoing. 26. The method of claim 25, wherein said at least one surfactant comprises a surfactant selected from the group consisting of: 3,4-dimethyl-1-hexyn-3-ol; 2,4,7,9-tetramethyl-5-decyn-4,7-diol; and fluorinated surfactants. 27. The method of claim 1, wherein the precursor has a concentration not exceeding about 40% by weight, based on the weight of the supercritical fluid in the composition. 28. The method of claim 1, wherein the precursor comprises a polymeric precursor. 29. The method of claim 1, wherein the precursor comprises an oligomeric precursor. 30. The method of claim 1, wherein the precursor comprises a thin film precursor. 31. The method of claim 1, wherein the precursor comprises a precursor selected from the group consisting of metal precursors and dielectric material precursors. 32. The method of claim 31, wherein the supercritical fluid comprises a supercritical fluid selected from the group consisting of carbon dioxide, methane, ethane, methanol, dimethyl ketone and sulfur hexafluoride. 33. The method of claim 1, wherein the precursor comprises a precursor selected from the group consisting of organometallic compounds and complexes, and Lewis base adducts thereof. 34. The method of claim 1, wherein the deposition composition further comprises at least one Lewis base. 35. The method of claim 1, wherein the precursor comprises a precursor selected from the group consisting of alkyl silanes, siloxanes and organic-based non-silicon-containing low k dielectric precursors. 36. The method of claim 1, wherein the precursor comprises a precursor selected from the group consisting of siloxanes. 37. The method of claim 36, wherein the precursor comprises an alkyl siloxane. 38. The method of claim 36, wherein the precursor comprises a cyclosiloxane. 39. The method of claim 36, wherein the precursor comprises a cyclosiloxane selected from the group consisting of tetramethylcyclotetrasiloxane (TMCTS) and octamethyltetracyclosiloxane (OMCTS). 40. The method of claim 1, wherein the precursor comprises a thermally unstable low k film precursor. 41. The method of claim 40, wherein the supereritical fluid comprises a supereritical fluid selected from the group consisting of carbon dioxide, methane, methanol, dimethyl ketone and sulfur hexafluoride. 42. The method of claim 1, wherein the precursor is insufficiently volatile for chemical vapor deposition in absence of the supercritical fluid. 43. The method of claim 1, wherein the precursor comprises a barrier layer precursor selected from the group consisting of titanium (liv) tetrakis-dialkylamides, titanium pyrozolates, titanium amido compounds, titanium imido compounds, Ta (IV) pentakis(dialkylamido) compounds, and corresponding W and Nb analogs of such titanium and tantalum compounds. 44. The method of claim 1, wherein the precursor comprises a barrier layer precursor selected from the group consisting of tetrakis diethylamido titanium (TDEAT), tetrakis dimethylamino titanium (TDMAT), pentakis ethylmethylamido tantalum (PEMAT), pentakis dimethylamido tantalum (PDMAT), pentakis diethylamido tantalum (PDEAT), and corresponding W and Nb analogs of such titanium and tantalum compounds. 45. The method of claim 1, wherein the precursor comprises a metal precursor selected from the group consisting of metal beta-diketonates, metal formates metal acetates, and Lewis base adducts of the foregoing. 46. The method of claim 45, wherein the metal precursor comprises a metal selected from the group consisting of copper, aluminum, titanium, tantalum, niobium, tungsten, molybdenum, chromium, and cobalt. 47. The method of claim 1, wherein the precursor comprises a copper precursor. 48. The method of claim 47, wherein the copper precursor is selected from the group consisting of: copper (II) β-diketonates, copper (II) carboxylates, copper (I) cyclopentadienes, copper (I) phenyls, copper (I) amides, and Lewis base adducts of the aforementioned copper (I) and copper (II) species. 49. The method of claim 47, wherein the copper precursor is selected from the group consisting of: β-diketonate copper compounds and complexes; copper (carboxylate)2 compounds and complexes; cyclopentadienyl copper-ligand complexes; copper aryl tetramers; and copper amides. 50. The method of claim 47, wherein the copper precursor is selected from the group consisting of: copper (β-diketonato)2 compounds and complexes; copper (carboxylate)2 compounds and complexes, wherein each carboxylate moiety is independently selected from the group consisting of C1-C40 carboxylate moieties; cyclopentadienyl copper-ligand complexes; copper phenyl tetramers; and copper amides. 51. The method of claim 47, wherein the copper precursor is selected from the group consisting of: Cu (II) (acac)2, Cu (II) (thd)2, Cu (tod)2, Cu (formate)2, Cu (acetate)2, CpCu(I)PMe3, Cu (I) pentaflurophenyl, Cu (I) t-butyl phenyl tetramer, and Cu(I) bis(trimethylsilylamide) tetramer. 52. The method of claim 1, wherein the deposition composition further comprises an additive selected from the group consisting of hydrogen and ammonia. 53. The method of claim 1, wherein the precursor comprises a barrier layer or metallization precursor and the supercritical fluid comprises a supercritical fluid species selected from the group consisting of CO2, NH3, CH4, SF6, N2O, and CO. 54. The method of claim 1, wherein the deposition composition is devoid of fluorine-containing components. 55. The method of claim 1, wherein the precursor comprises a copper (II) carboxylate compound or complex. 56. The method of claim 55, wherein the precursor comprises copper formate. 57. The method of claim 55, wherein the precursor comprises a copper formate polyamine complex. 58. The method of claim 1, wherein the precursor comprises a copper precursor, and the deposition composition further comprises a reducing agent. 59. The method of claim 58, wherein the reducing agent comprises at least one reducing agent selected from the group consisting of hydrogen, formaldehyde and alcohols. 60. The method of claim 58, wherein the reducing agent comprises hydrogen. 61. The method of claim 58, wherein the reducing agent comprises formaldehyde. 62. The method of claim 58, wherein the reducing agent comprises isopropanol. 63. The method of claim 62, wherein isopropanol is present in said composition at a concentration of from about 0.1% to about 99.9% by weight, based on the weight of the supercritical fluid. 64. The method of claim 1, wherein the precursor comprises a copper precursor selected from the group consisting of copper carboxylates, copper β-diketonates, and complexes and adducts thereof, and the supercritical fluid is selected from the group consisting of CO2, CH4, C2H6, CH3OH, C2H5OH, (CH3)2CHOH, CH3COCH3 and SF6. 65. The method of claim 1, wherein the precursor comprises a silicon precursor. 66. The method of claim 65, wherein the silicon precursor comprises a siloxane and an alkylsilane. 67. The method of claim 66, wherein the alkylsilane comprises trimethylsilane. 68. The method of claim 66, wherein the alkylsilane comprises tetramethylsilane. 69. The method of claim 1, wherein the silicon precursor comprises a siloxane, and the composition further comprises a porogen effective in combination with the siloxane to form a porous low k film on the substrate. 70. The method of claim 1, wherein the substrate comprises a semiconductor wafer. 71. The method of claim 1, wherein the substrate comprises a heated substrate and said depositing comprises contacting the deposition composition with the heated substrate for forming said material as a layer on the heated substrate. 72. The method of claim 71, wherein the precursor comprises a source reagent compound or complex and said material comprises a metal or dielectric film. 73. The method of claim 71, wherein said depositing comprises continuously delivering the deposition composition to the heated substrate, to deposit the material thereon from the precursor. 74. The method of claim 73, wherein said depositing is carried out in a deposition chamber and generates deposition by-products, and said method further comprises continuously discharging the deposition by-products from the deposition chamber during said depositing. 75. The method of claim 71, wherein said depositing is carried out in a batch mode, wherein the deposition composition is contacted with the substrate, and process condition(s) of the deposition composition are altered to effect said depositing of material on the substrate from the precursor in the deposition composition. 76. The method of claim 75, wherein the process condition(s) that are altered comprise at least one of temperature and pressure. 77. The method of claim 75, wherein the process condition(s) that are altered comprise temperature. 78. The method of claim 75, wherein the process condition(s) that are altered comprise pressure. 79. The method of claim 75, wherein the process condition(s) that are altered comprise temperature and pressure. 80. The method of claim 1, wherein said depositing comprises chemical vapor deposition. 81. The method of claim 1, wherein said precursor comprises a polymeric or oligomeric precursor, said method further comprises dissolving the polymeric or oligomeric precursor species in the supercritical fluid to form the deposition composition, rendering the deposition composition into a finely divided fluid form, and transporting the finely divided fluid form deposition composition to the substrate for said depositing of material thereon. 82. The method of claim 81, wherein the material comprises a low k film. 83. The method of claim 1, wherein said deposition composition is rapidly expanded to form vapor particles comprising the precursor, and said vapor particles are contacted with the substrate in said depositing. 84. The method of claim 1, and said precursor comprises a silicon source reagent. 85. The method of claim 84, wherein said silicon source reagent comprises a reagent selected from the group consisting of alkyl silanes and siloxanes. 86. The method of claim 85, wherein the supercritical fluid comprises a fluid selected from the group consisting of carbon dioxide, methane, methanol, dimethyl ketone and sulfur hexafluoride. 87. A thin film deposited using the method of claim 1. 88. A method of forming a metal material on a substrate, comprising depositing the metal material on the substrate from a deposition composition comprising a precursor of said metal material, and a supercritical fluid, wherein said precursor comprises a metal selected from the group consisting of chromium and cobalt. 89. The method of claim 88, wherein the precursor comprises a metal precursor selected from the group consisting of metal beta-diketonates, metal formates, metal acetates, and Lewis base adducts of the foregoing. 90. The method of claim 88, wherein the deposition composition further comprises at least one component selected from the group consisting of co-solvents, co-reactants, surfactants, diluents, and deposition-enhancing agents. 91. The method of claim 88, wherein the supercritical fluid comprises a fluid selected from the group consisting of: carbon dioxide, oxygen, argon, krypton, xenon, ammonia, methane, ethane, methanol, ethanol, isopropanol, dimethyl ketone, sulfur hexafluoride, carbon monoxide, dinitrogen oxide, forming gas, hydrogen, and mixtures thereof.