CN106057637A - 通过原子层沉积和原子层蚀刻沉积共形膜 - Google Patents
通过原子层沉积和原子层蚀刻沉积共形膜 Download PDFInfo
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- CN106057637A CN106057637A CN201610206201.6A CN201610206201A CN106057637A CN 106057637 A CN106057637 A CN 106057637A CN 201610206201 A CN201610206201 A CN 201610206201A CN 106057637 A CN106057637 A CN 106057637A
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- QGGUMTNPIYCTSF-UHFFFAOYSA-N hexylsilane Chemical group CCCCCC[SiH3] QGGUMTNPIYCTSF-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 238000010849 ion bombardment Methods 0.000 description 1
- 238000005468 ion implantation Methods 0.000 description 1
- BMFVGAAISNGQNM-UHFFFAOYSA-N isopentylamine Chemical compound CC(C)CCN BMFVGAAISNGQNM-UHFFFAOYSA-N 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000012705 liquid precursor Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000005007 materials handling Methods 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- IFVRUKGTKXWWQF-UHFFFAOYSA-N methylaminosilicon Chemical compound CN[Si] IFVRUKGTKXWWQF-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 150000002831 nitrogen free-radicals Chemical class 0.000 description 1
- 239000001272 nitrous oxide Substances 0.000 description 1
- 238000001208 nuclear magnetic resonance pulse sequence Methods 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920000548 poly(silane) polymer Polymers 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- YYVGYULIMDRZMJ-UHFFFAOYSA-N propan-2-ylsilane Chemical compound CC(C)[SiH3] YYVGYULIMDRZMJ-UHFFFAOYSA-N 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 125000001339 silanediyl group Chemical group [H][Si]([H])(*)* 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- OLRJXMHANKMLTD-UHFFFAOYSA-N silyl Chemical compound [SiH3] OLRJXMHANKMLTD-UHFFFAOYSA-N 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000007592 spray painting technique Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- NBRKLOOSMBRFMH-UHFFFAOYSA-N tert-butyl chloride Chemical compound CC(C)(C)Cl NBRKLOOSMBRFMH-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000003942 tert-butylamines Chemical class 0.000 description 1
- KNSVRQSOPKYFJN-UHFFFAOYSA-N tert-butylsilicon Chemical compound CC(C)(C)[Si] KNSVRQSOPKYFJN-UHFFFAOYSA-N 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 125000005207 tetraalkylammonium group Chemical group 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 1
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 1
- 239000005052 trichlorosilane Substances 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
- H01L21/02123—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon
- H01L21/0217—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material being a silicon nitride not containing oxygen, e.g. SixNy or SixByNz
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
- H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
- H01L21/02263—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase
- H01L21/02271—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition
- H01L21/0228—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition deposition by cyclic CVD, e.g. ALD, ALE, pulsed CVD
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/32—Carbides
- C23C16/325—Silicon carbide
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/34—Nitrides
- C23C16/345—Silicon nitride
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/40—Oxides
- C23C16/401—Oxides containing silicon
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
- C23C16/45527—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
- C23C16/45527—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations
- C23C16/45536—Use of plasma, radiation or electromagnetic fields
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
- C23C16/45544—Atomic layer deposition [ALD] characterized by the apparatus
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/50—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges
- C23C16/505—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges using radio frequency discharges
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/52—Controlling or regulating the coating process
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
- H01J37/32—Gas-filled discharge tubes
- H01J37/32009—Arrangements for generation of plasma specially adapted for examination or treatment of objects, e.g. plasma sources
- H01J37/32082—Radio frequency generated discharge
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
- H01J37/32—Gas-filled discharge tubes
- H01J37/32009—Arrangements for generation of plasma specially adapted for examination or treatment of objects, e.g. plasma sources
- H01J37/32082—Radio frequency generated discharge
- H01J37/32091—Radio frequency generated discharge the radio frequency energy being capacitively coupled to the plasma
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02205—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition
- H01L21/02208—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02205—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition
- H01L21/02208—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si
- H01L21/02211—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si the compound being a silane, e.g. disilane, methylsilane or chlorosilane
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
- H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
- H01L21/02263—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase
- H01L21/02271—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition
- H01L21/02274—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition in the presence of a plasma [PECVD]
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
- H01L21/28008—Making conductor-insulator-semiconductor electrodes
- H01L21/28017—Making conductor-insulator-semiconductor electrodes the insulator being formed after the semiconductor body, the semiconductor being silicon
- H01L21/28158—Making the insulator
- H01L21/28167—Making the insulator on single crystalline silicon, e.g. using a liquid, i.e. chemical oxidation
- H01L21/28194—Making the insulator on single crystalline silicon, e.g. using a liquid, i.e. chemical oxidation by deposition, e.g. evaporation, ALD, CVD, sputtering, laser deposition
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- H—ELECTRICITY
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Abstract
本发明涉及通过原子层沉积和原子层蚀刻沉积保形膜。提供了用于在原子层沉积过程中使用含卤素的蚀刻剂沉积共形膜的方法。所述方法包括在衬底暴露于第一前体和衬底暴露于第二等离子体活化的反应物之间将衬底暴露于含卤素的蚀刻剂,例如暴露于三氟化氮。可沉积的共形膜的实例包括含硅膜和含金属膜。还提供了相关的装置。
Description
技术领域
本发明总体上涉及半导体领域,具体涉及通过原子层沉积和原子层蚀刻沉积保形膜。
背景技术
例如半导体器件之类的器件的制造会涉及在衬底上的凸起或凹陷的特征内或其上沉积各种介电膜、导电膜、以及半导体膜。与下伏的衬底形貌共形的膜的沉积会是具有挑战性的,尤其是随着特征的深宽比的增大和关键尺寸的减小。
可在器件制造中使用的膜的一个实施例是氮化硅(SiN)。氮化硅薄膜具有独特的物理、化学和机械性能,因此被用于各种应用中。对于半导体器件,例如,SiN膜可以在扩散阻挡层、栅极绝缘体、侧壁垫层、封装层、在晶体管内的应变膜等内使用。沉积SiN膜的常规方法在用于沉积高深宽比特征的SiN膜时,可能会产生悬垂物(overhang)。随着器件尺寸不断缩小,在高深宽比特征内沉积共形的SiN膜和其它类型的膜的需求日益增加。
发明内容
本发明提供了用于处理衬底的方法和装置,一个方面涉及一种处理在室中的衬底的方法,该方法包括:(a)提供具有一个或多个特征的衬底,每个特征包括特征开口;(b)在使得含硅前体能吸附到所述衬底的表面上的条件下,将所述衬底暴露于所述含硅前体,由此形成含硅前体吸附层;(c)在将所述衬底暴露于所述含硅前体后,将所述衬底暴露于含卤素的蚀刻剂;以及(d)将所述衬底暴露于含氮反应物并点燃等离子体,以在所述特征开口处或其附近选择性地蚀刻所述第一前体吸附层并形成氮化硅膜。
可以在使所述含卤素的蚀刻剂能选择性地吸附到所述第一前体吸附层的条件下,使所述衬底暴露于所述含卤素的蚀刻剂。含卤素的蚀刻剂的实例包括三氟化氮、氯、三氟甲烷、四氟化碳、以及它们的组合。在一些实施方式中,所述含卤素的蚀刻剂是化学式为CnF2n+2或CnF2n的化合物,其中n>1。
在一些实施方式中,在将所述衬底暴露于所述含卤素的蚀刻剂之后清扫所述室。可以通过使清扫气体流动来清扫所述室,所述清扫气体如氩气、氦气、氮气和氢气。
含硅前体的实例是硅烷、乙硅烷、丙硅烷、丁硅烷、三甲硅烷基胺、氨基硅烷、和卤代硅烷。含氮反应物的实例是氮、氨、肼和胺。
在一些实施方式中,所述方法包括重复(a)-(d)。在一些实施方式中,(a)-(d)在同一室中进行。
另一方面涉及一种处理在室中的衬底的方法,该方法包括:通过执行一个或多个循环来沉积膜,循环包括:(a)提供具有一个或多个特征的衬底,每个特征包括特征开口;(b)在使得第一前体能吸附到所述衬底的表面上的条件下,将所述衬底暴露于所述第一前体,由此形成第一前体吸附层;(c)在将所述衬底暴露于所述第一前体后,将所述衬底暴露于含卤素的蚀刻剂;以及(d)将所述衬底暴露于第二反应物并点燃等离子体,以在所述特征开口处或其附近选择性地蚀刻所述第一前体吸附层并形成膜。
含卤素的蚀刻剂的实例包括三氟化氮、氯、三氟甲烷、四氟化碳、以及它们的组合。在一些实施方式中,所述含卤素的蚀刻剂是化学式为CnF2n+2或CnF2n的化合物,其中n>1。
在多种实施方式中,在(d)之前清扫所述室。例如,所述膜可以为电介质膜或金属膜。在一些实施方式中,所述膜是含硅膜,例如氮化硅、碳化硅和氧化硅。所述第二反应物可以是氧化剂或还原剂。在多种实施方式中,每n个循环才执行(d),其中n是等于或大于1的整数。
另一个方面涉及一种用于处理衬底的装置,该装置包括:(a)至少一个处理室,所述处理室包含用于保持衬底的基座;(b)至少一个出口,所述出口用于耦合到真空;(c)一个或多个处理气体进口,所述处理气体进口耦合到一个或多个含硅前体源和一种或多种含卤素的蚀刻剂;(d)射频(RF)产生器;和(e)用于控制所述装置中的操作的控制器,所述控制器包括用于以下操作的机器可读指令:(i)将含硅前体引入所述处理室;(ii)在将所述含硅前体引入之后,将含卤素的蚀刻剂引入所述室;以及(iii)将含氮反应物引入所述室并点燃等离子体以形成氮化硅膜。
所述控制器还可以包括用于以下操作的机器可读指令:在将所述含氮反应物引入之前引入清扫气体以清扫所述室。
含卤素的蚀刻剂的实例包括三氟化氮、氯、三氟甲烷、四氟化碳、以及它们的组合。在一些实施方式中,所述含卤素的蚀刻剂是化学式为CnF2n+2或CnF2n的化合物,其中n>1。
还有一个方面涉及一种用于处理衬底的装置,该装置包括:(a)至少一个处理室,所述处理室包含用于保持衬底的基座;(b)至少一个出口,所述出口用于耦合到真空;(c)一个或多个处理气体进口,所述处理气体进口耦合到一个或多个前体源和一种或多种含卤素的蚀刻剂;(d)射频(RF)产生器;和(e)用于控制所述装置中的操作的控制器,所述控制器包括用于以下操作的机器可读指令:(i)将前体引入所述处理室;(ii)在将所述含硅前体引入之后,将含卤素的蚀刻剂引入所述室;以及(iii)将第二反应物引入所述室并点燃等离子体以形成膜。
具体而言,本发明的一些方面可以描述如下:
1.一种处理在室中的衬底的方法,该方法包括:
(a)提供具有一个或多个特征的衬底,每个特征包括特征开口;
(b)在使得含硅前体能吸附到所述衬底的表面上的条件下,将所述衬底暴露于所述含硅前体,由此形成含硅前体吸附层;
(c)在将所述衬底暴露于所述含硅前体后,将所述衬底暴露于含卤素的蚀刻剂;以及
(d)将所述衬底暴露于含氮反应物并点燃等离子体,以在所述特征开口处或其附近选择性地蚀刻所述第一前体吸附层并形成氮化硅膜。
2.根据条款1所述的方法,其中在使所述含卤素的蚀刻剂能选择性地吸附到所述第一前体吸附层上的条件下,使所述衬底暴露于所述含卤素的蚀刻剂。
3.根据条款1所述的方法,其中所述含卤素的蚀刻剂选自由三氟化氮、氯、三氟甲烷、四氟化碳、以及它们的组合组成的组。
4.根据条款1所述的方法,其中所述含卤素的蚀刻剂包括化学式为CnF2n+2或CnF2n的化合物,其中n>1。
5.根据条款1-4中任一项所述的方法,其中在将所述衬底暴露于所述含卤素的蚀刻剂之后清扫所述室。
6.根据条款5所述的方法,其中通过使清扫气体流动来清扫所述室,所述清扫气体选自由氩气、氦气、氮气和氢气组成的组。
7.根据条款1-4中任一项所述的方法,其中所述含硅前体选自由硅烷、乙硅烷、丙硅烷、丁硅烷、三甲硅烷基胺、氨基硅烷、和卤代硅烷组成的组。
8.根据条款1-4中任一项所述的方法,其中所述含氮反应物选自由氮、氨、肼和胺类组成的组。
9.根据条款1-4中任一项所述的方法,其还包括重复(a)-(d)。
10.根据条款1-4中任一项所述的方法,其中(a)-(d)在同一室中进行。
11.一种处理在室中的衬底的方法,该方法包括:
通过执行一个或多个循环来沉积膜,循环包括:
(a)提供具有一个或多个特征的衬底,每个特征包括特征开口;
(b)在使得第一前体能吸附到所述衬底的表面上的条件下,将所述衬底暴露于所述第一前体,由此形成第一前体吸附层;
(c)在将所述衬底暴露于所述第一前体后,将所述衬底暴露于含卤素的蚀刻剂;以及
(d)将所述衬底暴露于第二反应物并点燃等离子体,以在所述特征开口处或其附近选择性地蚀刻所述第一前体吸附层并形成膜。
12.根据条款11所述的方法,其中所述含卤素的蚀刻剂选自由三氟化氮、氯、三氟甲烷、四氟化碳、以及它们的组合组成的组。
13.根据条款11或12所述的方法,其中在(d)之前清扫所述室。
14.根据条款11或12所述的方法,其中所述膜为电介质膜或金属膜。
15.根据条款11或12所述的方法,其中所述膜选自由氮化硅、碳化硅和氧化硅组成的组。
16.根据条款11或12所述的方法,其中所述第二反应物是氧化剂或还原剂。
17.根据条款11或12所述的方法,其中每n个循环才执行(d),其中n是等于或大于1的整数。
18.一种用于处理衬底的装置,该装置包括:
(a)至少一个处理室,所述处理室包含用于保持衬底的基座;
(b)至少一个出口,所述出口用于耦合到真空;
(c)一个或多个处理气体进口,所述处理气体进口耦合到一个或多个含硅前体源和一种或多种含卤素的蚀刻剂;
(d)射频(RF)产生器;和
(e)用于控制所述装置中的操作的控制器,所述控制器包括用于以下操作的机器可读指令:
(i)将含硅前体引入所述处理室;
(ii)在将所述含硅前体引入之后,将含卤素的蚀刻剂引入所述室;以及
(iii)将含氮反应物引入所述室并点燃等离子体以形成氮化硅膜。
19.根据条款18所述的装置,其中,所述控制器还包括用于以下操作的机器可读指令:在将所述含氮反应物引入之前引入清扫气体以清扫所述室。
20.根据条款18所述的装置,其中,所述含卤素的蚀刻剂选自由三氟化氮、氯、三氟甲烷、四氟化碳、以及它们的组合组成的组。
这些和其它方面将在下面参照相关附图进行说明。
附图说明
图1是描述根据所公开的实施方式所述的方法的操作的工艺流程图。
图2A和图2B是用于根据所公开的实施方式沉积膜的机理的实例的示意图。
图3是显示根据所公开的实施方式所述的方法中的循环的实施例的时序示意图。
图4是用于执行所公开的实施方式的示例性处理室的示意图。
图5是用于执行所公开的实施方式的示例性处理工具的示意图。
图6A是在具有特征的衬底上沉积的氮化硅膜的图像。
图6B是在根据所公开的实施方式进行的试验中的在具有特征的衬底上沉积的氮化硅膜的图像。
具体实施方式
在下面的描述中,阐述了许多具体细节以提供对所呈现的实施方式的透彻理解。在没有这些具体细节中的一些或所有的情形下可以实施所公开的实施方式。在其它情形下,未详细描述公知的处理操作,以避免不必要地模糊所公开的实施方式。虽然将结合具体的实施方式描述所公开的实施方式,但是应理解的是并不意在限制所公开的实施方式。
以下公开的实现方式描述了在例如晶片之类衬底或其它工件上的材料的沉积。工件可以是各种形状、尺寸、和材料。除了半导体晶片外,在本发明公开的实现方式可以使用的其它工件还包括不同的物品,如印刷电路板等。所述工艺和装置可以用于半导体器件、显示器、发光二极管、光伏电池板等的制造中。
在一个实例中,氮化硅可以在半导体器件的制造中用作扩散阻挡层、栅极绝缘体、侧壁垫层、和封装层。在特定的应用中,氮化硅被用作在存储器装置中的存储器封装层。在这样的器件中,碳层可以在加热时相改变的相变层上沉积。该相变层如果损坏,就可能不会改变相。该相变层也可以是对光敏感的。为了防止对相变层的任何损害,可以在相变层上沉积氮化硅共形存储器封装层。该存储器封装层很少或几乎没有其它化合物的污染,并在低温下沉积,以避免损坏器件。也可以在其它应用中使用共形氮化硅层。
本发明提供了通过将原子层蚀刻(ALE)技术与原子层沉积(ALD)结合来沉积共形膜的方法。所公开的实施方式包括沉积氮化硅从而形成具有足够的反应性以与含氮等离子体反应的含硅前体吸附层的方法。注意,尽管本文所提供的实施例描述了氮化硅保形沉积,应当理解的是,其它材料可以使用所公开的实施方式来沉积。例如,本文提供的方法可以用于沉积氧化硅、碳化硅、掺杂的含硅膜、含金属(如氮化铝和氮化钛)膜、以及在器件制造中的其它共形膜。
所沉积的膜是共形的。膜的共形性可以通过台阶覆盖率来测量。台阶覆盖率可通过在特征的底部、侧壁、或顶部上沉积的膜的平均厚度与在特征的底部、侧壁、或顶部上沉积的膜的平均厚度进行比较来计算。例如,台阶覆盖率可以按以下方式计算:将在特征的侧壁上沉积的膜的平均厚度除以在特征的顶部沉积的膜的平均厚度,再将所得值乘以100,以获得百分比值。某些公开的实施方式涉及在原子层沉积循环期间,在将衬底暴露于前体和将衬底暴露于第二反应物之间,在等离子体环境中,通过将衬底暴露于蚀刻剂在衬底上沉积共形层。
本发明提供的方法涉及通过将一些ALE技术与ALD结合来沉积膜。ALE是一种使用连续的自限性反应去除薄材料层的技术。典型地,ALE循环包括改性操作以形成反应层,接着是去除操作,以仅除去或蚀刻此改性层。举例而言,ALE循环可以包括以下的操作:(i)输送反应物气体至容纳衬底的室,(ii)从该室清扫反应物气体,(iii)输送去除气体和任选的等离子体,以及(iv)清扫该室。
ALD是一种使用连续的自限性反应沉积薄材料层的技术。通常,ALD循环包括以下操作:输送和吸附至少一种反应物到衬底表面上,然后使被吸附的反应物与一种或多种反应物反应,以形成部分的膜层。举例而言,氮化硅沉积循环可包括以下的操作:(i)输送/吸附含硅前体,(ii)从室清扫含硅前体,(iii)输送氮等离子体,和(iv)从室清扫等离子体。其它类型的膜可以使用各种前体和共反应物的脉冲来沉积。
不像化学气相沉积(CVD)技术,ALD工艺使用表面介导的沉积反应以逐层地沉积膜。在ALD工艺的一个实施例中,包含表面活性位点群的衬底表面暴露于按剂量提供到容纳衬底的室的气相分布的第一前体,如含硅前体。该第一前体的分子被吸附在衬底表面,包含第一前体的化学吸附物质和/或物理吸附分子。应当理解的是,当如本文所述,化合物被吸附到衬底表面时,吸附层可以包含该化合物以及该化合物的衍生物。例如,含硅前体的吸附层可包含含硅前体以及含硅前体的衍生物。在第一前体投配之后,接着将室排空,以去除气相中剩余的第一前体的绝大部分或全部,使得主要或仅仅所吸附的物质剩余。在一些实现方式中,室可以不完全排空。例如,反应器可以排空,使得在气相中的第一前体的局部压强足够低,以减缓反应。将第二反应物(例如含氮反应物)引入到室,使得这些分子中的一些与吸附在表面上的第一前体反应。在一些工艺中,第二反应物与所吸附的第一前体立即反应。在其它实施方式中,第二反应物仅在临时施加活化源之后反应。然后可将室再次排空以去除未结合的第二反应物分子。如上所述,在一些实施例中,室可以不被完全排空。附加的ALD循环可被用于构建膜厚。
在某些实施方式中,ALD第一前体的剂量部分地充满衬底的表面。在一些实施方式中,在使前体接触衬底以均匀地充满表面之前,结束ALD循环的投配阶段。典型地,在这时将前体流关断或转移,并且仅仅清扫气体流动。通过在这种亚饱和状态下工作,ALD工艺减少了循环时间并提高了吞吐量。但是,由于前体吸附不是饱和受限的,因此被吸附的前体浓度在整个衬底表面可以略有变化。在亚饱和状态操作ALD工艺的实施例在2013年10月23日提交的、名称为“SUB-SATURATED ATOMIC LAYERDEPOSITION AND CONFORMAL FILM DEPOSITION,”的美国专利申请No.14/061587中被提供,该专利文件通过引用整体并入本发明。
在一些实现方式中,所述ALD方法包含等离子体活化。如本文所述,本文所述的ALD方法和装置可以是共形膜沉积(CFD)法,其概括地描述在2011年4月11日提交的名称为“PLASMA ACTIVATEDCONFORMAL FILM DEPOSITION”的美国专利申请No.13/084399(现在的美国专利No.8728956)和2011年4月11日提交的名称“SILICON NITRIDEFILMS AND METHODS”的美国专利申请No.13/084305中,这些专利文件通过引用整体并入本文。
图1提供了用于执行根据所公开的实施方式的操作的工艺流程图。虽然本文所提供的实施例在沉积氮化硅膜的背景下描述所公开的实施方式,但是应该理解的是,这些方法也可以用于通过ALD沉积任何材料膜。
在图1的操作101中,将衬底提供至单站式室或多站式室的处理站。所述衬底可以是硅晶片,例如,200mm的晶片,300mm的晶片或450mm的晶片,包括具有一个或更多个材料层的晶片,该材料例如沉积在该晶片上的电介质、导电材料或半导电材料。衬底可具有“特征”,例如通孔或接触孔,其可表征为一个或更多个狭窄的和/或内凹的(re-entrant)开口、特征内的收缩部和高深宽比。所述特征可以在一个或更多个上述层中形成。特征的一个示例是半导体衬底中的或该衬底上的层中的孔或通孔。另一个示例是衬底或层中的沟槽。在多个实施方式中,所述特征可以具有下层,例如阻挡层或粘合层。下层的非限制性实施例包括介电层和导电层,例如,硅氧化物、硅氮化物、硅碳化物、金属氧化物、金属氮化物、金属碳化物和金属层。
在一些实施方式中,所述特征可以具有至少约2:1、至少约4:1、至少约6:1、至少约10:1、或更高的深宽比。该特征也可具有接近开口的尺寸,例如,介于约10纳米(nm)至500nm之间的开口直径或线宽度,例如介于约25nm至约300nm之间的开口直径或线宽度。所公开的方法可以在具有特征的衬底上进行,该特征具有小于约150nm的开口。通孔、沟槽或其它凹陷特征可以被称为未填充的特征或特征。根据多种实施方式,特征轮廓可以逐步缩小和/或包含在特征开口的悬垂部。内凹的轮廓是从特征的底部、封闭端、或内部向特征开口变窄的轮廓。内凹的轮廓可通过在图案化期间不对称的蚀刻动力学和/或由于在前面的膜沉积(例如扩散阻挡层沉积)中的非共形膜的台阶覆盖率所形成的悬垂部而产生。在多种实施例中,特征可以具有比特征的底部的宽度小的在特征的顶部的开口中的宽度。
在图1的操作103-115中,可以使惰性气体流动。在多种实施方式中,惰性气体用作载气。示例性的载气包含氩气、氦气和氖气。在一些实施方式中,载气不是氢,使得很少的氢甚至没有氢被掺入沉积的氮化硅膜中。在一些实施方式中,可以使用含氢的载气。在一些实施方式中,载气在一些操作中被用作清扫气体。在一些实施方式中,使载气转向。可以提供惰性气体以协助处理室的压强和/或温度控制、液体反应物的蒸发、更迅速地输送反应物和/或作为打扫气体用于从处理室和/或处理室管道去除处理气体。
各种所公开的实施方式可在介于约0.1托至约20托之间的室压强下进行。在许多实施方式中,所公开的方法可以在低于约650℃的衬底温度下进行,或在低于约450℃,或在介于约50℃和约650℃之间,例如约200℃的衬底温度下进行。在这样的实施方式中,基座可以被设置到低于约450℃的温度来控制衬底温度。在一些实施方式中,在较高的温度下,如大于约250℃,或大于450℃的温度下执行所述方法。
在图1的操作103中,使衬底暴露于第一前体,使得第一前体吸附在衬底表面上。虽然本文中所描述的实施例使用含硅前体作为第一前体,但应理解的是,第一前体可以是用于在衬底上沉积膜(例如氮化硅膜、氧化硅膜、碳化硅膜、氮化铝膜、氮化钨膜、氮化钛膜、氮化钽膜、氧化钛膜等等)的任何适当的前体。
操作103可以是ALD循环的一部分。如上所述,通常,ALD循环是用于进行一次表面沉积反应的最小的一组操作。在一些实施方式中,一个循环的结果是在衬底表面上产生氮化硅膜层的至少一部分。所述循环可包括某些辅助操作,例如打扫反应物或副产物中的一种和/或处理所沉积的膜的部分。通常,循环包括独特系列操作的一个示例。如上所述,通常,循环是用于进行一次表面沉积反应的最小的一组操作。一个循环的结果是在衬底表面上产生至少一部分膜层,例如一部分氮化硅膜层。
在操作103期间,衬底被暴露于第一前体,使得第一前体被吸附到衬底表面以形成吸附层。在一些实施方式中,含硅前体以自限制方式吸附到衬底表面上,使得一旦活性位点是由含硅前体占据,几乎没有或没有附加的含硅前体将被吸附在衬底表面上。例如,含硅前体可以被吸附到衬底表面的约60%上。在多种实施方式中,当含硅前体流到室中时,该含硅前体吸附在衬底的表面上的活性位点上,从而在该表面上形成薄的含硅前体层。在各种实施方式中,该层可以小于一个单层,以及可具有介于约0.2埃和约0.4埃之间的厚度。本文所提供的方法可以在低于约450℃的温度下进行。在高于约450℃的工艺温度时,某些含硅前体会分解以形成硅层。
含硅前体是用于制造含硅膜的单一试剂或试剂的混合物,其中所述试剂或试剂混合物含有至少一种硅化合物。在一些实施方案中,含硅前体可以是,例如,硅烷、卤代硅烷、或氨基硅烷。然而,在多种实施方式中,含硅前体是不含卤素的。不含卤素的硅烷可以包含氢和/或碳基团,但不包含卤素。
适合于根据所公开的实施方式使用的含硅前体包括聚硅烷(H3Si-(SiH2)n-SiH3),其中n>0。硅烷的实施例是硅烷(SiH4)、乙硅烷(Si2H6)和有机硅烷,有机硅烷如甲基硅烷、乙基硅烷、异丙基硅烷、叔丁基硅烷、二甲基硅烷、二乙基硅烷、二叔丁基硅烷、烯丙基硅烷、仲丁基硅烷、叔己基硅烷(thexylsilane)、异戊硅烷,叔丁基乙硅烷、二叔丁基乙硅烷等。
卤代硅烷含有至少一个卤素基团,并且可以含有或可以不含有氢和/或碳基团。卤代硅烷的实例是碘硅烷、溴硅烷、氯硅烷和氟硅烷。虽然卤代硅烷,尤其是氟硅烷,可以在等离子体被激励时形成可以蚀刻硅材料的反应性卤化物,但在本发明所描述的某些实施方式中,当等离子体被激励时,卤代硅烷可以不引入室中,因此,由卤代硅烷形成的反应性卤化物可以减少。具体的氯硅烷是四氯硅烷、三氯硅烷、二氯硅烷、单氯硅烷、氯烯丙基硅烷、氯甲基硅烷、二氯甲基硅烷、氯二甲基硅烷、氯乙基硅烷、叔丁基氯硅烷、二-叔丁基氯硅烷、氯异丙基硅烷、氯仲丁基硅烷、叔丁基二甲基氯硅烷、叔己基二甲基氯硅烷(thexyldimethylchlorosilane)、以及类似物。
氨基硅烷包含键合到硅原子的至少一个氮原子,而且也可以含有氢、氧、卤素和碳。氨基硅烷的实例是单氨基硅烷、二氨基硅烷、三氨基硅烷和四氨基硅烷(分别为H3Si(NH2)4,H2Si(NH2)2,HSi(NH2)3和Si(NH2)4),以及经取代的单氨基硅烷、二氨基硅烷、三氨基硅烷和四氨基硅烷,例如,叔丁基氨基硅烷、甲基氨基硅烷、叔丁基硅烷胺,双(叔丁基氨基)硅烷(SiH2(NHC(CH3)3)2(BTBAS)、叔丁基甲硅烷基氨基甲酸酯、SiH(CH3)-(N(CH3)2)2、SiHCl-(N(CH3)2)2、(Si(CH3)2NH)3、以及类似物。氨基硅烷的另一个实例是三甲硅烷基胺(N(SiH3)3)。
可以被用来代替在操作103的含硅前体的其它第一前体的实例在下面给出。
图2A和图2B是根据图1所述的方法中的各个阶段的实施例的示意图。图2A和2B示出了在衬底的表面上的在特征开口处或其附近的分子的示例,其可以是在特征的顶部或顶部附近。在一些实施方式中,在沿着特征的侧壁或底部的在特征内的衬底表面可以表现出如在图2A和2B所描绘的化学机理之类的化学机理。在图2A和图2B所提供的实施例中,含硅前体是乙硅烷,蚀刻剂是三氟化氮,而第二反应物是氮。应该理解的是,其它含硅的前体、蚀刻剂和第二反应物可在所公开的实施方式中使用,并且在一些实施方式中可以经历与诸如相对于图2A和2B所描述的化学机理类似的化学机理。
在图2A中的201,衬底200被暴露于乙硅烷,由此乙硅烷分子211、221和231吸附到衬底200的表面上,从而形成乙硅烷吸附层。
回到图1,在操作105中,处理室被任选地清扫以除去气相中的未吸附到衬底表面的过量的含硅前体。清扫该室可以包括使清扫气体或打扫气体流动,清扫气体或打扫气体可以是在其它操作中使用的载气,或者可以是不同的气体。在一些实施方案中,清扫可包括抽空该室。示例性的清扫气体包含氩气、氮气、氢气和氦气。在一些实施方式中,操作105可以包含用于抽空处理室的一个或多个抽空子阶段。可替代地,应当理解,在一些实施方式中可以省略操作105。操作105可具有任何适当的持续时间,例如介于约0秒至约60秒之间,例如约0.01秒。在一些实施方式中,增大一种或多种清扫气体的流率可以减少操作105的持续时间。清扫气体流率可以根据各种反应物的热力学特性和/或处理室和/或处理室管道的几何特征进行调整以修改操作105的持续时间。在一非限制性实施例中,清扫阶段的持续时间可以通过调节清扫气体的流率进行调节。这可能会减少沉积循环时间,从而可以提高衬底吞吐量。在清扫后,该含硅前体保持吸附在衬底表面上。
在操作107中,衬底被暴露于含卤素的蚀刻剂。含卤素的蚀刻剂可以是任何含卤素的化合物,如含氟化合物或含氯化合物。在多种实施方式中,含卤素的蚀刻剂是三氟化氮、氯、或含碳的蚀刻剂、或它们的组合。在一些实施方式中,含碳的蚀刻剂是CHF3,或化学式为CnF2n+2或为CnF2n的化合物,其中n>1,例如CF4。在执行ALD以沉积氮化物的一些实施方式中,可避免含氯的蚀刻剂化合物。这是因为含氯蚀刻剂一般不容易蚀刻氮化物。
执行操作107的频率可取决于从沉积的ALD层观察到的悬垂物的量。在各种实施方式中,每一个至每50个ALD循环执行才操作107。在一些实施例中,每个ALD循环执行操作107。在一些实施方式中,每50个或更多个ALD循环才执行操作107。操作107可在非等离子体环境中进行。在等离子体环境中执行操作107可以产生高数量的反应性卤化物物质,由此在衬底上蚀刻的比所希望的多。例如,反应性卤化物物质可以蚀刻大部分或整个吸附在衬底表面上的第一前体,从而降低了产量且降低了沉积速率。
不受具体理论的限制,相信,该含卤素化合物吸附于含硅前体吸附层的表面上。例如,在图2的203中,三氟化氮分子243被引入到室,使得所述三氟化氮分子243吸附在衬底200的乙硅烷吸附层上。在许多实施方式中,所述含卤素的蚀刻剂流入室中持续足以吸附在大部分或全部的衬底表面上的时间。在一些实施方式中,含卤素的蚀刻剂可以选择性吸附在特征开口处或其附近。在一些实施方式中,含卤素的蚀刻剂可选择性吸附,使得更多的含卤素的蚀刻剂被吸附在特征的顶部或在该顶部附近,诸如对于垂直特征而言,在特征开口附近,而不是在特征的底部或在该底部附近。促进选择性吸附在特征的顶部或在该顶部附近的适当的工艺条件在下文描述。
回到图1,在操作109中,清扫室以除去残余的蚀刻剂,例如残留在气相中和未吸附在第一前体吸附层的表面上的蚀刻剂。清扫条件和方法可以是上文相对于操作105所描述的清扫条件和方法中的任何一些。在一些实施方法中,执行操作109,以便防止残留的蚀刻剂在随后的操作中去除太多的第一前体吸附层。例如,如果在等离子体被点燃时,残留的三氟化氮气体存在于室中,则受激励的氟会撞击衬底,由此蚀刻衬底的表面,使得相比于沉积执行较多的蚀刻。在一些实施方式中,如果当等离子体被点燃时,气相中的残留的蚀刻剂是存在于室中,则沉积的效率和沉积速率会下降。
在操作111中,将衬底暴露于第二反应物,并且点燃等离子体。在各种实施方式中,第二反应物流和等离子体可被同时接通。在一些实施方式中,第二反应物流可以在接通等离子体之前接通,例如,以使第二反应物流动能够稳定。在多种实施方式中,第二反应物是含氮的反应物,以在衬底的表面上形成至少部分氮化硅膜。含氮的反应物是含有至少一个氮的反应物或反应物的混合物,例如氨,肼,胺类(含碳的胺类),如甲胺,二甲胺,乙胺,异丙胺,叔丁胺,二叔丁胺,环丙胺,仲丁胺,环丁胺,异戊胺,2-甲基丁-2-胺,三甲胺,二异丙胺,二乙基异丙胺,乙二胺,叔丁胺,二叔丁基肼,以及含芳烃的胺类,如苯胺,吡啶,和苄胺。胺类可以是伯胺、仲胺、叔胺或季胺(例如,四烷基铵化合物)。含氮的反应物可含有除氮以外的杂原子,例如,羟基胺、叔丁氧羰基胺和N-叔丁基羟基胺是含氮的反应物。示例性的含氮反应剂包含氮气、氨和胺类。
对于其它含硅材料的沉积,其它反应物可以用作第二反应物以沉积不同的材料膜。例如,对于使用所公开的实施方式进行的碳化硅的膜沉积,第二反应物可以是含碳反应物。例如,对于氧化硅的沉积,可以使用氧化剂或含氧化合物。对于掺杂膜的沉积,掺杂剂也可以作为第二反应物加入。注意,在ALD循环点燃等离子体时,术语“第二反应物”可用于描述引入到室的一种或多种气体。
在各种实施方式中,在操作111过程中,等离子体能量被提供以激励第二反应物(例如含氮气体)成为与所述第一前体吸附层进行反应的离子和自由基以及其它活性物质。例如,等离子体可以直接或间接激活含氮气相分子以形成氮自由基或离子。等离子体也可激励被吸附的蚀刻剂,由此形成受激励的蚀刻剂物质,其可以蚀刻第一前体并将其从衬底移除。可监控室的条件,使得足够的蚀刻剂被激励以调节特征轮廓并提高共形性。例如,等离子体条件可以被控制以优先地蚀刻特征开口处或其附近,而在特征的侧壁处或其附近或朝向特征的底部形成较少的受激励的蚀刻剂。促进选择性吸附在特征的顶部或其附近的适当的工艺条件在下文描述。
在多种实施方式中,等离子体是原位等离子体,以使得等离子体在室中的衬底表面的正上方形成。原位等离子体可以以介于约0.2122瓦/平方厘米至约2.122瓦/平方厘米之间的每衬底面积的功率点燃。例如,对于处理4个300毫米晶片的室,功率范围可为介于约150W至约6000W之间、或者约600W至约6000W之间、或者介于约800W至约4000W之间。例如,用于ALD工艺的等离子体可通过使用两个电容耦合板施加射频(RF)场给气体而产生。这些板之间的气体通过RF场进行的电离点燃等离子体,从而在等离子体放电区域产生自由电子。这些电子被RF场加速,并且会与气相反应物分子发生碰撞。这些电子与反应物分子的碰撞可形成参与沉积过程的自由基物质。应该理解的是,RF场可以经由任何合适的电极耦合。在多种实施方式中,使用高频等离子体,其具有至少约13.56MHz,或至少约27MHz,或至少约40MHz,或至少约60MHz的频率。在一些实施方式中,可以使用基于微波的等离子体。电极的非限制性实例可以包括处理气体分配喷头和衬底支撑基座。应当理解,用于ALD工艺的等离子体可以通过与电容耦合RF场到气体不同的一种或多种合适的方法形成。在一些实施方式中,等离子体是远程等离子体,使得第二反应物在室上游的远程等离子体产生器中点燃,然后输送到容纳衬底的室内。
工艺条件精心设计以通过选择性蚀刻获得共形膜。合适的蚀刻温度、蚀刻剂流量、清扫操作、等离子体条件、和蚀刻压强的结合可以帮助获得理想的共形性。如果对于每种正在沉积的膜类型没有适当地调整蚀刻共形性,则这可能会导致非共形沉积,其中台阶覆盖率差。工艺条件可能使得非共形蚀刻(也称为选择性蚀刻)被执行。
在较高温度下,进入的蚀刻剂物质,如氟原子,很容易反应和在特征入口蚀刻,从而导致较不共形的蚀刻;在较低温度下,进入的蚀刻剂物质能够扩散并进一步蚀刻到特征内,从而产生较共形的蚀刻。在操作109期间较短的清扫使蚀刻剂物质保留在室内和衬底上,从而导致更多的蚀刻剂物质扩散并进一步蚀刻到特征内。在操作107过程中,对蚀刻剂的短的暴露将趋向于发生反应并在特征入口蚀刻,从而产生较共形的蚀刻。在一些情况下,蚀刻剂在操作107中流动,使得含卤素的蚀刻剂被优先吸附在特征顶部或其附近,而在操作111期间,当等离子体被点燃时,该特征的顶部比在特征内的侧壁蚀刻得较多。较低的蚀刻剂流率将导致吸附在衬底表面上的蚀刻剂分子较少。较高的压强会导致蚀刻剂物质(如氟自由基)形成分子氟的较多的重组。分子氟比氟自由基具有较低的粘附系数,并且因此更容易在蚀刻前扩散到特征内,从而导致较不共形的蚀刻。
如在图2A中所示,在205期间,将衬底200暴露于第二反应物(在本实施例中为氮),同时点燃等离子体,从而产生受激励的氮物质260,受激励的氮物质260尤其可包含离子、自由基(例如,在205示出的·N)、以及中性物质。在所提供的实施例中,等离子体还激励吸附的三氟化氮,三氟化氮由此离解成受激励的氮·N和受激励的氟物质250(例如,·F)。一些氟物质250可以通过撞击乙硅烷的硅中心而与吸附的乙硅烷进行反应,而一些受激励的氮物质260,无论是来自三氟化氮还是氮,都通过撞击乙硅烷的硅中心而与吸附的乙硅烷进行反应。
结果,在图2B的207中,受激励的氟与乙硅烷反应以从衬底200的表面蚀刻乙硅烷并形成六氟化二硫(217和227),从而现在氟255被健合到硅。与此同时,如果受激励的氮与衬底表面上的乙硅烷发生反应,则可以形成Si-N键(265),由此在该表面上形成至少部分的氮化硅层(237)。注意,在一些实施方式中,蚀刻工艺可经历不同的机理,并且在207所描绘的机理是可能的机理中的一个实施例。
回到图1,在操作118中,该室可任选清扫以除去被蚀刻掉的物质和任何残余的副产物。如图2中所示,在209,清扫该室后,将部分的氮化硅层237保留在衬底200的表面上。注意,虽然在201吸附的乙硅烷层覆盖较多的表面积,但由于来自蚀刻剂三氟化氮的局部蚀刻,因而只有一部分氮化硅层沉积,如图209所示。在每个循环期间,相比于特征的靠近特征的底部或沟槽的表面,特征的在特征开口处或其附近的表面可以沉积部分的氮化硅的较少部分。结果,在特征开口处或其附近的沉积可调节,并且整体沉积是高度共形的。
在图1的操作115中,确定膜的所需的厚度是否已沉积。如果没有,则重复操作103-113足够的循环以沉积所需的膜厚度。沉积循环的任何适当数量可被包含在ALD工艺中,以沉积氮化硅的所需的膜厚度。例如,大约50个沉积循环可被执行以使用所公开的实施方式在衬底上沉积膜。如上所述,操作107可以或可以不在每个沉积循环中进行。
图3是根据所公开的实施方式的示例性脉冲的时序图。图3示出了在一个示例性的ALD工艺300中针对各种工艺参数的阶段,如针对载气流、第一前体、蚀刻剂流、等离子体和第二反应物流的阶段。线相应地表示所述流或等离子体相应地被接通和关断的时间。示例性的工艺参数包含但不限于,惰性物质和反应物质的流率、等离子体功率和频率、衬底温度、和处理室的压强。描绘了两个沉积循环310A和310B。每个沉积循环包含多个阶段。例如,沉积循环310A包含第一前体暴露阶段320A、清扫阶段340A(其可以是任选的)、蚀刻剂阶段350A、清扫阶段355A、第二反应物与等离子体暴露阶段360A、和另一任选的清扫阶段380A。同样地,沉积循环310B包含第一前体暴露阶段320B、清扫阶段340B(其可以是任选的)、蚀刻剂阶段350B、清扫阶段355B、第二反应物与等离子体暴露阶段360B、和另一任选的清扫阶段380B。如图所示,在该示例性过程300中,载气在整个过程中流动。在多种实施方式中,载气被用作清扫气体。注意,在一些实施方式中,载气可以与清扫气体不同。在一些实施方式中,载气仅在清扫阶段(例如,340A、355A、380A、340B、355B、和380B)流动。载气可以是上文参照图1的操作105所描述的那些载气中的任何载气。
在第一前体暴露阶段(320A和320B),接通第一前体,但不接通蚀刻剂、不接通等离子体、且不接通第二反应物。该阶段可对应于图1的操作103。在可对应于图1中的操作105的清扫阶段340A中,载气流动,同时第一前体、蚀刻剂、等离子体和第二反应物被关断。在可对应于图1中的操作107的蚀刻剂阶段350中,蚀刻剂与载气流动,同时第一前体、等离子体、和第二反应物被关断。在可对应于图1中的操作109的清扫阶段355A中,载气流动,同时第一前体、蚀刻剂、等离子体和第二反应物被关断。在第二反应物与等离子体暴露阶段360A,等离子体被接通,同时第二反应物与载气流动,并且第一前体和蚀刻剂流被关断。在可对应于图1中的操作111的清扫阶段380A中,载气流动,同时第一前体、蚀刻剂、等离子体和第二反应物被关断。在该示例性过程300中,在图1的操作115中确定,所沉积的膜没有足够的厚度或没有所需的厚度,所以重复沉积循环(显示为310B)。
在一些实施方式中,包含蚀刻剂阶段的沉积循环可以仅不包含蚀刻剂阶段的许多沉积循环已经执行之后执行。例如,包含蚀刻剂阶段的沉积循环可以在约50个不包含蚀刻剂阶段的沉积循环之后进行。
如上所述,虽然本文所提供的实施例沉积氮化硅膜,但其它材料的膜也可以使用所公开的实施方式沉积。例如,所沉积的膜可以包含金属。可以形成的含有金属的膜的实例包含铝、钛、铪、钽、钨、锰、镁、锶等的氧化物和氮化物,以及金属元素膜。示例性的前体可以包括金属烷基胺、金属醇盐、金属烷基酰胺、金属卤化物、金属β-二酮、金属羰基化合物、有机金属化合物等。合适的含金属的前体将包括被期望掺入膜中的金属。例如,含钽层可通过使五(二甲氨基)钽与氨或另一还原剂反应来沉积。可以使用的含金属的前体的进一步的实例包括三甲基铝、四乙氧基钛、四二甲基氨基钛、四(乙基甲基酰胺)铪、双(环戊二烯基)锰和双(正丙基环戊二烯基)镁。用于沉积氧化物的第二反应物的实施例包含氧化剂,该氧化剂可以是氧气与弱氧化剂的混合物,弱氧化剂如一氧化二氮、一氧化碳、二氧化碳、一氧化氮、二氧化氮、氧化硫、二氧化硫、含氧烃(如CxHyOz)和/或水。在其它实现方式中,氧化反应物可以完全是弱氧化剂。可替代地,该氧化反应物可以包含臭氧。
装置
图4绘出了具有用于保持低压环境的处理室主体402的原子层沉积(ALD)处理站400的一实施方式的示意图。多个ALD处理站400可以包含在通常低压处理工具环境中。例如,图5绘出了多站式处理工具500的一实施方式。在一些实施方式中,ALD处理站400的一个或一个以上的硬件参数(包含下文详细讨论的那些)可以由一个或一个以上的计算机控制器450以编程方式调节。
ALD处理站400与反应物输送系统401a流体连通,以将处理气体输送至分配喷头406。反应物输送系统401a包含混合容器404,混合容器404用于混合和/或调节处理气体以输送至喷头406,处理气体如含卤素的蚀刻剂气体、或含硅气体、或含氮气体。一个或一个以上的混合容器入口阀420可以对处理气体导入至混合容器404进行控制。
举例而言,图4的实施方式包含汽化点403,汽化点403用于汽化将供应至混合容器404的液体反应物。在一些实施方式中,汽化点403可以是加热的蒸发器。从这样的蒸发器产生的饱和的反应物蒸气会在下游输送管道凝结。不兼容气体暴露至凝结的反应物会产生小颗粒。这些小颗粒可能阻塞管道、阻碍阀操作、污染衬底等。处理这些问题的一些方法涉及清扫和/或排空输送管道以去除残留反应物。然而,清扫输送管道会增加处理站循环时间,降低处理站吞吐量。因此,在一些实施方式中,汽化点403下游的输送管道可以被热追踪。在一些实施例中,混合容器304也可以被热追踪。在一个非限制性示例中,汽化点403下游的管道具有增大的温度分布,在混合容器404处从约100℃延伸至约150℃。
在一些实施方式中,液体前体或者液体反应物可以在液体喷射器处汽化。例如,液体喷射器可以将液体反应物的脉冲喷射到混合容器上游的载体气体流中。在一个实施方式中,液体喷射器可以通过将液体从较高压闪变到较低压来汽化反应物。在另一个示例中,液体喷射器可以将液体雾化为接下来在加热的输送管中汽化的分散的微滴。较小的液滴比较大的液滴可以较快汽化,从而减小了在液体注入和完成汽化之间的延迟。较快的汽化可以减小汽化点403下游的管道长度。在一个方案中,液体喷射器可以直接装载到混合容器404。在另一个方案中,液体喷射器可以直接装载到喷头406。
在一些实施方式中,可以在汽化点403上游设置液体流控制器(LFC)来控制用于汽化并输送至处理站400的液体的质量流量。例如,LFC可以包含位于LFC下游的热质量流量计(MFM)。然后可以响应于由与MFM电通信的比例积分微分(PID)控制器提供的反馈控制信号,来调节LFC的柱塞阀。然而,其可以采取一秒或一秒以上来使用反馈控制以稳定液体流。这可以延长投配液体反应物的时间。因此,在一些实施方式中,LFC可以在反馈控制模式和直接控制模式之间动态切换。在一些实施方式中,这可以通过禁用PID控制器和LFC的感测管道来执行。
喷头406朝衬底412分配处理气体。在图4所示的实施方式中,衬底412位于喷头406下方,并且示出为安置在基座408上。喷头406可以具有任何适当的形状,并可以具有任何适当数量和布置的端口,以将处理气体分配至衬底412。
在一些实施方式中,基座408可以升高或降低以暴露衬底412给衬底412和喷头406之间的体积。应理解的是,在一些实施方式中,基座高度可以经由合适的计算机控制器450通过编程方式进行调节。
在另一种情况下,调节基座408的高度可以使得等离子体密度在包含在工艺中的等离子体活化循环期间内改变。在处理阶段结束时,基座408可以在另一衬底传送阶段被降低以使得衬底412能从基座408移走。
在一些实施方式中,喷头406的位置可以相对于基座408调节以改变衬底412和喷头406之间的体积。此外,应当理解的是,基座408和/或喷头406的垂直位置可以通过本公开内容的范围内的任何合适的机构来改变。在一些实施方式中,基座408可包含用于旋转衬底412的方位的旋转轴线。应该理解的是,在一些实施方式中,这些示例性调节中的一种或多种可以通过一个或多个适当的计算机控制器450以编程方式执行。
在如上所述可以使用等离子体的一些实施方式中,喷头406和基座408电连接射频(RF)功率源414和匹配网络416来对等离子体提供功率。在一些实施方式中,等离子体的能量可通过控制处理站的压强、气体的浓度、RF源功率、RF源频率以及等离子体功率脉冲时序中的一个或多个来控制。例如,RF功率源414和匹配网络416可在任何合适的功率下进行操作,以形成具有所期望的自由基物质的组分的等离子体。合适的功率的实施例包含在上文中。同样,RF功率源414可以提供任何适当频率的RF功率。在一些实施方式中,RF功率源414可以被配置为控制彼此独立的高频RF功率源和低频RF功率源。示例性的低频RF频率可以包含,但不限于,介于0kHz和500kHz之间的频率。示例性的高频RF频率可以包含,但不限于,介于1.8MHz和2.45GHz之间的频率,例如,或大于约13.56MHz、或大于27MHz、或大于40MHz、或大于60MHz的频率。应当理解,任何合适的参数可被离散地或连续地调制以提供用于表面反应的等离子体能量。等离子体条件可以被控制和/或维持,使得从蚀刻剂所产生的等离子体优先在特征开口处或其附近进行蚀刻,而不是在特征的侧壁或底部进行蚀刻。在一个非限制性实例中,等离子体功率可以间歇地施以脉冲,以相对于被连续提供功率的等离子体减少对衬底表面的离子轰击。
在一些实施方式中,等离子体可由一个或多个等离子体监控器原位监控。在一种情形中,等离子体功率可通过一个或多个电压、电流传感器(例如,VI探针)进行监控。在另一种情况下,等离子体密度和/或处理气体的浓度可以由一个或多个光发射光谱传感器(OES)来测量。在一些实施方式中,一个或多个等离子体参数可基于来自这样的原位等离子体监控器的测量结果通过编程方式进行调节。例如,OES传感器可用于反馈回路中以提供对等离子体功率的编程式控制。应理解的是,在一些实施方式中,可使用其它监控器来监控等离子体和其它工艺特性。这样的监控器可包含,但不限于,红外(IR)监控器、声学监控器、以及压力传感器。
在一些实施方式中,可以经由输入/输出控制(IOC)测序指令来提供用于控制器450的指令。在一个示例中,用于设置工艺阶段的条件的指令可被包含在工艺配方的相应的配方阶段中。在某些情况下,工艺配方阶段可按顺序排列,使得用于工艺阶段的所有指令与该工艺阶段同时执行。在一些实施方式中,用于设定一个或多个反应器参数的指令可以被包含在配方阶段中。例如,第一配方阶段可以包含用于设置惰性气体和/或反应物气体(例如,第一前体,如乙硅烷)的流率的指令、用于设置载气(诸如氩气)的流率的指令;以及用于第一配方阶段的时延指令。接下来的第二配方阶段可以包含用于调制或者停止惰性气体和/或反应物气体的流率的指令、用于调制载气或者清扫气体的流率的指令、以及用于第二配方阶段的时延指令。第三配方阶段可以包含用于设定反应物气体(其可以是含卤素的气体,例如三氟化氮)的流率的指令、用于调节载气的流率的指令、以及用于第三配方阶段的时延指令。第四配方阶段可以包含用于调节或者停止反应物气体的流率的指令、用于调节载气或者清扫气体的流率的指令;以及用于第四配方阶段的时延指令。第五配方阶段可以包含用于设置第二反应物(例如氮)的流率的指令、用于调节载气或者清扫气体的流率的指令;以及用于第五配方阶段的时延指令。应该理解的是,在本公开的范围内,这些配方阶段可以进一步细分和/或以任何适当的方式重复。
在一些实施方式中,基座408可以经由加热器410进行温度控制。此外,在一些实施方式中,对于处理站400的压力控制可以由蝶形阀418提供。如在图4的实施方式中所示,蝶形阀418对由下游真空泵(未示出)提供的真空进行调节。然而,在一些实施方式中,对处理站400的压力控制还可以通过改变引入至处理站400的一种或多种气体的流率来调节。
如上所述,一个或一个以上的处理站可以包含在多站处理工具中。图5示出了多站式处理工具500的实施方式的概要视图,其具有入站装载锁502和出站装载锁504,其一者或者两者可以包含远程等离子体源。处于大气压的机械手506被配置为将晶片从通过舱508装载的盒经由大气端口510移动至入站装载锁502内。晶片由机械手506放置在入站装载锁502中的基座512上,关闭大气端口510,且抽空装载锁。当入站装载锁502包含远程等离子体源时,晶片在被引入处理室514之前,可以暴露至装载锁中的远程等离子体处理。此外,晶片另外也可以在入站装载锁502中加热,例如以移除湿气和吸附的气体。接下来,通向处理室514的室传输端口516被打开,且另一个机械手(未示出)将晶片放置到在反应器中被示出的第一站的基座上的反应器中以用于处理。尽管在图5中绘出的实施方式包含装载锁,但应该理解的是,在一些实施方式中,可以使衬底直接进入处理站。
绘出的处理室514包含4个处理站,图5所示的实施方式中编号为1至4。每个站具有加热的基座(对于站1示出为518)和气体管线入口。应该理解的是,在一些实施方式中,每个处理站可以具有不同或者多个用途。例如,在一些实施方式中,处理站可以是可在ALD与等离子体增强的ALD处理模式之间切换的。附加地或替代地,在一些实施方式中,处理室514可以包含一个或多个ALD和等离子体增强的ALD处理站的匹配对。尽管绘出的处理室514包含4个站,但要理解的是,根据本公开所述的处理室可以具有任何适当数量的站。例如,在一些实施方式中,处理室可以具有5个或5个以上的站,而在其它实施方式中,处理室可以具有3个或者更少的站。
图5绘出了用于在处理室514内传输晶片的晶片搬运系统590的实施方式。在一些实施方式中,晶片搬运系统590可以在各种处理站之间和/或处理站与装载锁之间传输晶片。应该理解的是,可以采用任何适当的晶片搬运系统。非限制性示例包含晶片转盘和搬运晶片的机械手。图5还绘出了采用来控制处理工具500的处理条件和硬件状态的系统控制器550的实施方式。系统控制器550可以包含一个或多个存储器设备556、一个或多个海量存储设备554和一个或多个处理器552。处理器552可以包含计算机或者CPU、模拟和/或数字输入/输出连接、步进马达控制器板等。
在一些实施方式中,系统控制器550控制处理工具500的所有活动。系统控制器550执行存储在海量存储设备554、载入存储器设备556、并由处理器552执行的系统控制软件558。可替代地,控制逻辑可以在控制器550中硬编码。特定应用集成电路、可编程逻辑设备(例如现场可编程栅极阵列、或者FPGA)等可以用于这些目的。在下面的讨论中,无论使用“软件”还是“代码”,可以使用功能上相当的硬编码的逻辑来取代。系统控制软件558可以包含用于控制时序、气体的混合、气体流率、室和/或站压强、室和/或站温度、晶片温度、目标功率电平、RF功率电平、衬底基座、卡盘和/或底座位置、以及由处理工具500执行的特定处理的其它参数的指令。系统控制软件558可以以任何适当的方式配置。例如,各种处理工具组件子程序或者控制对象可以写入以控制用于执行各种处理工具处理的处理工具组件的操作。系统控制软件558可以以任何适当的计算机可读编程语言来编码。
在一些实施方式中,系统控制软件558可以包含用于控制上述各种参数的输入/输出控制(IOC)测序指令。在一些实施方式中可以采用与系统控制器550关联的、存储在海量存储设备554和/或存储器设备556的其它计算机软件和/或程序。用于该目的的程序或者程序段的示例包含衬底定位程序、处理气体控制程序、压力控制程序、加热器控制程序、以及等离子体控制程序。
衬底定位程序可以包含用于处理工具组件的程序代码,该处理工具组件用于将衬底装载到基座518,并控制衬底和处理工具500的其它部分之间的间隔。
处理气体控制程序可包含用于控制气体组成(例如,如本文所述的含硅气体、含氮气体、和含卤素的蚀刻剂气体以及清扫气体)和流率的代码和任选地用于使气体在沉积之前流到一个或多个处理站中以稳定在处理站中的压强的代码。压强控制程序可以包含用于通过调节例如在处理站的排放系统中的节流阀、流入处理站内的气流等等来控制处理站内的压强的代码。
加热器控制程序可包含用于控制流向用于加热衬底的加热单元的电流的代码。可替代地,加热器控制程序可控制传热气体(如氦气)朝向衬底上的传送。
等离子体控制程序可包含用于根据本文的实施方式设置施加到一个或多个处理站内的处理电极的RF功率电平的代码。
压强控制程序可以包含用于根据本文的实施方式保持反应室内的压强的代码。
在一些实施方式中,可以存在与系统控制器550相关联的用户界面。用户界面可以包含显示屏、装置和/或工艺条件的图形软件显示器、以及诸如定点设备、键盘、触摸屏、麦克风等用户输入设备。
在一些实施方式中,由系统控制器550调节的参数会涉及工艺条件。非限制性实例包含处理气体组成和流率、温度、压强、等离子体条件(例如,RF偏置功率电平)、压强、温度等。这些参数可以以配方的形式提供给用户,配方可以利用所述用户界面输入。
用于监控处理的信号可以由系统控制器550的模拟和/或数字输入连接件从各种处理工具传感器提供。用于控制处理的信号可以通过处理工具500的模拟和/或数字输出连接件输出。可被监控的处理工具传感器的非限制性实例包含质量流量控制器、压力传感器(例如压力计)、热电偶等等。经适当编程的反馈和控制算法可以与来自这些传感器的数据一起使用,以保持工艺条件。
系统控制器550可以提供用于执行上述沉积处理的程序指令。所述程序指令可以控制多种处理参数,如DC功率电平、RF偏置功率电平、压强、温度等。所述指令可以控制这些参数以根据本发明所描述的多种实施方式操作膜叠层的原位沉积。
系统控制器550将通常包含一个或多个存储器设备和被配置成执行指令的一个或多个处理器以使该装置将执行根据所公开的实施方式所述的方法。包含用于控制根据所公开的实施方式的处理操作的指令的机器可读的介质可以耦合到系统控制器550。
在一些实现方式中,系统控制器550是系统的一部分,该系统可以是上述实施例的一部分。这种系统可以包含半导体处理设备,该半导体处理设备包含一个或多个处理工具、一个或多个处理室、用于处理的一个或多个平台和/或具体的处理组件(晶片基座、气流系统等)。这些系统可以与用于控制它们在处理半导体晶片或衬底之前、期间和之后的操作的电子器件一体化。电子器件可以称为“控制器”,该控制器可以控制一个或多个系统的各种元件或子部件。根据处理要求和/或系统的类型,系统控制器550可以被编程以控制本文公开的任何工艺,包含控制处理气体输送、温度设置(例如,加热和/或冷却)、压强设置、真空设置、功率设置、射频(RF)产生器设置、RF匹配电路设置、频率设置、流速设置、流体输送设置、位置及操作设置、晶片转移进出工具和其它转移工具和/或与具体系统连接或通过接口连接的装载锁。
广义而言,系统控制器550可以定义为接收指令、发布指令、控制操作、启用清洁操作、启用端点测量等等的具有各种集成电路、逻辑、存储器和/或软件的电子器件。集成电路可以包含存储程序指令的固件形式的芯片、数字信号处理器(DSP)、定义为专用集成电路(ASIC)的芯片和/或一个或多个微处理器或执行程序指令(例如,软件)的微控制器。程序指令可以是以各种单独设置的形式(或程序文件)传送到系统控制器550的指令,该设置定义用于在半导体晶片或系统上或针对半导体晶片或系统执行特定处理的操作参数。在一些实施方式中,操作参数可以是由工艺工程师定义的用于在制备晶片的一或多个(种)层、材料、金属、氧化物、硅、二氧化硅、表面、电路和/或管芯期间完成一个或多个处理步骤的配方(recipe)的一部分。
在一些实现方式中,系统控制器550可以是与系统集成、耦合或者说是通过网络连接系统或它们的组合的计算机的一部分或者与该计算机耦合。例如,系统控制器550可以在“云端”或者是fab主机系统的全部或一部分,从而可以允许远程访问晶片处理。计算机可以启用对系统的远程访问以监控制造操作的当前进程,检查过去的制造操作的历史,检查多个制造操作的趋势或性能标准,改变当前处理的参数,设置处理步骤以跟随当前的处理或者开始新的工艺。在一些实施例中,远程计算机(例如,服务器)可以通过网络给系统提供工艺配方,网络可以包含本地网络或互联网。远程计算机可以包含允许输入或编程参数和/或设置的用户界面,该参数和/或设置然后从远程计算机传送到系统。在一些实施例中,系统控制器550接收数据形式的指令,该指令指明在一个或多个操作期间将要执行的每个处理步骤的参数。应当理解,参数可以针对将要执行的工艺类型以及工具类型,系统控制器550被配置成连接或控制该工具类型。因此,如上所述,系统控制器550可以例如通过包含一个或多个分立的控制器而为分布式,这些分立的控制器通过网络连接在一起并且朝着共同的目标(例如,本文所述的工艺和控制)工作。用于这些目的的分布式控制器的实施例可以是与结合以控制室内工艺的一个或多个远程集成电路(例如,在平台水平或作为远程计算机的一部分)通信的室上的一个或多个集成电路。
在非限制性的条件下,示例的系统可以包含等离子体蚀刻室或模块、沉积室或模块、旋转清洗室或模块、金属电镀室或模块、清洁室或模块、倒角边缘蚀刻室或模块、物理气相沉积(PVD)室或模块、化学气相沉积(CVD)室或模块、ALD室或模块、原子层蚀刻(ALE)室或模块、离子注入室或模块、轨道室或模块、以及在半导体晶片的制备和/或制造中可以关联上或使用的任何其它的半导体处理系统。
如上所述,根据工具将要执行的一个或多个工艺步骤,系统控制器550可以与一个或多个其它的工具电路或模块、其它工具组件、组合工具、其它工具界面、相邻的工具、邻接工具、位于整个工厂中的工具、主机、另一个控制器、或者在将晶片的容器往来于半导体制造工厂中的工具位置和/或装载口搬运的材料搬运中使用的工具通信。
用于执行本文公开的方法的适当装置在2011年4月11日提交的名称为“等离子体激活的共形膜沉积”的美国专利申请No.13/084399(现在的美国专利No.8,728,956);2011年4月11日提交的名称为“氮化硅膜和方法”的美国专利申请No.13/084305中进一步讨论并说明,这些专利中的每个整体并入本文。
本文所述的装置/工艺可以与光刻图案化工具或工艺结合使用,例如,用于制备或制造半导体器件、显示器、LED、光伏电池板等。通常,虽然不是必要地,这些工具/工艺将在共同的制造设施中一起使用或操作。膜的光刻图案化通常包含以下操作中的一些或所有,每个操作启用多个可行的工具:(1)使用旋涂或喷涂工具在工件,即,衬底上涂覆光致抗蚀剂;(2)使用热板或加热炉或UV固化工具固化光致抗蚀剂;(3)使用例如晶片步进曝光机之类的工具使光致抗蚀剂暴露于可见光或紫外线或x-射线;(4)使抗蚀剂显影以便选择性地去除抗蚀剂并且从而使用例如湿式工作台之类的工具将其图案化;(5)通过使用干式或等离子体辅助蚀刻工具将抗蚀剂图案转印到下方的膜或工件上;并且(6)使用例如射频或微波等离子体抗蚀剂剥离器之类的工具去除抗蚀剂。
试验
试验1
进行实验,将通过常规ALD工艺沉积的氮化硅膜的共形性与通过所公开的实施方式沉积的氮化硅膜的共形性进行比较。
在第一个试验中,将衬底暴露于50个循环的原子层沉积,每个循环包括将衬底暴露于乙硅烷、清扫室、将衬底暴露于氮并点燃等离子体、以及清扫该室。在图6A示出了衬底600的在特征上沉积有氮化硅610的图像。注意,在特征的顶部的膜比在侧壁的膜明显较厚。
在第二个试验中,将衬底暴露于根据所公开的实施方式的50个原子层沉积循环,每个循环包括将衬底暴露于乙硅烷、清扫室、将衬底暴露于三氟化氮(含卤素的蚀刻剂)、清扫室、将衬底暴露于氮并点燃等离子体、以及清扫该室。用于两个试验的吹扫气体是氩气。在每个循环将衬底暴露于三氟化氮。在图6B示出了衬底600的在特征上沉积有氮化硅680的图像。注意,相比于图6A,在图6B中的特征的顶部的膜的厚度与在侧壁的膜上的厚度较相似。
对于两种试验,氮化硅膜的厚度是在特征的顶部、在特征的侧壁的顶端部分、在特征的侧壁的底端部分、以及在特征的底部测得的。计算比率以确定这些不种组件之间的共形性。比率越接近100%,则膜越共形。结果示于下表1。
表1 在利用和不利用蚀刻剂(NF3)的情况下的硅氮化物沉积
如表1所示,相比于没有利用蚀刻剂沉积的膜的比率,利用蚀刻剂沉积的膜的比率更加接近100%。例如,对于利用蚀刻剂沉积的膜,侧壁底端比侧壁顶端的比率为52%,相比而言,对于没有利用蚀刻剂沉积的膜,侧壁底端比侧壁顶端的比率为29%。这些结果表明,使用所公开的实施方式沉积的膜的共形性被改善,所公开的实施方式涉及将蚀刻剂暴露并入到原子层沉积工艺中。
结论
虽然上述实施例已经为了清楚理解的目的在一些细节方面进行了描述,但显而易见的是,某些变化和修改方案可在所附权利要求的范围内实施。例如,尽管各种操作可以被以特定顺序显示或描述,但实现方式可以包括以其它顺序执行操作的工艺,除非另有明确规定。例如,在一些实施方式中,本文所公开的操作可以以与附图中描绘的或在说明书或权利要求书阐述的顺序不同的顺序执行,并且仍然获得有益的结果。此外,在一些实现方式中,各种操作可以被消除,或者除了所说明的操作外,还可以执行一个或多个附加的操作。
应当注意的是,具有实施本发明的实施方式的工艺、系统和装置的许多替代方式。因此,本发明的实施方式应被视为是说明性的而不是限制性的,并且所述实施方式并不限于本文所给出的细节。
Claims (10)
1.一种处理在室中的衬底的方法,该方法包括:
(a)提供具有一个或多个特征的衬底,每个特征包括特征开口;
(b)在使得含硅前体能吸附到所述衬底的表面上的条件下,将所述衬底暴露于所述含硅前体,由此形成含硅前体吸附层;
(c)在将所述衬底暴露于所述含硅前体后,将所述衬底暴露于含卤素的蚀刻剂;以及
(d)将所述衬底暴露于含氮反应物并点燃等离子体,以在所述特征开口处或其附近选择性地蚀刻所述第一前体吸附层并形成氮化硅膜。
2.根据权利要求1所述的方法,其中在使所述含卤素的蚀刻剂能选择性地吸附到所述第一前体吸附层上的条件下,使所述衬底暴露于所述含卤素的蚀刻剂。
3.根据权利要求1所述的方法,其中所述含卤素的蚀刻剂选自由三氟化氮、氯、三氟甲烷、四氟化碳、以及它们的组合组成的组。
4.根据权利要求1所述的方法,其中所述含卤素的蚀刻剂包括化学式为CnF2n+2或CnF2n的化合物,其中n>1。
5.根据权利要求1-4中任一项所述的方法,其中在将所述衬底暴露于所述含卤素的蚀刻剂之后清扫所述室。
6.根据权利要求5所述的方法,其中通过使清扫气体流动来清扫所述室,所述清扫气体选自由氩气、氦气、氮气和氢气组成的组。
7.根据权利要求1-4中任一项所述的方法,其中所述含硅前体选自由硅烷、乙硅烷、丙硅烷、丁硅烷、三甲硅烷基胺、氨基硅烷、和卤代硅烷组成的组。
8.根据权利要求1-4中任一项所述的方法,其中所述含氮反应物选自由氮、氨、肼和胺类组成的组。
9.一种处理在室中的衬底的方法,该方法包括:
通过执行一个或多个循环来沉积膜,循环包括:
(a)提供具有一个或多个特征的衬底,每个特征包括特征开口;
(b)在使得第一前体能吸附到所述衬底的表面上的条件下,将所述衬底暴露于所述第一前体,由此形成第一前体吸附层;
(c)在将所述衬底暴露于所述第一前体后,将所述衬底暴露于含卤素的蚀刻剂;以及
(d)将所述衬底暴露于第二反应物并点燃等离子体,以在所述特征开口处或其附近选择性地蚀刻所述第一前体吸附层并形成膜。
10.一种用于处理衬底的装置,该装置包括:
(a)至少一个处理室,所述处理室包含用于保持衬底的基座;
(b)至少一个出口,所述出口用于耦合到真空;
(c)一个或多个处理气体进口,所述处理气体进口耦合到一个或多个含硅前体源和一种或多种含卤素的蚀刻剂;
(d)射频(RF)产生器;和
(e)用于控制所述装置中的操作的控制器,所述控制器包括用于以下操作的机器可读指令:
(i)将含硅前体引入所述处理室;
(ii)在将所述含硅前体引入之后,将含卤素的蚀刻剂引入所述室;以及
(iii)将含氮反应物引入所述室并点燃等离子体以形成氮化硅膜。
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US9502238B2 (en) | 2016-11-22 |
US20160293398A1 (en) | 2016-10-06 |
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