CN109075021B - 利用间歇性空气-水暴露的改良自组装单层阻挡 - Google Patents
利用间歇性空气-水暴露的改良自组装单层阻挡 Download PDFInfo
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- CN109075021B CN109075021B CN201780019657.4A CN201780019657A CN109075021B CN 109075021 B CN109075021 B CN 109075021B CN 201780019657 A CN201780019657 A CN 201780019657A CN 109075021 B CN109075021 B CN 109075021B
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- dimethylamino
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- 239000013545 self-assembled monolayer Substances 0.000 title claims abstract description 156
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- 238000000034 method Methods 0.000 claims abstract description 84
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 44
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- 238000000151 deposition Methods 0.000 claims description 27
- 239000012080 ambient air Substances 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 8
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- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 5
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- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 claims description 3
- 229910000077 silane Inorganic materials 0.000 claims description 3
- -1 silane amine Chemical class 0.000 claims description 3
- 150000003573 thiols Chemical class 0.000 claims description 3
- MZFUHFWRXGYVSB-UHFFFAOYSA-N CN(C)[Si](CCCCC)(N(C)C)N(C)C Chemical compound CN(C)[Si](CCCCC)(N(C)C)N(C)C MZFUHFWRXGYVSB-UHFFFAOYSA-N 0.000 claims description 2
- JOVJSJNDGJZSNA-UHFFFAOYSA-N CN(C)[Si](CCCCCCCCC)(N(C)C)N(C)C Chemical compound CN(C)[Si](CCCCCCCCC)(N(C)C)N(C)C JOVJSJNDGJZSNA-UHFFFAOYSA-N 0.000 claims description 2
- NJHTUVVFQQLWPR-UHFFFAOYSA-N CN(C)[Si](CCCCCCCCCCC)(N(C)C)N(C)C Chemical compound CN(C)[Si](CCCCCCCCCCC)(N(C)C)N(C)C NJHTUVVFQQLWPR-UHFFFAOYSA-N 0.000 claims description 2
- GCSSIVWNVUZJMI-UHFFFAOYSA-N CN(C)[Si](CCCCCCCCCCCCC)(N(C)C)N(C)C Chemical compound CN(C)[Si](CCCCCCCCCCCCC)(N(C)C)N(C)C GCSSIVWNVUZJMI-UHFFFAOYSA-N 0.000 claims description 2
- QDTWUXXCSDOPKU-UHFFFAOYSA-N CN(C)[Si](CCCCCCCCCCCCCCC)(N(C)C)N(C)C Chemical compound CN(C)[Si](CCCCCCCCCCCCCCC)(N(C)C)N(C)C QDTWUXXCSDOPKU-UHFFFAOYSA-N 0.000 claims description 2
- VGVMMTATKCNSRV-UHFFFAOYSA-N CN(C)[Si](CCCCCCCCCCCCCCCCC)(N(C)C)N(C)C Chemical compound CN(C)[Si](CCCCCCCCCCCCCCCCC)(N(C)C)N(C)C VGVMMTATKCNSRV-UHFFFAOYSA-N 0.000 claims description 2
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- ZXJWJAQZELLKGE-UHFFFAOYSA-N N-[bis(dimethylamino)-heptylsilyl]-N-methylmethanamine Chemical compound CN(C)[Si](CCCCCCC)(N(C)C)N(C)C ZXJWJAQZELLKGE-UHFFFAOYSA-N 0.000 claims description 2
- ZETNTFPLEKWPLQ-UHFFFAOYSA-N N-[bis(dimethylamino)-hexadecylsilyl]-N-methylmethanamine Chemical compound CN(C)[Si](CCCCCCCCCCCCCCCC)(N(C)C)N(C)C ZETNTFPLEKWPLQ-UHFFFAOYSA-N 0.000 claims description 2
- UPEJPVOEZXBAII-UHFFFAOYSA-N N-[bis(dimethylamino)-hexylsilyl]-N-methylmethanamine Chemical compound CCCCCC[Si](N(C)C)(N(C)C)N(C)C UPEJPVOEZXBAII-UHFFFAOYSA-N 0.000 claims description 2
- PZVDSEMMSUQGSR-UHFFFAOYSA-N N-[bis(dimethylamino)-octadecylsilyl]-N-methylmethanamine Chemical compound C(CCCCCCCCCCCCCCCCC)[Si](N(C)C)(N(C)C)N(C)C PZVDSEMMSUQGSR-UHFFFAOYSA-N 0.000 claims description 2
- OKKNBLRDTXEMFS-UHFFFAOYSA-N N-[bis(dimethylamino)-tetradecylsilyl]-N-methylmethanamine Chemical compound CN(C)[Si](CCCCCCCCCCCCCC)(N(C)C)N(C)C OKKNBLRDTXEMFS-UHFFFAOYSA-N 0.000 claims description 2
- XGZGKDQVCBHSGI-UHFFFAOYSA-N butyl(triethoxy)silane Chemical compound CCCC[Si](OCC)(OCC)OCC XGZGKDQVCBHSGI-UHFFFAOYSA-N 0.000 claims description 2
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- DZQISOJKASMITI-UHFFFAOYSA-N decyl-dioxido-oxo-$l^{5}-phosphane;hydron Chemical compound CCCCCCCCCCP(O)(O)=O DZQISOJKASMITI-UHFFFAOYSA-N 0.000 claims description 2
- YGUFXEJWPRRAEK-UHFFFAOYSA-N dodecyl(triethoxy)silane Chemical compound CCCCCCCCCCCC[Si](OCC)(OCC)OCC YGUFXEJWPRRAEK-UHFFFAOYSA-N 0.000 claims description 2
- SCPWMSBAGXEGPW-UHFFFAOYSA-N dodecyl(trimethoxy)silane Chemical compound CCCCCCCCCCCC[Si](OC)(OC)OC SCPWMSBAGXEGPW-UHFFFAOYSA-N 0.000 claims description 2
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- VCOCWGTYSUNGHT-UHFFFAOYSA-N heptadecylphosphonic acid Chemical compound CCCCCCCCCCCCCCCCCP(O)(O)=O VCOCWGTYSUNGHT-UHFFFAOYSA-N 0.000 claims description 2
- VRINOTYEGADLMW-UHFFFAOYSA-N heptyl(trimethoxy)silane Chemical compound CCCCCCC[Si](OC)(OC)OC VRINOTYEGADLMW-UHFFFAOYSA-N 0.000 claims description 2
- VAJFLSRDMGNZJY-UHFFFAOYSA-N heptylphosphonic acid Chemical compound CCCCCCCP(O)(O)=O VAJFLSRDMGNZJY-UHFFFAOYSA-N 0.000 claims description 2
- RSKGMYDENCAJEN-UHFFFAOYSA-N hexadecyl(trimethoxy)silane Chemical compound CCCCCCCCCCCCCCCC[Si](OC)(OC)OC RSKGMYDENCAJEN-UHFFFAOYSA-N 0.000 claims description 2
- JDPSFRXPDJVJMV-UHFFFAOYSA-N hexadecylphosphonic acid Chemical compound CCCCCCCCCCCCCCCCP(O)(O)=O JDPSFRXPDJVJMV-UHFFFAOYSA-N 0.000 claims description 2
- CZWLNMOIEMTDJY-UHFFFAOYSA-N hexyl(trimethoxy)silane Chemical compound CCCCCC[Si](OC)(OC)OC CZWLNMOIEMTDJY-UHFFFAOYSA-N 0.000 claims description 2
- GJWAEWLHSDGBGG-UHFFFAOYSA-N hexylphosphonic acid Chemical compound CCCCCCP(O)(O)=O GJWAEWLHSDGBGG-UHFFFAOYSA-N 0.000 claims description 2
- 239000005055 methyl trichlorosilane Substances 0.000 claims description 2
- YACKEPLHDIMKIO-UHFFFAOYSA-N methylphosphonic acid Chemical compound CP(O)(O)=O YACKEPLHDIMKIO-UHFFFAOYSA-N 0.000 claims description 2
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 claims description 2
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 claims description 2
- FHBURLBCXNMPJX-UHFFFAOYSA-N n-[bis(dimethylamino)-ethylsilyl]-n-methylmethanamine Chemical compound CC[Si](N(C)C)(N(C)C)N(C)C FHBURLBCXNMPJX-UHFFFAOYSA-N 0.000 claims description 2
- AHKKZIUZTWZKDR-UHFFFAOYSA-N n-[bis(dimethylamino)-methylsilyl]-n-methylmethanamine Chemical compound CN(C)[Si](C)(N(C)C)N(C)C AHKKZIUZTWZKDR-UHFFFAOYSA-N 0.000 claims description 2
- JSIUWTSVPJWBNO-UHFFFAOYSA-N n-[bis(dimethylamino)-octylsilyl]-n-methylmethanamine Chemical compound CCCCCCCC[Si](N(C)C)(N(C)C)N(C)C JSIUWTSVPJWBNO-UHFFFAOYSA-N 0.000 claims description 2
- NQYXALRANHLJAO-UHFFFAOYSA-N n-[bis(dimethylamino)-propylsilyl]-n-methylmethanamine Chemical compound CCC[Si](N(C)C)(N(C)C)N(C)C NQYXALRANHLJAO-UHFFFAOYSA-N 0.000 claims description 2
- PIZDPXXHLAAKFM-UHFFFAOYSA-N n-[butyl-bis(dimethylamino)silyl]-n-methylmethanamine Chemical compound CCCC[Si](N(C)C)(N(C)C)N(C)C PIZDPXXHLAAKFM-UHFFFAOYSA-N 0.000 claims description 2
- FNCPFEWAXAOHNQ-UHFFFAOYSA-N n-[decyl-bis(dimethylamino)silyl]-n-methylmethanamine Chemical compound CCCCCCCCCC[Si](N(C)C)(N(C)C)N(C)C FNCPFEWAXAOHNQ-UHFFFAOYSA-N 0.000 claims description 2
- YNESSCJHABBEIO-UHFFFAOYSA-N nonadecane-1-thiol Chemical compound CCCCCCCCCCCCCCCCCCCS YNESSCJHABBEIO-UHFFFAOYSA-N 0.000 claims description 2
- RWYACTMFBZKJIX-UHFFFAOYSA-N nonadecylphosphonic acid Chemical compound C(CCCCCCCCCCCCCCCCCC)P(O)(O)=O RWYACTMFBZKJIX-UHFFFAOYSA-N 0.000 claims description 2
- OLGGYSFJQGDOFX-UHFFFAOYSA-N nonylphosphonic acid Chemical compound CCCCCCCCCP(O)(O)=O OLGGYSFJQGDOFX-UHFFFAOYSA-N 0.000 claims description 2
- FTMKAMVLFVRZQX-UHFFFAOYSA-N octadecylphosphonic acid Chemical compound CCCCCCCCCCCCCCCCCCP(O)(O)=O FTMKAMVLFVRZQX-UHFFFAOYSA-N 0.000 claims description 2
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- 229960003493 octyltriethoxysilane Drugs 0.000 claims description 2
- ULIMUQCIZMJOHK-UHFFFAOYSA-N pentadecylphosphonic acid Chemical compound CCCCCCCCCCCCCCCP(O)(O)=O ULIMUQCIZMJOHK-UHFFFAOYSA-N 0.000 claims description 2
- CKVICYBZYGZLLP-UHFFFAOYSA-N pentylphosphonic acid Chemical compound CCCCCP(O)(O)=O CKVICYBZYGZLLP-UHFFFAOYSA-N 0.000 claims description 2
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- BVQJQTMSTANITJ-UHFFFAOYSA-N tetradecylphosphonic acid Chemical compound CCCCCCCCCCCCCCP(O)(O)=O BVQJQTMSTANITJ-UHFFFAOYSA-N 0.000 claims description 2
- HLWCOIUDOLYBGD-UHFFFAOYSA-N trichloro(decyl)silane Chemical compound CCCCCCCCCC[Si](Cl)(Cl)Cl HLWCOIUDOLYBGD-UHFFFAOYSA-N 0.000 claims description 2
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- RYPYGDUZKOPBEL-UHFFFAOYSA-N trichloro(hexadecyl)silane Chemical compound CCCCCCCCCCCCCCCC[Si](Cl)(Cl)Cl RYPYGDUZKOPBEL-UHFFFAOYSA-N 0.000 claims description 2
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- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
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- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
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- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
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- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
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- 238000004544 sputter deposition Methods 0.000 description 1
- BNCXNUWGWUZTCN-UHFFFAOYSA-N trichloro(dodecyl)silane Chemical compound CCCCCCCCCCCC[Si](Cl)(Cl)Cl BNCXNUWGWUZTCN-UHFFFAOYSA-N 0.000 description 1
- ZOYFEXPFPVDYIS-UHFFFAOYSA-N trichloro(ethyl)silane Chemical compound CC[Si](Cl)(Cl)Cl ZOYFEXPFPVDYIS-UHFFFAOYSA-N 0.000 description 1
- SRQHGWJPIZXDTA-UHFFFAOYSA-N trichloro(heptyl)silane Chemical compound CCCCCCC[Si](Cl)(Cl)Cl SRQHGWJPIZXDTA-UHFFFAOYSA-N 0.000 description 1
- LFXJGGDONSCPOF-UHFFFAOYSA-N trichloro(hexyl)silane Chemical compound CCCCCC[Si](Cl)(Cl)Cl LFXJGGDONSCPOF-UHFFFAOYSA-N 0.000 description 1
- PYJJCSYBSYXGQQ-UHFFFAOYSA-N trichloro(octadecyl)silane Chemical compound CCCCCCCCCCCCCCCCCC[Si](Cl)(Cl)Cl PYJJCSYBSYXGQQ-UHFFFAOYSA-N 0.000 description 1
- RCHUVCPBWWSUMC-UHFFFAOYSA-N trichloro(octyl)silane Chemical compound CCCCCCCC[Si](Cl)(Cl)Cl RCHUVCPBWWSUMC-UHFFFAOYSA-N 0.000 description 1
- DOEHJNBEOVLHGL-UHFFFAOYSA-N trichloro(propyl)silane Chemical compound CCC[Si](Cl)(Cl)Cl DOEHJNBEOVLHGL-UHFFFAOYSA-N 0.000 description 1
- WLWBNHYYFCNHRR-UHFFFAOYSA-N trichloro(tridecyl)silane Chemical compound CCCCCCCCCCCCC[Si](Cl)(Cl)Cl WLWBNHYYFCNHRR-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02296—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer
- H01L21/02299—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer pre-treatment
- H01L21/02307—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer pre-treatment treatment by exposure to a liquid
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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]
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- 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 at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/32—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers using masks
-
- 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
-
- 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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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- 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
- H01L21/02164—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 oxide, e.g. SiO2
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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
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- 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
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- H—ELECTRICITY
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- 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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Abstract
在此所述的实施方式大体上涉及用于制造半导体装置的工艺,其中使用自组装单层(SAM)来实现选择性区域沉积。在此所述的方法涉及交替的SAM分子和羟基部分暴露操作,其可用以形成适于阻挡随后沉积材料的沉积的SAM层。
Description
技术领域
于此所述的实施方式大体上涉及用于制造半导体装置的工艺,其中使用自组装单层来实现选择性区域沉积。
背景技术
可靠地生产亚半微米(sub-half micron)和更小的特征结构是半导体装置的下一代较大规模集成(very large scale integration,VLSI)和超大规模积体(ultra largescale integration,ULSI)的关键技术挑战之一。然而,随着电路技术的限制的推进,VLSI和ULSI技术的缩小尺寸已经对处理能力提出了额外的要求。
随着用于下一代装置的电路密度增加,互连件(诸如过孔、沟槽、接触件(contact)、栅极结构和其它特征结构以及其间的介电材料)的宽度减小到45nm和32nm的尺寸并且超过该尺寸。为了能够制造下一代装置和结构,通常利用半导体芯片中的特征结构的三维(3D)堆叠。特别地,鳍状场效应晶体管(fin field effect transistor,FinFET)通常用于在半导体芯片中形成三维(3D)结构。藉由在三维而不是传统的二维中布置晶体管,可将多个晶体管放置在彼此非常接近的集成电路(IC)中。随着电路密度和堆叠增加,选择性地将随后的材料沉积在先前沉积的材料上的能力变得越来越期望。
自组装单层(SAM)可用作掩模材料,以改良随后的材料沉积选择性。SAM通常是表面化学依赖性的,且可优先在各种材料上形成。然而,SAM可能在沉积层中显示针孔或空隙,这可能不能有效地防止后续材料层的沉积。SAM的另一个缺点是沉积时间可能非常长且在半导体制造工艺中是不经济可行的。
因此,存在有用于SAM形成的改进方法的需求。
发明内容
在一个实施方式中,提供了一种处理基板的方法。方法包括将基板暴露于自组装单层(“SAM”)分子,以实现SAM在第一材料上的选择性沉积,其中基板包括暴露的第一材料和暴露的第二材料。可将基板暴露于羟基部分,且将基板暴露于SAM分子和将基板暴露于羟基部分可分别以约1:1和约100:1之间的时间比例而重复。在执行重复之后,可将基板暴露于SAM分子,第三材料可选择性地沉积在暴露的第二材料上,并且SAM可从第一材料移除。
在另一实施方式中,提供了一种处理基板的方法。方法包括将基板暴露于自组装单层(“SAM”)分子,以实现SAM在第一处理腔室中的第一材料上的选择性沉积,其中基板包括暴露的第一材料和暴露的第二材料。可将基板转移到第二处理腔室,且可在第二处理腔室中将基板暴露于由水蒸汽所形成的羟基部分。在第一处理腔室中将基板暴露于SAM分子和在第二处理腔室中将基板暴露于羟基部分可分别以约1∶1至约100:1之间的时间比例而重复。在执行重复之后,可在第一处理腔室中将基板暴露于SAM分子,第三材料可选择性地沉积在暴露的第二材料上,并且SAM可从第一材料移除。
在又一实施方式中,提供了一种处理基板的方法。方法包括将基板暴露于自组装单层(“SAM”)分子,以实现SAM在处理腔室中的第一材料上的选择性沉积,其中基板包括暴露的第一材料和暴露的第二材料。可将基板转移到周围空气环境,并暴露于由在周围空气环境中的周围空气所形成的羟基部分。在处理腔室中将基板暴露于SAM分子和于周围空气环境中将基板暴露于羟基部分可分别以约1:1至约100:1之间的时间比例而重复。在执行重复之后,可于处理腔室中将基板暴露于SAM分子,第三材料可选择性地沉积在暴露的第二材料上,并且SAM可从第一材料移除。
附图说明
可通过参照实施方式(其中一些实施方式图示在附图中)来详细理解本公开内容的上述特征以及以上简要概述的有关本公开内容的更具体的描述。然而,应注意附图仅图示示例性的实施方式,且因此不被认为是对本公开内容的范围的限制,可允许其他等效的实施方式。
图1图解了描绘根据在此所述的实施方式的利用SAM材料的选择性沉积的方法的流程图。
图2A-2D图解了根据在此所述的实施方式而处理的工件的示意性截面图。
为了便于理解,已尽可能地使用相同的参考数字来标示各图共有的的相同元件。预期一个实施方式的元件和特征可有利地并入其他实施方式中,而无需进一步详述。
具体实施方式
以下的公开内容描述了用于制造半导体装置的方法,其中使用自组装单层来实现选择性沉积。在以下的描述以及图1和图2A-2B中阐述了某些细节,以提供对本公开内容的各种实施方式的透彻理解。描述通常与半导体装置和自组装单层相关联的结构和系统的其它细节未在以下的公开内容中阐述,以避免不必要地混淆各种实施方式的描述。
图中所示的许多细节、尺寸、角度和其它特征仅仅是特定实施方式的说明。因此,在不背离本公开内容的精神或范围的情况下,其他实施方式可具有其他细节、部件和特征。另外,本公开内容的进一步的实施方式可在没有以下描述的几个细节的情况下实施。
如在此所使用的,“自组装单层”(“SAM”)通常是指附接(如,藉由化学键结)到表面并且已经相对于那个表面且甚至相对于彼此而采取优选取向的分子层。SAM通常包括双亲性分子的组织层,其中分子的一端,“头部基”显示对基板的特定的、可逆的亲和性。头部基的选择将取决于SAM的应用,具有基于所使用的基板的SAM化合物的类型。通常地,头部基连接到烷基链或氟化烷基链,其中尾部或“末端”可被官能化,(例如)以改变润湿性质和界面性质。形成SAM的分子将相对于另一种材料而选择性地附接到一种材料(如,金属相对于电介质),且若具有足够的密度,则可成功地操作随后的沉积,从而允许在未涂布有SAM的材料上进行选择性沉积。
现有技术通常使用至少6小时的SAM沉积,以形成足够致密以操作金属沉积的SAM膜。现有技术通常利用至少48小时的SAM膜沉积,以操作金属氧化物。当前的气相沉积系统仅使用加热的SAM分子溶液的蒸汽压力,在非常低的压力(如,2mTorr)下输送SAM分子,以将化学物质暴露于基板。这种低蒸汽压力导致气相中的低浓度,并且对于致密形成需要48小时。因此,形成没有针孔的致密高质量SAM膜花费大量时间。若SAM的形成时间太短,则SAM含有许多针孔,沉积可能经由针孔而发生。
在于此所述的一些实施方式中,提供了用于增加具有减少的针孔形成的致密SAM膜的形成速率的方法。在于此所述的一些实施方式中,还提供了将形成的SAM膜进行处理以操作形成的针孔的方法。两者允许形成具有减少的针孔的SAM膜。
图1是描绘根据在此所述的实施方式的使用SAM膜的选择性沉积的方法100的流程图。在制造工艺期间在工件上执行方法100。方法100可用于形成如图2A-2D中所示的制造阶段的序列中所示的结构,其在下面更详细地讨论。图2A-2D描绘了在基板上所形成的装置结构的制造步骤的截面示意图。尽管参照具体结构而描述了图1,但是应当理解对具体结构的参照仅仅是说明性的,且图1中所描述的工艺可应用于期望在含有多种材料的基板上选择性地沉积膜的任何工艺,其中期望有减少的针孔形成。
在操作110处,具有至少暴露的第一材料和暴露的第二材料的基板为了用于SAM沉积而制备。基板可类似于图2A-2D中所示的基板210。在一个实施方式中,基板210可包括诸如结晶硅(如,Si<100>或Si<111>)、氧化硅、应变硅、硅锗、掺杂或未掺杂的多晶硅、掺杂或未掺杂的硅晶片、图案化或非图案化的晶片、绝缘体上硅(SOI)、碳掺杂氧化硅、氮化硅、掺杂硅、锗、砷化镓、玻璃、蓝宝石及其组合的材料。基板210可具有用于圆形基板的各种尺寸,诸如200mm、300mm、450mm或其它直径。基板210还可为任何的多边形、正方形、矩形、曲形或其它非圆形工件,诸如在制造平板显示器中所使用的多边形玻璃基板。除非另有说明,在此所述的实施方式和例子在具有200mm直径、300mm直径或450mm直径基板的基板上进行。
基板210可包括由第一材料216(如,介电材料)所形成的特征结构212。特征结构212例如可包括沟槽、过孔、孔、开口、线、类似者及其组合。特征结构212具有开口214,开口214被设置在基板210上的第二材料218(如,导电材料)所填充,如图2A中所示。应理解第一材料216和第二材料218皆可为介电材料。例如,第一材料216可为氧化硅层,且第二材料218可为氮化硅层。
在准备沉积SAM膜时,可在后续操作的SAM膜形成工艺之前,将基板210暴露于任选的预清洁工艺。预清洁工艺可为能够从暴露的表面移除原生氧化物(native oxide)、污染物或两者的任何预清洁工艺。预清洁工艺可为干式化学清洁工艺、湿式化学清洁工艺或两者。预清洁工艺可为适于执行干式蚀刻工艺的远程等离子体清洁或原位等离子体清洁。一种示例性的干式清洁工艺是可从加州圣克拉拉市的应用材料公司所取得的SICONITM预清洁工艺,SICONITM预清洁工艺通过使用NF3和NH3的低温、两部分干式化学清洁工艺而移除原生氧化物。可预期来自其他制造商的其他适当配置的清洁工艺也可根据在此所述的实施方式而有利地实现。
在操作120处,将基板210暴露于SAM前驱物,以实现SAM前驱物选择性吸附在第一材料216的表面222上,其中在第二材料218的表面224上的吸附最少或没有吸附,如图2B中所示。取决于所使用的材料和所使用的SAM前驱物,SAM前驱物可为基于溶液的前驱物或气态前驱物。SAM前驱物可包括一个或多个SAM分子230、形成SAM分子230的前驱物或两者。吸附的SAM分子230形成SAM 240。
SAM 240包括SAM分子230的组织层,组织层可为双亲性的,其中分子的一端,头部基232对特征结构212的第一材料216显示特定的、可逆的亲和性。头部基232通常连接到烷基链,其中末端“R”234可被官能化。SAM 240藉由将头部基232化学吸附到特征结构212的第一材料216上,接着疏水性的尾部基的二维组织而形成。
根据在此所述的实施方式而使用的合适的SAM分子230的例子包括下文所述的材料,除了在半导体制造工艺中具有适于阻挡随后沉积的材料的沉积的特征的其他SAM分子之外,包括其组合、混合物和接枝物(graft)。在一个实施方式中,SAM分子230可为羧酸材料,诸如甲基羧酸、乙基羧酸、丙基羧酸、丁基羧酸、戊基羧酸、己基羧酸、庚基羧酸、辛基羧酸、壬基羧酸、癸基羧酸、十一烷基羧酸、十二烷基羧酸、十三烷基羧酸、十四烷基羧酸、十五烷基羧酸、十六烷基羧酸、十七烷基羧酸、十八烷基羧酸和十九烷基羧酸。
在一个实施方式中,SAM分子230可为膦酸材料,诸如甲基膦酸、乙基膦酸、丙基膦酸、丁基膦酸、戊基膦酸、己基膦酸、庚基膦酸、辛基膦酸、壬基膦酸、癸基膦酸、十一烷基膦酸、十二烷基膦酸、十三烷基膦酸、十四烷基膦酸、十五烷基膦酸、十六烷基膦酸、十七烷基膦酸、十八烷基膦酸和十九烷基膦酸。
在另一个实施方式中,SAM分子230可为硫醇材料,诸如甲硫醇、乙硫醇、丙硫醇、丁硫醇、戊硫醇、己硫醇、庚硫醇、辛硫醇、壬硫醇、癸硫醇、十一烷硫醇、十二烷硫醇、十三烷硫醇、十四烷硫醇、十五烷硫醇、十六烷硫醇、十七烷硫醇、十八烷硫醇和十九烷硫醇。
在另一个实施方式中,SAM分子230可为硅烷胺(silylamine)材料,诸如三(二甲氨基)甲基硅烷、三(二甲氨基)乙基硅烷、三(二甲氨基)丙基硅烷、三(二甲氨基)丁基硅烷、三(二甲氨基)戊基硅烷、三(二甲氨基)己基硅烷、三(二甲氨基)庚基硅烷、三(二甲氨基)辛基硅烷、三(二甲氨基)壬基硅烷、三(二甲氨基)癸基硅烷、三(二甲氨基)十一烷基硅烷、三(二甲氨基)十二烷基硅烷、三(二甲氨基)十三烷基硅烷、三(二甲氨基)十四烷基硅烷、三(二甲氨基)十五烷基硅烷、三(二甲氨基)十六烷基硅烷、三(二甲氨基)十七烷基硅烷、三(二甲氨基)十八烷基硅烷和三(二甲氨基)十九烷基硅烷。
在另一个实施方式中,SAM分子230可为氯硅烷材料,诸如甲基三氯硅烷、乙基三氯硅烷、丙基三氯硅烷、丁基三氯硅烷、戊基三氯硅烷、己基三氯硅烷、庚三氯硅烷、辛基三氯硅烷、壬基三氯硅烷、癸基三氯硅烷、十一烷基三氯硅烷、十二烷基三氯硅烷、十三烷基三氯硅烷、十四烷基三氯硅烷、十五烷基三氯硅烷、十六烷基三氯硅烷、十七烷基三氯硅烷、十八烷基三氯硅烷和十九烷基三氯硅烷。
在另一个实施方式中,SAM分子230可为氧硅烷材料,诸如甲基三甲氧基硅烷、甲基三乙氧基硅烷、乙基三甲氧基硅烷、乙基三乙氧基硅烷、丙基三甲氧基硅烷、丙基三乙氧基硅烷、丁基三甲氧基硅烷、丁基三乙氧基硅烷、戊基三甲氧基硅烷、戊基三乙氧基硅烷、己基三甲氧基硅烷、己基三乙氧基硅烷、庚基三甲氧基硅烷、庚基三乙氧基硅烷、辛基三甲氧基硅烷、辛基三乙氧基硅烷、壬基三甲氧基硅烷、壬基三乙氧基硅烷、癸基三甲氧基硅烷、癸基三乙氧基硅烷、十一烷基三甲氧基硅烷、十一烷基三乙氧基硅烷、十二烷基三甲氧基硅烷、十二烷基三乙氧基硅烷、十三烷基三甲氧基硅烷、十三烷基三乙氧基硅烷、十四烷基三甲氧基硅烷、十四烷基三乙氧基硅烷、十五烷基三甲氧基硅烷、十五烷基三乙氧基硅烷、十六烷基三甲氧基硅烷、十六烷基三乙氧基硅烷、十七烷基三甲氧基硅烷、十七烷基三乙氧基硅烷、十八烷基三甲氧基硅烷、十八烷基三乙氧基硅烷、十九烷基三甲氧基硅烷和十九烷基三乙氧基硅烷。在另一个实施方式中,SAM分子230可具有氟化R基,诸如(1,1,2,2-全氟癸基)三氯硅烷、三氯(1,1,2,2-全氟辛基)硅烷、(十三氟-1,1,2,2-四氢辛基)三氯硅烷、(十三氟-1,1,2,2-四氢辛基)三乙氧基硅烷、(十三氟-1,1,2,2-四氢辛基)甲基二氯硅烷、(十三氟-1,1,2,2-四氢辛基)二甲基氯硅烷和(十七氟-1,1,2,2-四氢癸基)三氯硅烷等。藉由将基板210浸入含有SAM分子230的稀释溶液中,可从溶液发生SAM吸附。在一个实施方式中,经由从溶液旋涂而沉积SAM 240。SAM吸附也可藉由将基板210暴露于气态前驱物而从气相沉积发生。吸附的分子最初形成无序的分子质量,且接着开始在特征结构212的第一材料216上形成结晶或半结晶结构。SAM 240的厚度可藉由调节SAM分子230的烷基链的碳链长度而调节。通常,SAM 240可形成在与SAM分子230具有化学反应能力的表面上。在一个实施方式中,SAM吸附可为气相沉积工艺。在这个实施方式中,SAM分子可在以在约25℃和约300℃之间,诸如约125℃和约200℃之间维持的温度下的安瓿中蒸发。基板210可以维持在约25℃和约400℃之间,诸如在约50℃和约200℃之间,例如在约100℃和约175℃之间的温度下。基板处理环境(诸如处理腔室的处理容积)的压力可以维持在约1mTorr和约1520Torr之间,诸如在约5Torr和约600Torr之间的压力下。可采用载气以促进气相SAM分子的输送,取决于处理腔室的容积,载气可以约25sccm和约3000sccm之间,诸如约50sccm和约1000sccm之间的流量输送。合适的载气包括在SAM吸附条件下通常为惰性的气体(诸如稀有气体或类似者),载气有助于将SAM分子输送到基板表面。在操作130中,SAM分子可暴露于基板210持续在约1秒和约48小时之间的时间量,例如在约1分钟和约120分钟之间。在图2B中所示的实施方式中,用以形成SAM 240的SAM前驱物经选择以与特征结构212的表面222(如,氧化硅材料)化学反应,而不是与第二材料218的表面224(如,导电材料)化学反应。藉由这样做,SAM 240可主要形成在基板210上的特征结构212上,使得第二材料218的表面224没有SAM 240。在操作130处,可将基板210暴露于羟基部分。羟基部分可为具有或有助于在表面222或SAM分子230上形成-OH官能团的材料。尽管不意欲受理论束缚,但相信表面222和/或SAM分子230的反应性位点的羟基化作用可促进形成密集堆积的SAM 240,密集堆积的SAM 240表现出减少或消除的针孔。相信羟基化作用可降低阻挡配位基的反应性位点的发生率,阻挡配位基的反应性位点会引起空间位阻。结果,SAM分子230可能够更容易地以紧密堆积的取向吸附在表面222上。例如,相信羟基化作用可促进SAM分子在表面222上的吸附优先于已经存在于表面222上的SAM配位基的聚合。
在替代实施方式中,在操作120处,基板210可暴露于羟基部分,且随后在操作130处暴露于SAM前驱物。在另一个类似的实施方式中,在操作120中,基板210可暴露于羟基部分,同时在操作130中将基板210暴露于SAM前驱物。
在其它实施方式中,SAM前驱物和羟基部分以交替方式产生脉冲。此外,SAM前驱物和羟基部分可以脉冲或连续方式一起共同流动。在一个实施方式中,SAM前驱物和羟基部分在交替的气相暴露操作中浸泡基板210。例如,将SAM前驱物输送到腔室,且在将SAM前驱物从腔室排出之前将腔室加压一段时间。随后,将羟基部分输送至腔室,且在将羟基部分从腔室排出之前将腔室加压一段时间。在这些实施方式中,基板210以交替方式浸泡在SAM/羟基中。在另一个实施方式中,将SAM前驱物和羟基部分同时输送到腔室,且将腔室加压,以允许基板210在从腔室排空SAM/羟基之前在SAM/羟基环境中浸泡一段时间。在又一个实施方式中,基板210暴露于SAM前驱物并随后暴露于周围空气。
取决于所需的实施方式,以上所述的脉冲和浸泡实施方式可执行各种持续时间。预期脉冲和/或浸泡的持续时间可根据方法的进展而改变。例如,在方法100开始时的脉冲/浸泡持续时间可相对于在方法100结束附近的脉冲/浸泡持续时间更长。相信SAM前驱物/羟基部分暴露持续时间和任何浸泡/脉冲持续时间的任何组合可一起利用,以获得具有减少或消除的针孔的SAM沉积。
合适的羟基部分前驱物的例子包括周围空气、水溶液或蒸汽、过氧化氢溶液或蒸汽、有机醇溶液或蒸汽(诸如甲醇、异丙醇、乙醇和二醇)等。氢气和氧气也可组合使用以形成羟基部分。预期根据在此所述的实施方式也可利用其它非羟基部分前驱物。非羟基部分前驱物可包括氮气、(二)异氰酸酯、硫化氢和氨等。
在操作120中,在将基板210暴露于SAM分子之后,可连续地在操作130中执行将基板210暴露于羟基部分。替代地,在操作130中将基板210暴露于羟基部分可与在操作120中将基板210暴露于SAM分子同时地执行。
在一个实施方式中,在操作120中将基板210暴露于SAM分子之后,在操作130中基板210可暴露于周围空气。在这个实施方式中,在操作130期间,基板210的温度可在具有约1mTorr和约1520Torr之间的压力的处理环境中,维持在约25℃和约400℃之间的温度下。基板210可暴露于周围空气在持续约30秒和约600秒之间的时间量。在这个实施方式中,周围空气暴露可在加压到大气压的真空腔室中进行,或者基板210可从真空处理腔室环境移除并维持在大约大气压力下的周围空气中。
在另一实施方式中,在操作120中将基板210暴露于SAM分子之后,在操作130中基板210可暴露于液态水或水蒸汽。在这个实施方式中,基板210可暴露于液态水或水蒸汽,持续约1秒和约600秒之间的时间量。在液态水暴露的实施方式中,可向处理环境提供合适量的水,诸如在约25ml和约50ml之间(对于300mm基板而言)以促进液态水暴露。在足以发生羟基化作用的时间之后,可从处理环境移除水。
在水蒸汽的实施方式中,基板210的温度可维持在约20℃和约400℃之间,且处理环境的压力可维持在约2Torr和约1520Torr之间。
操作130的暴露于羟基部分可在与操作120的将基板210暴露于SAM分子相同的处理环境中进行。替代地,暴露于羟基部分可在与用于将基板210暴露于SAM分子的处理环境不同的处理环境中进行。例如,可利用群集工具,且操作120可在第一处理腔室中执行,且操作130可在第二处理腔室中执行。在某些实施方式中,取决于所需的处理条件(亦即,水蒸汽或周围空气暴露),基板210可在真空下在第一处理腔室和第二处理腔室之间转移,或在近似大气压力下在第一处理腔室和第二处理腔室之间转移。
在操作140处,可任选地以顺序或同时的方式重复操作120和操作130。例如,操作120和操作130可在约1次和约500次之间重复。在一个实施方式中,可第一次执行操作120,可第一次执行操作130,且可第二次执行操作120。在这个实施方式中,可顺序地执行操作。在另一实施方式中,操作120和操作130可在约5次和约50次之间重复。在这个实施方式中,操作140之后可为额外操作120,使得在操作150之前立即执行将基板210暴露于SAM分子230。
在以顺序方式重复操作120和操作130的某些实施方式中,操作120与操作130的时间比例可在约1∶1的操作120:操作130和约100:1的操作120:操作130之间,例如,约10:1的操作120:操作130。在这个实施方式中,操作120可执行在约1分钟和约10分钟之间的时间量,且操作130可执行在约1分钟和约10分钟之间的时间量。操作140之后可为额外操作120,额外操作120执行的时间量实质等于在操作140的每一循环暴露工艺期间所执行的操作120的时间量,然而,预期可有利地实现对于额外操作120的更大或更小的时间量。例如,在以上所述的实施方式中,额外操作120可执行在约1分钟和约10分钟之间的时间量,诸如约5分钟。
相信环状SAM分子和羟基部分暴露可提供用于具有改良的材料阻挡性质(亦即,减少的针孔)的SAM。例如,使用环状羟基部分暴露所处理的SAM相对于未使用环状羟基部分暴露所处理的SAM(水接触角约100°)展现出增加的水接触角(亦即110°),这表明了改进的阻挡性能。
在操作150处,接着执行沉积工艺(沉积工艺是对具有选定前驱物的表面条件高度敏感的工艺),以在第二材料218的表面224上选择性地形成结构280,如图2C中所示。结构280可藉由各种技术形成,例如包括化学气相沉积(CVD)(诸如等离子体增强CVD(PE-CVD)、脉冲CVD、低压CVD(LPCVD))、外延生长、物理气相沉积(PVD)(诸如溅射或蒸发)、原子层沉积(ALD)、电镀、其它技术或其组合。选择要沉积的材料可受到基板210的表面性质的影响。结构280的厚度将根据待形成的材料和特定装置而变化。SAM 240防止材料沉积在第一材料216的表面222上。以这种方式,选择性沉积工艺可在基板上的不同位置处选择性地沉积不同的材料。
在一个实施方式中,沉积工艺是ALD工艺。由于ALD工艺对表面条件敏感,ALD适合于在基板的特定区域上选择性沉积材料。ALD工艺是具有自终止/限制生长的CVD工艺。ALD工艺产生仅几埃或单层水平的厚度。藉由将化学反应分布到循环地重复的两个单独的半反应中来控制ALD工艺。藉由ALD工艺所形成的材料的厚度取决于反应循环的数量。第一反应提供将在基板上吸附的分子层的第一原子层,且第二反应提供将在第一原子层上吸附的分子层的第二原子层。因此,材料的有序结构充当用于材料层的生长的模板。
在操作150的沉积工艺之后,在操作160处,从第一材料216的表面222移除SAM240。可藉由不会不利地影响结构280或第一材料216的表面222的任何工艺来移除SAM 240。用于移除SAM 240的工艺是SAM分子230的末端和头部基的选择的结果。可藉由湿式蚀刻工艺、干式蚀刻工艺、高温退火工艺(如,大于300℃)而移除SAM,以从第一材料216的表面222释放SAM。在操作160之后,可执行额外的处理操作,以制造半导体及其它装置特征结构。
虽然前述内容涉及本公开内容的实施方式,但是可在不背离本公开内容的基本范围的情况下,设计出本公开内容的其他和进一步的实施方式,且本公开内容的范围由以下权利要求书确定。
Claims (20)
1.一种处理基板的方法,包括以下步骤:
将基板暴露于自组装单层(“SAM”)分子持续从60秒至600秒的第一时间段,以实现SAM在第一材料上的选择性沉积,其中所述基板包括暴露的第一材料和暴露的第二材料;
将所述基板暴露于羟基部分持续从60秒至600秒的第二时间段;
将所述基板暴露于SAM分子和将所述基板暴露于羟基部分分别以1:1和100:1之间的所述第一时间段和所述第二时间段的时间比例重复;
在执行所述重复之后,将所述基板暴露于所述SAM分子;
选择性地沉积第三材料在所述暴露的第二材料上;和
从所述第一材料移除所述SAM。
2.如权利要求1所述的方法,其中羟基部分前驱物选自由周围空气、水溶液、水蒸汽、过氧化氢溶液、过氧化氢蒸汽、有机醇溶液和有机醇蒸汽所组成的组。
3.如权利要求2所述的方法,其中所述羟基部分前驱物选自由水溶液、水蒸汽和周围空气所组成的组。
4.如权利要求1所述的方法,其中羟基部分前驱物是水蒸汽。
5.如权利要求1所述的方法,其中羟基部分前驱物是周围空气。
6.如权利要求1所述的方法,其中将所述基板暴露于SAM分子和将所述基板暴露于羟基部分的时间比例为10:1。
7.如权利要求1所述的方法,其中在所述重复之后所执行的将所述基板暴露于所述SAM分子的时间量实质等于在所述重复的一个循环期间所执行的将所述基板暴露于SAM分子的时间量。
8.如权利要求1所述的方法,其中所述SAM分子选自由羧酸材料、膦酸材料、硫醇材料、硅烷胺材料、氯硅烷材料、氧硅烷材料及其组合所组成的组。
9.如权利要求8所述的方法,其中所述膦酸材料选自由甲基膦酸、乙基膦酸、丙基膦酸、丁基膦酸、戊基膦酸、己基膦酸、庚基膦酸、辛基膦酸、壬基膦酸、癸基膦酸、十一烷基膦酸、十二烷基膦酸、十三烷基膦酸、十四烷基膦酸、十五烷基膦酸、十六烷基膦酸、十七烷基膦酸、十八烷基膦酸、十九烷基膦酸及其组合所组成的组。
10.如权利要求8所述的方法,其中所述硫醇材料选自由甲硫醇、乙硫醇、丙硫醇、丁硫醇、戊硫醇、己硫醇、庚硫醇、辛硫醇、壬硫醇、癸硫醇、十一烷硫醇、十二烷硫醇、十三烷硫醇、十四烷硫醇、十五烷硫醇、十六烷硫醇、十七烷硫醇、十八烷硫醇、十九烷硫醇及其组合所组成的组。
11.如权利要求8所述的方法,其中所述硅烷胺材料选自由三(二甲氨基)甲基硅烷、三(二甲氨基)乙基硅烷、三(二甲氨基)丙基硅烷、三(二甲氨基)丁基硅烷、三(二甲氨基)戊基硅烷、三(二甲氨基)己基硅烷、三(二甲氨基)庚基硅烷、三(二甲氨基)辛基硅烷、三(二甲氨基)壬基硅烷、三(二甲氨基)癸基硅烷、三(二甲氨基)十一烷基硅烷、三(二甲氨基)十二烷基硅烷、三(二甲氨基)十三烷基硅烷、三(二甲氨基)十四烷基硅烷、三(二甲氨基)十五烷基硅烷、三(二甲氨基)十六烷基硅烷、三(二甲氨基)十七烷基硅烷、三(二甲氨基)十八烷基硅烷、三(二甲氨基)十九烷基硅烷及其组合所组成的组。
12.如权利要求8所述的方法,其中所述氯硅烷材料选自由甲基三氯硅烷、乙基三氯硅烷、丙基三氯硅烷、丁基三氯硅烷、戊基三氯硅烷、己基三氯硅烷、庚三氯硅烷、辛基三氯硅烷、壬基三氯硅烷、癸基三氯硅烷、十一烷基三氯硅烷、十二烷基三氯硅烷、十三烷基三氯硅烷、十四烷基三氯硅烷、十五烷基三氯硅烷、十六烷基三氯硅烷、十七烷基三氯硅烷、十八烷基三氯硅烷、十九烷基三氯硅烷及其组合所组成的组。
13.如权利要求8所述的方法,其中所述氧硅烷材料选自由甲基三甲氧基硅烷、甲基三乙氧基硅烷、乙基三甲氧基硅烷、乙基三乙氧基硅烷、丙基三甲氧基硅烷、丙基三乙氧基硅烷、丁基三甲氧基硅烷、丁基三乙氧基硅烷、戊基三甲氧基硅烷、戊基三乙氧基硅烷、己基三甲氧基硅烷、己基三乙氧基硅烷、庚基三甲氧基硅烷、庚基三乙氧基硅烷、辛基三甲氧基硅烷、辛基三乙氧基硅烷、壬基三甲氧基硅烷、壬基三乙氧基硅烷、癸基三甲氧基硅烷、癸基三乙氧基硅烷、十一烷基三甲氧基硅烷、十一烷基三乙氧基硅烷、十二烷基三甲氧基硅烷、十二烷基三乙氧基硅烷、十三烷基三甲氧基硅烷、十三烷基三乙氧基硅烷、十四烷基三甲氧基硅烷、十四烷基三乙氧基硅烷、十五烷基三甲氧基硅烷、十五烷基三乙氧基硅烷、十六烷基三甲氧基硅烷、十六烷基三乙氧基硅烷、十七烷基三甲氧基硅烷、十七烷基三乙氧基硅烷、十八烷基三甲氧基硅烷、十八烷基三乙氧基硅烷、十九烷基三甲氧基硅烷、十九烷基三乙氧基硅烷及其组合所组成的组。
14.一种处理基板的方法,包括以下步骤:
将基板暴露于自组装单层(“SAM”)分子持续第一时间段,以实现SAM在第一处理腔室中的第一材料上的选择性沉积,其中所述基板包括暴露的第一材料和暴露的第二材料;
将所述基板转移到第二处理腔室;
在所述第二处理腔室中将所述基板暴露于由水蒸汽所形成的羟基部分持续第二时间段;
分别以1:1和100:1之间的时间比例重复在所述第一处理腔室中将所述基板暴露于SAM分子和在所述第二处理腔室中将所述基板暴露于由水蒸汽所形成的所述羟基部分;
在执行所述重复之后,在所述第一处理腔室中将所述基板暴露于所述SAM分子;
选择性地沉积第三材料在所述暴露的第二材料上;和
从所述第一材料移除所述SAM。
15.如权利要求14所述的方法,其中转移所述基板的步骤在真空下执行。
16.如权利要求14所述的方法,其中将所述基板暴露于由水蒸汽所形成的所述羟基部分在25℃和300℃之间的温度下、在1Torr和600Torr之间的压力下执行1秒和600秒之间的时间量。
17.如权利要求14所述的方法,其中将所述基板暴露于SAM分子和将所述基板暴露于由水蒸汽所形成的所述羟基部分的时间比例为1:1和10:1之间。
18.一种处理基板的方法,包括以下步骤:
将基板暴露于自组装单层(“SAM”)分子持续第一时间段,以实现SAM在处理腔室中的第一材料上的选择性沉积,其中所述基板包括暴露的第一材料和暴露的第二材料;
将所述基板转移到周围空气环境;
将所述基板暴露于由在所述周围空气环境中的周围空气所形成的羟基部分持续第二时间段;
分别以1:1和100:1之间的所述第一时间段和所述第二时间段的时间比例重复在所述处理腔室中将基板暴露于SAM分子和于所述周围空气环境中将所述基板暴露于羟基部分;
在执行所述重复之后,在所述处理腔室中将所述基板暴露于所述SAM分子;
选择性地沉积第三材料在所述暴露的第二材料上;和
从所述第一材料移除所述SAM。
19.如权利要求18所述的方法,其中将所述基板暴露于由周围空气所形成的羟基部分在25℃和400℃之间的温度下、1mTorr和1520Torr之间的压力下执行30秒和600秒之间的时间量。
20.如权利要求18所述的方法,其中将所述基板暴露于SAM分子和将所述基板暴露于由周围空气所形成的羟基部分的时间比例为1∶1和10∶1之间。
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