CN111512430B - 在导电表面上沉积阻挡层的方法 - Google Patents
在导电表面上沉积阻挡层的方法 Download PDFInfo
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- CN111512430B CN111512430B CN201880082786.2A CN201880082786A CN111512430B CN 111512430 B CN111512430 B CN 111512430B CN 201880082786 A CN201880082786 A CN 201880082786A CN 111512430 B CN111512430 B CN 111512430B
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- 238000000034 method Methods 0.000 title claims abstract description 51
- 230000004888 barrier function Effects 0.000 title claims abstract description 37
- 238000000151 deposition Methods 0.000 title claims abstract description 25
- 239000000758 substrate Substances 0.000 claims abstract description 49
- -1 alkyl phosphonic acid Chemical compound 0.000 claims abstract description 13
- 239000004020 conductor Substances 0.000 claims description 21
- 239000002253 acid Substances 0.000 claims description 18
- 239000003989 dielectric material Substances 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 125000003342 alkenyl group Chemical group 0.000 claims description 10
- 125000000304 alkynyl group Chemical group 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 10
- 229910017052 cobalt Inorganic materials 0.000 claims description 9
- 239000010941 cobalt Substances 0.000 claims description 9
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 8
- 239000010949 copper Substances 0.000 claims description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 229910052721 tungsten Inorganic materials 0.000 claims description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 239000011651 chromium Substances 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 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 claims description 4
- 229910001092 metal group alloy Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 150000004767 nitrides Chemical class 0.000 claims description 4
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims description 4
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 claims description 4
- 229910001936 tantalum oxide Inorganic materials 0.000 claims description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 4
- 239000010937 tungsten Substances 0.000 claims description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- 125000006539 C12 alkyl 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])C([H])([H])C([H])([H])* 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- 238000011065 in-situ storage Methods 0.000 abstract description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 39
- 239000000463 material Substances 0.000 description 14
- 150000001735 carboxylic acids Chemical class 0.000 description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- 229910052581 Si3N4 Inorganic materials 0.000 description 10
- 230000000903 blocking effect Effects 0.000 description 10
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 230000008021 deposition Effects 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 239000013545 self-assembled monolayer Substances 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000002094 self assembled monolayer Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- ZDPHROOEEOARMN-UHFFFAOYSA-N undecanoic acid Chemical compound CCCCCCCCCCC(O)=O ZDPHROOEEOARMN-UHFFFAOYSA-N 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 3
- 230000010354 integration Effects 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- CFTHARXEQHJSEH-UHFFFAOYSA-N silicon tetraiodide Chemical compound I[Si](I)(I)I CFTHARXEQHJSEH-UHFFFAOYSA-N 0.000 description 2
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 2
- 239000005052 trichlorosilane Substances 0.000 description 2
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 1
- CPRNWMZKNOIIML-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-heptadecafluorooctylphosphonic acid Chemical compound OP(O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F CPRNWMZKNOIIML-UHFFFAOYSA-N 0.000 description 1
- AWQSAIIDOMEEOD-UHFFFAOYSA-N 5,5-Dimethyl-4-(3-oxobutyl)dihydro-2(3H)-furanone Chemical compound CC(=O)CCC1CC(=O)OC1(C)C AWQSAIIDOMEEOD-UHFFFAOYSA-N 0.000 description 1
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- 229910003691 SiBr Inorganic materials 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 238000004380 ashing Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000012707 chemical precursor Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 239000012761 high-performance material Substances 0.000 description 1
- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- FTMKAMVLFVRZQX-UHFFFAOYSA-N octadecylphosphonic acid Chemical compound CCCCCCCCCCCCCCCCCCP(O)(O)=O FTMKAMVLFVRZQX-UHFFFAOYSA-N 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 239000010980 sapphire Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- AIFMYMZGQVTROK-UHFFFAOYSA-N silicon tetrabromide Chemical compound Br[Si](Br)(Br)Br AIFMYMZGQVTROK-UHFFFAOYSA-N 0.000 description 1
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- LXEXBJXDGVGRAR-UHFFFAOYSA-N trichloro(trichlorosilyl)silane Chemical compound Cl[Si](Cl)(Cl)[Si](Cl)(Cl)Cl LXEXBJXDGVGRAR-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- 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
- H01L21/30—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
- H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
- H01L21/321—After treatment
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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
- H01L21/02296—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
- H01L21/02312—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 gas or vapour
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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
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
- H01L21/76801—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the dielectrics, e.g. smoothing
- H01L21/76829—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the dielectrics, e.g. smoothing characterised by the formation of thin functional dielectric layers, e.g. dielectric etch-stop, barrier, capping or liner layers
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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
- C23C16/04—Coating on selected surface areas, e.g. using masks
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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
- H01L21/02041—Cleaning
- H01L21/02057—Cleaning during device manufacture
- H01L21/02068—Cleaning during device manufacture during, before or after processing of conductive layers, e.g. polysilicon or amorphous silicon layers
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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
- 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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- H01L21/02—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
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- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
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- 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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- 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
- H01L21/02227—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a process other than a deposition process
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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
- H01L21/02225—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
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- H—ELECTRICITY
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- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02518—Deposited layers
- H01L21/02521—Materials
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Abstract
描述了优先于介电表面而在导电表面上选择性沉积阻挡层的方法。在一些实施方式中,将羧酸暴露于基板以选择性地形成阻挡层。在一些实施方式中,将酰肼暴露于基板,以选择性形成阻挡层。在一些实施方式中,将烷基膦酸暴露于基板,以选择性地形成阻挡层。在一些实施方式中,原位形成烷基膦酸且将该烷基膦酸暴露至基板。在一些实施方式中,在形成阻挡层之后,在介电表面上选择性地沉积层。
Description
技术领域
本公开内容的实施方式与在导电表面上沉积阻挡层的方法有关。尤其是,本公开内容的实施方式涉及在导电表面上沉积阻挡层以助膜沉积于图案化基板的介电表面上的方法。
背景技术
半导体工业在追求涉及纳米级特征的快速缩放器件的微型化时,面临许多挑战。这些问题包括,引入诸如多个光刻步骤之类的复杂的制造步骤和高效能材料的整合。为了维持器件微型化的节奏,选择性沉积已经展现前景,因为该选择性沉积有潜力通过简化整合方案而消除昂贵的光刻步骤。
能够以各种方式完成材料的选择性沉积。化学前驱物可以选择性与相对于另一表面的一个表面反应(金属或介电)。可调节工艺参数(例如压力、基板温度、前驱物分压、和/或气流),以调节特定表面反应的化学动力学。另一种可能的方案涉及表面前处理,能够使用该表面前处理使关注表面对进入的膜沉积前驱物呈活化或去活化。
本领域中一直需要去活化或阻挡导电表面的处理方法。
发明内容
本公开内容的一或多个实施方式涉及选择性沉积阻挡层的方法。该方法包括,将基板暴露于羧酸,以优先于第二表面而在第一表面上选择性形成阻挡层且形成阻挡的第一表面,该基板包括导电材料与介电材料,该导电材料具有该第一表面,该介电材料具有该第二表面。该羧酸包括至少一种具有通式RCOOH的化合物,其中R选自C4至C20烷基、全氟烷基、烯基、或炔基基团。
本公开内容的额外实施方式涉及一种选择性沉积阻挡层的方法,该方法包括:将基板暴露于酰肼(hydrazide),以优先于第二表面而在第一表面上选择性形成阻挡层且形成阻挡的第一表面,该基板包括导电材料与介电材料,该导电材料具有该第一表面,该介电材料具有该第二表面。该酰肼包括至少一种具有通式RC(O)NHNR’2的化合物,其中R选自C4至C20烷基、全氟烷基、烯基、或炔基基团,且每一R’独立地选自H或C1至C4烷基,或是能够接合在一起而形成包括2至5个碳原子的环。
本公开内容的额外实施方式涉及一种选择性沉积阻挡层的方法,该方法包括:将基板暴露于气态烷基膦酸(alkyl phosphonic acid),以优先于第二表面而在第一表面上选择性形成阻挡层且形成阻挡的第一表面,该基板包括导电材料与介电材料,该导电材料具有该第一表面,该介电材料具有该第二表面。该烷基膦酸包括至少一种具有通式RP(O)(OR”)2的化合物,其中R选自C4至C20烷基、全氟烷基、烯基、或炔基基团,且每一R”独立地选自H、C1至C12烷基或芳基。
附图说明
以上简要概述本公开内容的上述详述特征可以被详细理解的方式、以及对本公开内容的更特定描述,可通过参照实施方式来获得一些实施方式绘示在附图中。然而,应注意,附图仅说明本公开内容的典型实施方式,因此不应认为是对本公开内容的范围的限制,因为本公开内容可容许其他等同有效的实施方式。
附图图示根据本公开内容的一或多个实施方式的处理方法。
在附图中,类似的部件和/或特征可具有相同的附图标号。另外,相同类型的各种部件可通过使附图标号后跟随连接号及第二标号而区分,该第二符号区分类似部件。若在说明书中仅使用第一附图标号,则该描述适用于具有相同第一附图标号而无论第二附图标号为何的任何一个类似部件。
具体实施方式
本公开内容的实施方式提供用于在导电表面上选择性沉积阻挡层的方法。本公开内容的实施方式确认用于沉积可单独使用或结合使用的数个阻挡层的多种方法。
如本文所用,“基板表面”意指上面执行膜处理的基板的任何部分或基板上形成的材料表面的部分。例如,视应用而定,可在上面执行处理的基板表面包括:材料,诸如:硅、氧化硅、氮化硅、掺杂硅、锗、砷化镓、玻璃、蓝宝石;及任何其他材料,诸如金属、金属氮化物、金属合金、及其他导电材料。基板包括但不限于半导体晶片。可将基板暴露于前处理工艺,以抛光、蚀刻、还原、氧化、羟基化、退火、UV固化、电子束固化和/或烘烤基板表面。除了在基板本身的表面上直接执行膜处理之外,在本公开内容中,所公开的任何膜处理步骤也可以在基板上所形成的下层(underlayer)上进行,如下文更详细公开,且术语“基板表面”旨在包括上下文所指出的此下层。因此,举例而言,在已经将膜/层或部分膜/层沉积到基板表面上的情况中,新沉积的膜/层的暴露表面变成基板表面。基板可具有各种尺寸,例如直径为200mm或300mm的晶片,以及矩形或方形嵌板(pane)。在一些实施方式中,基板包括刚性、分立的材料。
本公开内容的实施方式有利地提供优先于介电表面而在导电表面上选择性形成阻挡层的方法。一些实施方式有利地提供了选择性地在介电表面上沉积层的进一步的方法。
如在本说明书和所附权利要求书中所使用的,短语“导电表面”或“介电表面”意味着,表面涉及具有所述的特性的材料。因此,导电表面是导电材料的表面,但是没有关于表面本身导电率的陈述。类似地,介电表面是介电材料的表面。
如在本说明书和所附权利要求书中所使用的,术语“优先于另一表面而在一个表面上选择性沉积膜”及类似术语意味着,第一量的膜沉积在第一表面上且第二量的膜沉积在第二表面上,其中该膜的该第二量小于该膜的该第一量,或者是没有膜沉积在第二表面上。在这方面使用的术语“优先于(over)”并不意味着一个表面在另一个表面上的物理定向,而是相对于另一个表面而与一个表面化学反应的热力学或动力学性质的关系。例如,将钴膜优先于介电表面而选择性沉积至铜表面上意味着,钴膜沉积在铜表面上,并且较少或没有钴膜沉积在该介电表面上;或者意味着,相对于在介电表面上形成钴膜,铜表面上钴膜的形成在热力学或动力学上是有利的。在一些实施方式中,“选择性”意味着,主体材料在选择的表面上以一速率形成,该速率大于或等于在非选择的表面上的形成速率的约10倍、15倍、20倍、25倍、30倍、35倍、40倍、45倍或50倍。换言之,主体材料相对于非选择的表面的选择性大于或等于约10:1、15:1、20:1、25:1、30:1、35:1、40:1、45:1、或50:1。
本公开内容的一些实施方式包含一般称作自组装单层(SAM)的阻挡层。自组装单层(SAM)由吸附在表面上的自发式组装的有机分子的有序排列所组成。这些分子一般包含对基板具有亲和力的一或多个部分(头部基团)和相对长、惰性、线性的碳氢化合物部分(尾部基团)。
在这种情况下,SAM的形成是以下述方式发生:经由在表面快速吸附分子头部基团,且经由范德华(van der Waals)相互作用分子尾部基团彼此缓慢联结。挑选SAM前驱物以使得在沉积期间头部基团选择性与待阻挡的基板材料反应。然后执行沉积,且SAM能够经由热分解(伴随任何副产物的脱附)或与整合兼容的灰化工艺而移除。
本公开内容的一或多个实施方式涉及优先于基板的第二表面而在基板的第一表面上选择性沉积阻挡层的方法。第一表面是导电材料的表面。第二表面是介电材料的表面。
基板的导电材料可为任何适合的材料。适合的导电材料包括但不限于金属、金属氮化物、一些金属氧化物、金属合金、上述材料的组合,及其他导电材料。在一些实施方式中,导电材料包括铬、锰、铁、铜、镍、钴、钨、钌、氧化钽、氮化钽、氧化钛、或氮化钛中的一或多种。在一些实施方式中,导电材料基本上由铬、锰、铁、铜、镍、钴、钨、钌、氧化钽、氮化钽、氧化钛、或氮化钛组成。如在本说明书和所附的权利要去书中所使用的,术语“基本上由……组成”意味着,在原子基础上,该材料大于或等于所述材料的约95%、98%或99%。
如在本说明书和所附的权利要求书中所使用的,术语“氧化物”或类似术语意味着,该材料含有指定的元素。该术语不应解释为暗示特定的元素比例。因此,“氧化物”或类似物可包括化学当量比的元素或非化学当量比的元素。
基板的介电材料可以是任何适合的材料。适合的介电材料包括但不限于氧化硅(例如SiO2)、氮化硅、碳化硅、及上述材料的组合(例如SiCON)。在一些实施方式中,介电材料基本上由二氧化硅(SiO2)组成。在一些实施方式中,该层包括氮化硅。在一些实施方式中,该层基本上由氮化硅组成。
参照该图,所归纳的方法100开始于基板105,基板105包括具有第一表面112的导电材料110和具有第二表面122的介电材料120。该基板105暴露于阻挡化合物(未示出),以优先于第二表面122在第一表面112上选择性形成阻挡层130,且形成阻挡的第一表面132。
在一些实施方式中,方法100以如下方式继续:优先于阻挡的第一表面132而在第二表面122上选择性沉积层125。在一些实施方式中,层125是介电材料。在一些实施方式中,该层包括氮化硅。
能够经由任何适合的工艺执行氮化硅的沉积。适合的工艺可包括,将基板暴露于卤化硅和氨。适合的卤化硅包括但不限于:二氯硅烷(DCS)、三氯硅烷(TCS)、四氯硅烷(SiCl4)、四溴硅烷(SiBr4)、四碘硅烷(SiI4)、和六氯乙硅烷(HCDS)。
在一些实施方式中,沉积有一厚度的氮化硅层,该厚度在约至约/>的范围内,或在约/>至约/>的范围内,或者在约/>至约/>的范围内。在一些实施方式中,重复形成阻挡层和沉积该层,直到该层的厚度大于或等于约/>大于或等于约/>大于或等于约/>或大于或等于约/>
在一些实施方式中,方法100以如下方式继续:移除阻挡层130以暴露第一表面112。在一些实施方式中,使用选择性蚀刻工艺移除阻挡层130。已知基于氧及基于氟的蚀刻会蚀刻类似于本文公开的阻挡层的基于碳的膜。
一个非限制性实例是,经由基于氧的远程等离子体移除该阻挡层。在此实例中,基于氧的远程等离子体蚀刻移除阻挡层也氧化第一表面。为了恢复原始的表面组成,所述表面能够被还原。适合的还原工艺包括但不限于,使用包含氢或氨的等离子体和包含氢或氨的热退火。在一些实施方式中,能够独立地远程或内部生成(及导电耦合或感应耦合)氧等离子体、氟等离子体、氢等离子体、和氨等离子体。
尽管未在图中示出,但本公开内容的方法可进一步包括,在将基板暴露于阻挡化合物之前清洁第一表面。在一些实施方式中,清洁第一表面包括,将第一表面暴露于包含乙酸和乙醇的溶液。在一些实施方式中,溶液是10%的乙酸的乙醇溶液(即在乙醇中10%v/v的乙酸,或在乙醇中10%w/w的乙酸)。在一些实施方式中,清洁第一表面包括,将第一表面暴露于氢气(H2)的等离子体。在一些实施方式中,氢等离子体是导电耦合等离子体(CCP)。在一些实施方式中,氢等离子体是感应耦合等离子体(ICP)。不受理论束缚,相信清洁该第一表面造成第一表面上更高程度地普遍存在H封端(H-termination)。相信这些封端是阻挡化合物的反应位点。
在一些实施方式中,阻挡化合物包含羧酸。在一些实施方式中,该方法包括,将基板暴露于羧酸,以优先于第二表面而在第一表面上选择性形成阻挡层且形成阻挡的第一表面,该基板包括导电材料与介电材料,该导电材料具有该第一表面,该介电材料具有该第二表面。
在一些实施方式中,该羧酸包括至少一种具有通式为RCOOH的化合物,其中R选自C4-C20的烷基、全氟烷基、烯基或炔基。如以此方式所用,字母“C”后跟随数字(例如“C4”)意味着,取代基包含指定数目的碳原子(例如,C4包含四个碳原子)。一些实施方式中,C4-C20烷基基本上由C-C单键和C-H键组成。在一些实施方式中,C4-C20全氟烷基基本上由C-C单键和C-F键组成。在一些实施方式中,C4-C20烯基基本上由C-C单键、至少一个C-C双键和C-H键组成。在一些实施方式中,C4-C20炔基基本上由C-C单键、至少一个C-C三键、和C-H键组成。在一些实施方式中,C4-C20基团包括一个或多个卤素原子和/或其他疏水部分。在一些实施方式中,C4-C20基团可以是直链基团(例如正丁基)、支链(branched chain)基团(例如叔丁基)、或环状基团(例如环己基)。在一些实施方式中,烷基、全氟烷基、烯基、或炔基是直链。在一些实施方式中,烷基、全氟烷基、烯基、或炔基是支链。
在一些实施方式中,羧酸包括庚酸、辛酸、十一烷酸或十八烷酸。在一些实施方式中,羧酸基本上由十一烷酸组成。
在一些实施方式中,长链羧酸可用作阻挡分子且与金属表面(具有或不具有原生氧化物)反应。在一些实施方式中,暴露于羧酸是在溶液中执行。在一些实施方式中,暴露于羧酸于在气相中执行。
在一些实施方式中,小且中等链长(<C12)的羧酸以气相递送。在一些实施方式中,长烷基链(≥C12)的羧酸可用作溶液相中的阻挡化合物。
不受理论束缚,金属(包括但不限于Cu、Co、W、Ru、TiN)通常是亲氧的(oxophilic)并且优先地与羧酸结合而在SiO2或SiN表面上成为RCOO-M。
在一些实施方式中,优先于第一阻挡表面而在第二表面上选择性地沉积氮化硅层。在一些实施方式中,氮化硅层的厚度在约30埃至约40埃的范围内。在一些实施方式中,以大于或等于约30:1的选择性沉积氮化硅层。在一些实施方式中,将基板维持在小于或等于约200℃的温度。
在一些实施方式中,阻挡化合物包含酰肼。在一些实施方式中,该方法包括,将基板暴露至酰肼,以越过第二表面而在第一表面上选择性形成阻挡层且形成阻挡的第一表面,该基板包括导电材料与介电材料,该导电材料具有该第一表面,该介电材料具有该第二表面。
在一些实施方式中,该酰肼包括至少一种具有通式为RC(O)NHNR’2的化合物,其中R选自C4-C20烷基、全氟烷基、烯基或炔基,并且每个R’独立地选自H或C1-C4烷基,或可以连接在一起形成包含2至5个碳原子的环。
不受理论束缚,预期酰肼形成热稳定的金属配合物。钴-酰肼配合物如双(叔丁基碳酰基肼基)钴,相对地较不易挥发并且至高达250℃仍热稳定。相信使用较长链的烷基能够进一步降低蒸气压并导致导电表面的阻挡。
在一些实施方式中,R是叔丁基。在一些实施方式中,每个R’是氢。在一些实施方式中,每个R’是甲基。
在一些实施方式中,阻挡化合物包含气态烷基膦酸。在一些实施方式中,该方法包括,将基板暴露于气态烷基膦酸,以优先于第二表面而在第一表面上选择性形成阻挡层且形成阻挡的第一表面,该基板包括导电材料与介电材料,该导电材料具有该第一表面,该介电材料具有该第二表面。如本说明书和所附的权利要求书中所用,描述词“气态”意指烷基膦酸以气相供应。
在一些实施方式中,烷基膦酸包括至少一种具有通式为RP(O)(OR”)2的化合物,其中R选自C4-C20烷基、全氟烷基、烯基或炔基,并且每个R”独立地选自H、C1-C12烷基、或芳基。
在一些实施方式中,R”独立地为C1-C12烷基或芳基。不受理论束缚,这些实施方式的烷基膦酸中氢键的缺乏增加了这些阻挡化合物的蒸气压。
在一些实施方式中,烷基膦酸包括十八烷基膦酸。在一些实施方式中,烷基膦酸包括全氟辛基膦酸。
在一些实施方式中,烷基膦酸通过二卤代烷基膦酸(dihaloalkylphosphonicacid)与醇的反应而原位产生。在一些实施方式中,二卤代烷基膦酸包括至少一种具有通式RP(O)X2的化合物,其中每个X是独立选择的卤素。在一些实施方式中,醇包括至少一种具有通式R”OH的化合物。
不受理论束缚,二卤代烷基膦酸和醇各自比它们产生的烷基膦酸更易挥发。因此,有可能在气相中输送二卤代烷基膦酸和醇,使得它们反应形成原本会难以挥发的烷基膦酸。
在一些实施方式中,R”是H。不受理论束缚,使用水作为这些实施方式的醇,原位提供烷基膦酸,否则原本烷基膦酸会由于氢键而具有低挥发性。
尽管已经参考特定实施方式描述了本公开内容,但应了解,这些实施方式仅为对本公开内容的原理及应用的说明。对于发明所属技术领域的技术人员显而易见的是,在不背离本公开内容的精神与范围的情况下,可对本公开内容的方法和设备进行各种修改和变型。因此,意欲本公开内容包括在所附的权利要求书及其等效形式的范围内的修改与变型。
Claims (17)
1.一种选择性沉积阻挡层的方法,所述方法包括:
将基板暴露于气态烷基膦酸,以优先于第二表面而在第一表面上选择性形成阻挡层且形成阻挡的第一表面,所述基板包括导电材料与介电材料,所述导电材料具有所述第一表面,所述介电材料具有所述第二表面,所述烷基膦酸包括至少一种具有通式RP(O)(OR”)2的化合物,其中R选自C4至C20烷基、全氟烷基、烯基、或炔基基团,且每一R”独立地选自C1至C12烷基或芳基。
2.如权利要求1所述的方法,其中所述导电材料包括金属、金属合金、金属氧化物、金属氮化物、或上述材料的组合。
3.如权利要求2所述的方法,其中所述导电材料包括下述一或多种材料:铬、锰、铁、铜、镍、钴、钨、钌、氧化钽、氮化钽、氧化钛或氮化钛。
4.如权利要求1所述的方法,进一步包括:优先于所述阻挡的第一表面而在所述第二表面上选择性沉积一层。
5.如权利要求4所述的方法,其中选择性沉积在所述第二表面上的所述层包括介电材料。
6.如权利要求1所述的方法,其中将所述基板暴露于所述气态烷基膦酸包括:使二卤代烷基膦酸与醇反应而形成所述烷基膦酸,所述二卤代烷基膦酸包括至少一种具有通式RP(O)X2的化合物,其中每一X是独立选择的卤素,所述醇包括至少一种具有通式R”OH的化合物。
7.如权利要求6所述的方法,其中R”是H。
8.如权利要求6所述的方法,进一步包括:优先于所述阻挡的第一表面而在所述第二表面上选择性沉积一层。
9.如权利要求8所述的方法,其中选择性沉积在所述第二表面上的所述层包括介电材料。
10.一种选择性沉积阻挡层的方法,所述方法包括:
将基板暴露于酰肼,以优先于第二表面而在第一表面上选择性形成阻挡层且形成阻挡的第一表面,所述基板包括导电材料与介电材料,所述导电材料具有所述第一表面,所述介电材料具有所述第二表面,所述酰肼包括至少一种具有通式RC(O)NHNR’2的化合物,其中R选自C4至C20烷基、全氟烷基、烯基、或炔基基团,且每一R’独立地选自H或C1至C4烷基,或是接合在一起而形成包括2至5个碳原子的环。
11.如权利要求10所述的方法,其中所述导电材料包括金属、金属合金、金属氧化物、金属氮化物、或上述材料的组合。
12.如权利要求11所述的方法,其中所述导电材料包括下述一或多种材料:铬、锰、铁、铜、镍、钴、钨、钌、氧化钽、氮化钽、氧化钛或氮化钛。
13.如权利要求10所述的方法,进一步包括:优先于所述阻挡的第一表面而在所述第二表面上选择性沉积一层。
14.如权利要求13所述的方法,其中选择性沉积在所述第二表面上的所述层包括介电材料。
15.如权利要求10所述的方法,其中R是叔丁基基团。
16.如权利要求10所述的方法,其中每一R’是氢。
17.如权利要求10所述的方法,其中每一R’是甲基基团。
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