TWI757565B - 在導電表面上沉積阻擋層的方法 - Google Patents
在導電表面上沉積阻擋層的方法 Download PDFInfo
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- TWI757565B TWI757565B TW107143569A TW107143569A TWI757565B TW I757565 B TWI757565 B TW I757565B TW 107143569 A TW107143569 A TW 107143569A TW 107143569 A TW107143569 A TW 107143569A TW I757565 B TWI757565 B TW I757565B
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- 238000000034 method Methods 0.000 title claims abstract description 41
- 238000000151 deposition Methods 0.000 title claims abstract description 22
- 230000000903 blocking effect Effects 0.000 title claims abstract description 16
- 239000000758 substrate Substances 0.000 claims abstract description 46
- -1 alkyl phosphonic acid Chemical compound 0.000 claims abstract description 6
- 230000004888 barrier function Effects 0.000 claims description 39
- 239000004020 conductor Substances 0.000 claims description 27
- 239000003989 dielectric material Substances 0.000 claims description 23
- 239000002253 acid Substances 0.000 claims description 20
- 150000001875 compounds Chemical class 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 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
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 239000010949 copper Substances 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 3
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 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 3
- 229910001092 metal group alloy Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 150000004767 nitrides Chemical class 0.000 claims description 3
- 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 3
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 claims description 3
- 229910001936 tantalum oxide Inorganic materials 0.000 claims description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 239000010937 tungsten Substances 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
- 125000004122 cyclic group Chemical group 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims 1
- 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 35
- 239000000463 material Substances 0.000 description 18
- 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
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 12
- 229910052581 Si3N4 Inorganic materials 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
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 125000003342 alkenyl group Chemical group 0.000 description 8
- 125000000304 alkynyl group Chemical group 0.000 description 8
- 230000008021 deposition Effects 0.000 description 8
- 125000005010 perfluoroalkyl group Chemical group 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 6
- 230000008569 process Effects 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 5
- 229910021529 ammonia Inorganic materials 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
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- 239000001301 oxygen Substances 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 238000011282 treatment Methods 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
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- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 239000000377 silicon dioxide 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
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 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
- 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
- 238000000206 photolithography Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- AIFMYMZGQVTROK-UHFFFAOYSA-N silicon tetrabromide Chemical compound Br[Si](Br)(Br)Br AIFMYMZGQVTROK-UHFFFAOYSA-N 0.000 description 2
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 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
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 235000012431 wafers Nutrition 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
- 229910003676 SiBr4 Inorganic materials 0.000 description 1
- 229910003910 SiCl4 Inorganic materials 0.000 description 1
- 229910004480 SiI4 Inorganic materials 0.000 description 1
- 229910004298 SiO 2 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
- WNLOBVNMCOTLMB-UHFFFAOYSA-N cobalt hydrazine Chemical class NN.[Co] WNLOBVNMCOTLMB-UHFFFAOYSA-N 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
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007792 gaseous phase Substances 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
- 150000004820 halides Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 239000012761 high-performance material Substances 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 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
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000203 mixture Substances 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
- 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
- CFTHARXEQHJSEH-UHFFFAOYSA-N silicon tetraiodide Chemical compound I[Si](I)(I)I CFTHARXEQHJSEH-UHFFFAOYSA-N 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
- 229910052718 tin Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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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
- H01L21/70—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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- 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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- 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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- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02041—Cleaning
- H01L21/02057—Cleaning during device manufacture
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- H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
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- 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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- 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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Abstract
本文描述越過介電表面而在導電表面上選擇性沉積阻擋層的方法。在一些實施例中,將羧酸暴露於基材以選擇性地形成阻擋層。在一些實施例中,將醯肼暴露於基材,以選擇性形成阻擋層。在一些實施例中,將烷基膦酸暴露於基材,以選擇性地形成阻擋層。在一些實施例中,原位形成烷基膦酸且將該烷基膦酸暴露至基材。 在一些實施例中,在形成阻擋層之後,在介電表面上選擇性地沉積層。
Description
本案揭露內容之實施例關於在導電表面上沉積阻擋層的方法。更特定而言,本案揭露內容之實施例涉及在導電表面上沉積阻擋層以助膜沉積於圖案化基材之介電表面上的方法。
半導體工業在追求元件微型化時,面臨許多挑戰,追求元件微型化涉及了奈米級特徵的快速縮放。這些問題包括,引入複雜的製造步驟(諸如多個光微影步驟)和高效能材料之整合。為了維持元件微型化的節奏,選擇性沉積已經展現前景,因為該選擇性沉積有潛力藉由簡化整合方案而消除昂貴的光微影步驟。
能夠以各種方式完成材料的選擇性沉積。化學前驅物可以相對於另一表面選擇性與一個表面反應(金屬或介電)。可調節製程參數(例如壓力、基材溫度、前驅物分壓、及/或氣流),以調節特定表面反應的化學動力條件。另一種可能的方案涉及表面前處理,能夠使用該表面前處理使目標表面對進入的膜沉積前驅物呈活化或去活化。
本領域中一直需要去活化或阻擋導電表面的處理方法。
本案揭露內容的一或多個實施例關於選擇性沉積阻擋層的方法。該方法包括,將基材暴露至羧酸,以越過第二表面而在第一表面上選擇性形成阻擋層且形成阻擋的第一表面,該基材包括導電材料與介電材料,該導電材料具有該第一表面,該介電材料具有該第二表面。該羧酸包括至少一種具有通式RCOOH的化合物,其中R選自C4至C20烷基、全氟烷基、烯基、或炔基基團。
本案揭露內容之額外實施例關於一種選擇性沉積阻擋層之方法,該方法包括:將基材暴露至醯肼,以越過第二表面而在第一表面上選擇性形成阻擋層且形成阻擋的第一表面,該基材包括導電材料與介電材料,該導電材料具有該第一表面,該介電材料具有該第二表面。該醯肼包括至少一種具有通式RC(O)NHNR’2
的化合物,其中R選自C4至C20烷基、全氟烷基、烯基、或炔基基團,且每一R’獨立地選自H或C1至C4烷基,或是能夠接合在一起而形成包括2至5個碳原子的環。
本案揭露內容之額外實施例關於一種選擇性沉積阻擋層之方法,該方法包括:將基材暴露至氣態烷基膦酸(alkyl phosphonic acid),以越過第二表面而在第一表面上選擇性形成阻擋層且形成阻擋的第一表面,該基材包括導電材料與介電材料,該導電材料具有該第一表面,該介電材料具有該第二表面。該烷基膦酸包括至少一種具有通式RP(O)(OR”)2
的化合物,其中R選自C4至C20烷基、全氟烷基、烯基、或炔基基團,且每一R”獨立地選自H、C1至C12烷基或芳基。
本案揭露內容的實施例提供用於在導電表面上選擇性沉積阻擋層的方法。本案揭露內容的實施例確認用於沉積阻擋層的多種方法,該等方法可以單獨使用或結合使用。
如本文所用,「基材表面」是上面執行膜處理的基材之任何部分或基材上形成的材料表面的部分。例如,可在上面執行處理的基材表面包括材料諸如:矽、氧化矽、氮化矽、摻雜矽、鍺、砷化鎵、玻璃、藍寶石,及任何其他材料,諸如金屬、金屬氮化物、金屬合金、及其他導電材料,這視應用而定。基材包括但不限於半導體晶圓。可將基材暴露於前處理製程,以研磨、蝕刻、還原、氧化、羥基化、退火、UV固化、電子束固化和/或烘烤基材表面。除了在基材本身的表面上直接執行膜處理之外,在本案揭露內容中,所揭露的任何膜處理步驟也可以在基材上所形成的下層(underlayer)上進行,如下文更詳細揭露,且術語「基材表面」旨在包括上下文所指出的此下層。因此,舉例而言,在已經將膜/層或部分膜/層沉積到基材表面上的情況中,新沉積的膜/層的暴露表面變成基材表面。基材可具有各種尺寸,例如直徑為200mm或300mm的晶圓,以及矩形或方形嵌板(pane)。在一些實施例中,基材包括剛性、分立的材料。
本案揭露內容的實施例有利地提供用於越過介電表面而在導電表面上選擇性形成阻擋層的方法。一些實施例有利地提供了進一步的方法以選擇性地在介電表面上沉積層。
如在本說明書和所附申請專利範圍中所使用的,詞彙「導電表面」或「介電表面」是意味,表面與有有所述之特性的材料相關。因此,導電表面是導電材料的表面,但是沒有關於表面本身導電度的陳述。類似地,介電表面是介電材料的表面。
如在本說明書和所附申請專利範圍中所使用的,術語「越過另一表面而在一個表面上選擇性沉積膜」及類似術語等意味,第一量的膜沉積在第一表面上且第二量的膜沉積在第二表面上,其中該膜的該第二量小於該膜的該第一量,或者是沒有膜沉積在第二表面上。在這方面使用的術語「越過(over)」並不意味著一個表面在另一個表面上的物理走向,而是化學反應與一個表面相對於另一個表面的熱力學或動力學性質的關係。例如,將鈷膜越過介電表面而選擇性沉積至銅表面上是意味,鈷膜沉積在銅表面上,並且較少或沒有鈷膜沉積在該介電表面上;或者是意味,相對於在介電表面上形成鈷膜,銅表面上鈷膜的形成在熱力學或動力學上是有利的。在一些實施例中,「選擇性」是指,主體材料在選擇的表面上以一速率形成,該速率大於或等於在非選的表面上的形成速率的約10倍、15倍、20倍、25倍、30倍、35倍、40倍、45倍或50倍。換言之,主體材料相對於非選的表面的選擇性大於或等於約10:1、15:1、20:1、25:1、30:1、35:1、40:1、45:1、或50:1。
本案揭露內容的一些實施例併有一般稱作自組裝單層(SAM)的阻擋層。自組裝單層(SAM)由吸附在表面上的自發式組裝的有機分子的有序排列所組成。這些分子一般包含一或多個對基材具有親和力的部分(頭部基團)和相對長、惰性、線性的碳氫化合物部分(尾部基團)。
在這種情況下,SAM的形成是以下述方式發生:透過在表面快速吸附分子頭基團,且藉由凡得瓦交互作用分子尾部基團彼此緩慢聯結。挑選SAM前驅物以使得在沉積期間頭部基團選擇性與待阻擋的基材之材料反應。然後執行沉積,且SAM能夠透過熱分解(伴隨任何副產物的脫附)或與整合相容的灰化製程而移除。
本案揭露內容的一或多個實施例涉及越過基材的第二表面而在基材的第一表面上選擇性沉積阻擋層的方法。第一表面是導電材料的表面。第二表面是介電材料的表面。
基材的導電材料可為任何適合的材料。適合的導電材料包括但不限於金屬、金屬氮化物、一些金屬氧化物、金屬合金、上述材料之組合,及其他導電材料。在一些實施例中,導電材料包括鉻、錳、鐵、銅、鎳、鈷、鎢、釕、氧化鉭、氮化鉭、氧化鈦、或氮化鈦中的一或多者。在一些實施例中,導電材料基本上由鉻、錳、鐵、銅、鎳、鈷、鎢、釕、氧化鉭、氮化鉭、氧化鈦、或氮化鈦組成。如在本說明書和所附申請專利範圍中所使用的,術語「基本上由……組成」是指,在原子基礎上,該材料大於或等於所述材料的約95%、98%或99%。
如在本說明書和所附申請專利範圍中所使用的,術語「氧化物」或類似術語意味,該材料含有指定的元素。該術語不應解釋為暗示特定的元素比例。因此,「氧化物」或類似物可包括化學當量比的元素或非化學當量比的元素。
基材的介電材料可以是任何適合的材料。適合的介電材料包括但不限於氧化矽(例如SiO2
)、氮化矽、碳化矽、及上述材料之組合(例如SiCON)。在一些實施例中,介電材料基本上由二氧化矽(SiO2
)組成。在一些實施例中,該層包括氮化矽。在一些實施例中,該層基本上由氮化矽組成。
參照該圖,所歸納的方法100開始於基材105,基材105包括具有第一表面112的導電材料110和具有第二表面122的介電材料120。該基材105暴露至阻擋化合物(未示出) ,以在第一表面112上越過第二表面122選擇性形成阻擋層130,且形成阻擋的第一表面132。
在一些實施例中,方法100繼續,在第二表面122上而越過阻擋的第一表面132選擇性沉積層125。在一些實施例中,該層125是介電材料。在一些實施例中,該層包括氮化矽。
能夠透過任何適合的製程執行氮化矽的沉積。適合的製程可包括,將基材暴露於鹵化矽和氨。適合的鹵化矽包括但不限於:二氯矽烷(DCS)、三氯矽烷(TCS)、四氯矽烷(SiCl4
)、四溴矽烷(SiBr4
)、四碘矽烷(SiI4
)、和六氯乙矽烷(HCDS)。
在一些實施例中,以一厚度沉積氮化矽層,該厚度在約10Å至約50Å的範圍內,或在約12Å至約35Å的範圍內,或者在約15Å至約20Å的範圍內。在一些實施例中,重覆形成阻擋層和沉積該層,直到該層的厚度大於或等於約50Å,大於或等於約75Å,大於或等於約100Å,或大於或等於約150Å。
在一些實施例中,方法100繼續,移除阻擋層130以暴露第一表面112。在一些實施例中,使用選擇性蝕刻製程移除阻擋層130。已知基於氧及基於氟的蝕刻會蝕刻類似於本文揭露的阻擋層的基於碳的膜。
一個非限制性範例是,藉由基於氧的遠端電漿移除該阻擋層。在此範例中,基於氧的遠端電漿蝕刻移除阻擋層也氧化第一表面。為了恢復原始的表面組成,能夠還原表面。適合的還原製程包括但不限於,使用包含氫或氨的電漿和包含氫或氨的熱退火。在一些實施例中,能夠獨立地遠端或內部生成(及導電耦合或感應耦合)氧電漿、氟電漿、氫電漿、和氨電漿。
儘管未在圖中顯示,但本案揭露內容的方法可進一步包括,在將基材暴露至阻擋化合物之前清潔第一表面。在一些實施例中,清潔第一表面包括,將第一表面暴露於包含乙酸和乙醇的溶液。在一些實施例中,溶液是10%的乙酸之乙醇溶液(即10%v/v的在乙醇中的乙酸,或10%w/w的在乙醇中的乙酸)。在一些實施例中,清潔第一表面包括,將第一表面暴露於氫電漿(H2
)。在一些實施例中,氫電漿是導電耦合電漿(CCP)。在一些實施例中,氫電漿是感應耦合電漿(ICP)。不受理論束縛,相信清潔該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)。相信這些封端是阻擋化合物的反應位點。
在一些實施例中,阻擋化合物包含羧酸。在一些實施例中,該方法包括,將基材暴露至羧酸,以越過第二表面而在第一表面上選擇性形成阻擋層且形成阻擋的第一表面,該基材包括導電材料與介電材料,該導電材料具有該第一表面,該介電材料具有該第二表面。
在一些實施例中,該羧酸包含至少一種具有通式為RCOOH的化合物,其中R選自C4-C20之烷基、全氟烷基、烯基或炔基。如以此方式所用,字母「C」後隨數字(例如「C4」)意味,取代基包含指定數目的碳原子(例如,C4包含四個碳原子)。一些實施例中,C4-C20烷基基本上由C-C單鍵和C-H鍵組成。在一些實施例中,C4-C20全氟烷基基本上由C-C單鍵和C-F鍵組成。在一些實施例中,C4-C20烯基基本上由C-C單鍵、至少一個C-C雙鍵和C-H鍵組成。在一些實施例中,C4-C20炔基基本上由C-C單鍵、至少一個C-C三鍵、和C-H鍵組成。在一些實施例中,C4-C20基團包括一個或多個鹵素原子及/或其他疏水部分。在一些實施例中,C4-C20基團可以是直鏈基團(例如正丁基)、支鏈(branched chain)基團(例如第三丁基)、或環狀基團(例如環己基)。在一些實施例中,烷基、全氟烷基、烯基、或炔基是直鏈。在一些實施例中,烷基、全氟烷基、烯基、或炔基是支鏈。
在一些實施例中,羧酸包括庚酸、辛酸、十一烷酸或十八烷酸。在一些實施例中,羧酸基本上由十一烷酸組成。
在一些實施例中,長鏈羧酸可用作阻擋分子且與金屬表面(具有或不具有原生氧化物)反應。在一些實施例中,對羧酸的暴露是在溶液中執行。在一些實施例中,對羧酸的暴露在氣相中執行。
在一些實施例中,小且中間鏈長(<C12)的羧酸以氣相遞送。在一些實施例中,長烷基鏈(≥C12)的羧酸可用作溶液相中的阻擋化合物。
不受理論束縛,金屬(包括但不限於Cu、Co、W、Ru、TiN)通常是親氧的並且優先與羧酸結合而在SiO2
或SiN表面上成為RCOO-M。
在一些實施例中,越過第一阻擋表面而在第二表面上選擇性地沉積氮化矽層。在一些實施例中,氮化矽層的厚度在約30埃至約40埃的範圍內。在一些實施例中,以大於或等於約30:1的選擇性沉積氮化矽層。在一些實施例中,將基材維持在小於或等於約200o
C的溫度。
在一些實施例中,阻擋化合物包含醯肼。在一些實施例中,該方法包括,將基材暴露至醯肼,以越過第二表面而在第一表面上選擇性形成阻擋層且形成阻擋的第一表面,該基材包括導電材料與介電材料,該導電材料具有該第一表面,該介電材料具有該第二表面。
在一些實施例中,該醯肼包含至少一種具有通式為RC(O)NHNR’2
的化合物,其中R選自C4-C20烷基、全氟烷基、烯基或炔基,並且每個R’獨立地選自H或C1-C4烷基,或可以連接在一起形成包含2至5個碳原子的環。
不受理論束縛,預期醯肼形成熱穩定的金屬錯合物。鈷-醯肼錯合物如雙(第三丁基碳醯基肼基)鈷,相對地較不易揮發並且至高達250o
C仍熱穩定。相信使用較長鏈的烷基能夠進一步降低蒸氣壓並導致導電表面的阻擋。
在一些實施例中,R是第三丁基。在一些實施例中,每個R’是氫。在一些實施例中,每個R’是甲基。
在一些實施例中,阻擋化合物包含氣態烷基膦酸。在一些實施例中,該方法包括,將基材暴露至氣態烷基膦酸,以越過第二表面而在第一表面上選擇性形成阻擋層且形成阻擋的第一表面,該基材包括導電材料與介電材料,該導電材料具有該第一表面,該介電材料具有該第二表面。如本說明書和所附申請專利範圍中所用,描述詞「氣態」是指烷基膦酸以氣相供應。
在一些實施例中,烷基膦酸包含至少一種具有通式為RP(O)(OR”)2
的化合物,其中R選自C4-C20烷基、全氟烷基、烯基或炔基,並且每個R”獨立地選自H、C1-C12烷基、或芳基。
在一些實施例中,R”獨立地為C1-C12烷基或芳基。不受理論束縛,這些實施例的烷基膦酸中氫鍵的缺乏增加了這些阻擋化合物的蒸氣壓。
在一些實施例中,烷基膦酸包含十八烷基膦酸。在一些實施例中,烷基膦酸包括全氟辛基膦酸。
在一些實施例中,烷基膦酸透過二鹵代烷基膦酸(dihaloalkylphosphonic acid)與醇的反應原位產生。在一些實施例中,二鹵代烷基膦酸包含至少一種具有通式RP(O)X2
的化合物,其中每個X是獨立選擇的鹵素。在一些實施例中,醇包含至少一種具有通式R”OH的化合物。
不受理論束縛,二鹵代烷基膦酸和醇各自比它們產生的烷基膦酸更易揮發。因此,可以在氣相中輸送二鹵代烷基膦酸和醇,使得它們反應形成原本會難以揮發的烷基膦酸。
在一些實施例中,R”是H。不受理論束縛,使用水作為這些實施例的醇原位提供烷基膦酸,否則原本烷基膦酸會由於氫鍵而具有低揮發性。
儘管已經參考特定實施例描述了本案揭露內容,但應了解,這些實施例僅為說明本案揭露內容之原理及應用。發明所屬技術領域中具有通常知識者明瞭,在不背離本案揭露內容的精神與範疇的情況下,可對本案揭露內容的方法和設備進行各種修改和變化。因此,希望本案揭露內容包括在所附申請專利範圍之範疇內的修改例與變化例及其等效例。
100‧‧‧方法
105‧‧‧基材
110‧‧‧導電材料
112‧‧‧第一表面
120‧‧‧介電材料
122‧‧‧第二表面
125‧‧‧層
130‧‧‧阻擋層
132‧‧‧阻擋的第一表面
透過參考實施例(其中一些在附圖中說明),可以獲得本文簡要總結的本案公開內容之更具體的描述,如此能夠詳細地了解本案揭露內容的上述特徵。然而,應注意,附圖僅說明本案揭露內容的典型實施例,因此不應認為是對本案揭露內容之範疇的限制,因為本案揭露內容可容許其他等效的實施例。
圖1顯示根據本案揭露內容的一或多個實施例的處理方法。
在附圖中,類似的部件及/或特徵可具有相同的元件符號。另外,相同類型的各種部件可透過使元件符號後加上虛線及第二符號而區分,該第二符號區分類似部件。若在說明書中僅使用第一元件符號,則該敘述適用於具有相同第一元件符號的任何一個類似部件,無論第二元件符號為何。
國內寄存資訊 (請依寄存機構、日期、號碼順序註記)
無
國外寄存資訊 (請依寄存國家、機構、日期、號碼順序註記)
無
100‧‧‧方法
105‧‧‧基材
110‧‧‧導電材料
112‧‧‧第一表面
120‧‧‧介電材料
122‧‧‧第二表面
125‧‧‧層
130‧‧‧阻擋層
132‧‧‧阻擋的第一表面
Claims (8)
- 一種選擇性沉積阻擋層之方法,該方法包括:將一基材暴露至一氣態烷基膦酸(alkyl phosphonic acid),以越過一第二表面而在一第一表面上選擇性形成該阻擋層且形成一阻擋的第一表面,該基材包括一導電材料與一介電材料,該導電材料具有該第一表面,該介電材料具有該第二表面,該烷基膦酸包括至少一種具有通式RP(O)(OR”)2的化合物,其中R選自C4至C20烷基基團、C4至C20全氟烷基基團、C4至C20烯基基團、或C4至C20炔基基團,且每一R”獨立地選自C1至C12烷基或芳基,其中該C4至C20烷基基團、該C4至C20全氟烷基基團、該C4至C20烯基基團、及該C4至C20炔基基團為直鏈(straight chain)、支鏈(branched)、或環狀(cyclic)。
- 如請求項1所述之方法,其中該導電材料包括金屬、金屬合金、金屬氧化物、金屬氮化物、或上述材料之組合。
- 如請求項2所述之方法,其中該導電材料包括下述一或多者:鉻、錳、鐵、銅、鎳、鈷、鎢、釕、氧化鉭、氮化鉭、氧化鈦或氮化鈦。
- 如請求項1所述之方法,進一步包括:越過 該阻擋的第一表面而在該第二表面上選擇性沉積一層。
- 如請求項4所述之方法,其中該層包括一介電材料。
- 如請求項1所述之方法,其中將該基材暴露至該氣態烷基膦酸包括:使二鹵代烷基膦酸(dihaloalkylphosphonic acid)與醇反應,而形成該烷基膦酸,該二鹵代烷基膦酸包括至少一種具有通式RP(O)X2的化合物,其中每一X是獨立地選擇的鹵素,該醇包括至少一種具有通式R”OH的化合物,其中R及R”如請求項1中所界定。
- 如請求項6所述之方法,進一步包括:越過該阻擋的第一表面而在該第二表面上選擇性沉積一層。
- 如請求項7所述之方法,其中該層包括一介電材料。
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