TWI576459B - 沉積錳與氮化錳的方法 - Google Patents
沉積錳與氮化錳的方法 Download PDFInfo
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- TWI576459B TWI576459B TW102113098A TW102113098A TWI576459B TW I576459 B TWI576459 B TW I576459B TW 102113098 A TW102113098 A TW 102113098A TW 102113098 A TW102113098 A TW 102113098A TW I576459 B TWI576459 B TW I576459B
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- Prior art keywords
- manganese
- substrate
- precursor
- reactant
- layer
- Prior art date
Links
- 239000011572 manganese Substances 0.000 title claims description 127
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims description 117
- 229910052748 manganese Inorganic materials 0.000 title claims description 114
- 238000000034 method Methods 0.000 title claims description 57
- 238000000151 deposition Methods 0.000 title claims description 35
- -1 manganese nitrides Chemical class 0.000 title claims description 7
- 239000000758 substrate Substances 0.000 claims description 84
- 239000002243 precursor Substances 0.000 claims description 61
- 239000000376 reactant Substances 0.000 claims description 41
- 239000002019 doping agent Substances 0.000 claims description 40
- 150000001336 alkenes Chemical class 0.000 claims description 31
- 239000004020 conductor Substances 0.000 claims description 22
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 18
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 16
- 125000003118 aryl group Chemical group 0.000 claims description 16
- 150000002902 organometallic compounds Chemical class 0.000 claims description 16
- 239000001257 hydrogen Substances 0.000 claims description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims description 15
- 238000004377 microelectronic Methods 0.000 claims description 14
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 150000002431 hydrogen Chemical group 0.000 claims description 10
- 229910021529 ammonia Inorganic materials 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- 229910052719 titanium Inorganic materials 0.000 claims description 7
- 229910052804 chromium Inorganic materials 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- 229910052758 niobium Inorganic materials 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 229910052720 vanadium Inorganic materials 0.000 claims description 5
- 229910052734 helium Inorganic materials 0.000 claims description 4
- 230000007704 transition Effects 0.000 claims description 4
- OAVRWNUUOUXDFH-UHFFFAOYSA-H 2-hydroxypropane-1,2,3-tricarboxylate;manganese(2+) Chemical compound [Mn+2].[Mn+2].[Mn+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O OAVRWNUUOUXDFH-UHFFFAOYSA-H 0.000 claims description 3
- 229910017840 NH 3 Inorganic materials 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 229940097206 manganese citrate Drugs 0.000 claims description 3
- 235000014872 manganese citrate Nutrition 0.000 claims description 3
- 239000011564 manganese citrate Substances 0.000 claims description 3
- 238000009832 plasma treatment Methods 0.000 claims description 3
- 125000002534 ethynyl group Chemical class [H]C#C* 0.000 claims 8
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims 4
- 150000002736 metal compounds Chemical class 0.000 claims 1
- 239000010410 layer Substances 0.000 description 137
- 239000010408 film Substances 0.000 description 62
- 230000004888 barrier function Effects 0.000 description 43
- 239000007789 gas Substances 0.000 description 37
- 239000010949 copper Substances 0.000 description 25
- 150000001345 alkine derivatives Chemical class 0.000 description 24
- 238000000231 atomic layer deposition Methods 0.000 description 24
- 229910052802 copper Inorganic materials 0.000 description 23
- 239000000463 material Substances 0.000 description 23
- 210000002381 plasma Anatomy 0.000 description 23
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 21
- 230000008021 deposition Effects 0.000 description 20
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 20
- 230000008569 process Effects 0.000 description 18
- 238000012545 processing Methods 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- RRZKHZBOZDIQJG-UHFFFAOYSA-N azane;manganese Chemical compound N.[Mn] RRZKHZBOZDIQJG-UHFFFAOYSA-N 0.000 description 10
- 238000005229 chemical vapour deposition Methods 0.000 description 10
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 10
- 229910052707 ruthenium Inorganic materials 0.000 description 9
- 238000009792 diffusion process Methods 0.000 description 7
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 238000005137 deposition process Methods 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 229910052715 tantalum Inorganic materials 0.000 description 6
- 239000010936 titanium Substances 0.000 description 6
- 229910000881 Cu alloy Inorganic materials 0.000 description 5
- 238000004891 communication Methods 0.000 description 5
- 239000011231 conductive filler Substances 0.000 description 5
- 239000012530 fluid Substances 0.000 description 5
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 5
- 239000010409 thin film Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229910052732 germanium Inorganic materials 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 150000004767 nitrides Chemical class 0.000 description 4
- 238000010926 purge Methods 0.000 description 4
- 239000012159 carrier gas Substances 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 3
- 235000012431 wafers Nutrition 0.000 description 3
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 description 2
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 229910000420 cerium oxide Inorganic materials 0.000 description 2
- 239000003989 dielectric material Substances 0.000 description 2
- ASTZLJPZXLHCSM-UHFFFAOYSA-N dioxido(oxo)silane;manganese(2+) Chemical compound [Mn+2].[O-][Si]([O-])=O ASTZLJPZXLHCSM-UHFFFAOYSA-N 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 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
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 2
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 2
- 229920005591 polysilicon Polymers 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- VZXTWGWHSMCWGA-UHFFFAOYSA-N 1,3,5-triazine-2,4-diamine Chemical compound NC1=NC=NC(N)=N1 VZXTWGWHSMCWGA-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- 229910017566 Cu-Mn Inorganic materials 0.000 description 1
- 229910017871 Cu—Mn Inorganic materials 0.000 description 1
- MHZGKXUYDGKKIU-UHFFFAOYSA-N Decylamine Chemical compound CCCCCCCCCCN MHZGKXUYDGKKIU-UHFFFAOYSA-N 0.000 description 1
- 229910002601 GaN Inorganic materials 0.000 description 1
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 description 1
- GPXJNWSHGFTCBW-UHFFFAOYSA-N Indium phosphide Chemical compound [In]#P GPXJNWSHGFTCBW-UHFFFAOYSA-N 0.000 description 1
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical group [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 1
- 229910018648 Mn—N Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 1
- 125000005257 alkyl acyl group Chemical group 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- WYEMLYFITZORAB-UHFFFAOYSA-N boscalid Chemical compound C1=CC(Cl)=CC=C1C1=CC=CC=C1NC(=O)C1=CC=CN=C1Cl WYEMLYFITZORAB-UHFFFAOYSA-N 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- SCCCLDWUZODEKG-UHFFFAOYSA-N germanide Chemical compound [GeH3-] SCCCLDWUZODEKG-UHFFFAOYSA-N 0.000 description 1
- 229940119177 germanium dioxide Drugs 0.000 description 1
- GPMBECJIPQBCKI-UHFFFAOYSA-N germanium telluride Chemical compound [Te]=[Ge]=[Te] GPMBECJIPQBCKI-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- MMIPFLVOWGHZQD-UHFFFAOYSA-N manganese(3+) Chemical compound [Mn+3] MMIPFLVOWGHZQD-UHFFFAOYSA-N 0.000 description 1
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(iii) oxide Chemical compound O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 239000010980 sapphire Substances 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000010421 standard material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002123 temporal effect Effects 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 238000005019 vapor deposition process Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/70—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
- H01L21/76838—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 conductors
- H01L21/76841—Barrier, adhesion or liner layers
- H01L21/76843—Barrier, adhesion or liner layers formed in openings in a dielectric
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/34—Nitrides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
- H01L21/283—Deposition of conductive or insulating materials for electrodes conducting electric current
- H01L21/285—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation
- H01L21/28506—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers
- H01L21/28512—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers on semiconductor bodies comprising elements of Group IV of the Periodic Table
- H01L21/28556—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers on semiconductor bodies comprising elements of Group IV of the Periodic Table by chemical means, e.g. CVD, LPCVD, PECVD, laser CVD
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
- H01L21/283—Deposition of conductive or insulating materials for electrodes conducting electric current
- H01L21/285—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation
- H01L21/28506—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers
- H01L21/28512—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers on semiconductor bodies comprising elements of Group IV of the Periodic Table
- H01L21/28556—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers on semiconductor bodies comprising elements of Group IV of the Periodic Table by chemical means, e.g. CVD, LPCVD, PECVD, laser CVD
- H01L21/28562—Selective deposition
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- H—ELECTRICITY
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- 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
- H01L21/76838—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 conductors
- H01L21/76841—Barrier, adhesion or liner layers
- H01L21/76843—Barrier, adhesion or liner layers formed in openings in a dielectric
- H01L21/76846—Layer combinations
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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
- H01L21/76838—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 conductors
- H01L21/76841—Barrier, adhesion or liner layers
- H01L21/76853—Barrier, adhesion or liner layers characterized by particular after-treatment steps
- H01L21/76855—After-treatment introducing at least one additional element into the layer
- H01L21/76856—After-treatment introducing at least one additional element into the layer by treatment in plasmas or gaseous environments, e.g. nitriding a refractory metal liner
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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
- H01L21/76838—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 conductors
- H01L21/76841—Barrier, adhesion or liner layers
- H01L21/76853—Barrier, adhesion or liner layers characterized by particular after-treatment steps
- H01L21/76861—Post-treatment or after-treatment not introducing additional chemical elements into the layer
- H01L21/76862—Bombardment with particles, e.g. treatment in noble gas plasmas; UV irradiation
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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
- H01L21/76838—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 conductors
- H01L21/76841—Barrier, adhesion or liner layers
- H01L21/76853—Barrier, adhesion or liner layers characterized by particular after-treatment steps
- H01L21/76861—Post-treatment or after-treatment not introducing additional chemical elements into the layer
- H01L21/76864—Thermal treatment
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/52—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames
- H01L23/522—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames including external interconnections consisting of a multilayer structure of conductive and insulating layers inseparably formed on the semiconductor body
- H01L23/532—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames including external interconnections consisting of a multilayer structure of conductive and insulating layers inseparably formed on the semiconductor body characterised by the materials
- H01L23/53204—Conductive materials
- H01L23/53209—Conductive materials based on metals, e.g. alloys, metal silicides
- H01L23/53228—Conductive materials based on metals, e.g. alloys, metal silicides the principal metal being copper
- H01L23/53238—Additional layers associated with copper layers, e.g. adhesion, barrier, cladding layers
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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
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- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
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Description
本發明的實施例大體上係關於半導體裝置中的阻障層及形成此類阻障層的方法。更特定而言,本發明的實施例係關於包含錳、氮化錳(MnNx)、矽酸錳及選擇的摻雜劑的薄膜。
微電子裝置(諸如半導體或積體電路)可包括數百萬的電子電路裝置,諸如電晶體、電容器等等。為了進一步增加積體電路上裝置的密度,希望有甚至更小的特徵尺寸。為了實現此等較小的特徵尺寸,必須減少導電接線、通孔及互連線、閘極等等的尺寸。多水平互連結構的可靠形成對於增加電路密度及品質亦為必需的。製造技術的發展已使得能夠使用銅用於導電接線、互連、通孔及其他結構。然而,隨著特徵尺寸的減小及銅用於互連的使用增加,互連結構中的電子遷移成為待克服的較大障礙。
氮化鉭(TaN)為薄膜厚度大於10埃的銅阻障,其中薄膜為連續的。然而,由於Ta原子直徑約為4埃,故厚度約為5埃的TaN薄膜不是連續的。對於需要更薄的TaN的較小
節點,TaN本身可為不連續的薄膜,由此限制TaN的銅阻障性質。當前的方法包括TaN層的頂部上的Ta層,該Ta層用作銅的潤濕層及提供阻障薄膜的連續性。然而,對於較小的節點(小於32 nm),此方法導致較大的線路電阻及由此不為適當的解決方法。
物理氣相沉積(physical vapor deposited;PVD)的氮化鉭(TaN)為用於銅互連中的擴散阻障的標準材料。由於銅與TaN的不良黏附,故鉭襯墊亦用於增強互連結構的耐久性。隨著銅互連的尺寸正減少至低於20 nm,PVD TaN阻障的非保形性質加上Ta襯墊已引起諸如銅間隙填充空洞及高線路電阻的問題。原子層沉積(atomic layer deposition;ALD)TaN正用作具有較好的保形性的先進技術;然而,ALD TaN的薄膜品質仍然需要明顯改良。
因此,在本發明所屬的技術領域存在對於可作為有效銅阻障之薄層的需求。
本發明的一或更多個實施例針對形成含錳薄膜的方法。提供基板,該基板暴露於第一前驅物及反應物。第一前驅物包含含錳有機金屬化合物以沉積含錳薄膜。含錳有機金屬化合物具有以下化學式:
其中每一A為獨立地選自碳或矽,且每一R為獨立地選自氫、甲基、經取代烷類或非經取代烷類、支鏈烷類或非支鏈烷類、經取代烯類或非經取代烯類、支鏈烯類或非支鏈烯類、經取代炔類或非經取代炔類、支鏈炔類或非支鏈炔類或經取代芳香族或非經取代芳香族。
本發明的一些實施例針對形成含錳薄膜的方法。提供基板,該基板包含位於該基板上的介電層,該介電層具有溝槽,該溝槽具有開口、側壁及底部。基板暴露於第一前驅物及反應物。第一前驅物包含含錳有機金屬化合物以在溝槽的側壁及/或底部的至少一部分上沉積含錳薄膜。含錳有機金屬化合物具有以下化學式:
其中每一A為獨立地選自碳或矽,且每一R為獨立地選自氫、甲基、經取代烷類或非經取代烷類、支鏈烷類或非支鏈烷類、經取代烯類或非經取代烯類、支鏈烯類或非支鏈烯類、經取代炔類或非經取代炔類、支鏈炔類或非支鏈炔類或經取代芳香族或非經取代芳香族。
在一些實施例中,該方法進一步包含以下步驟:在含錳薄膜的上方沉積包含銅的導電材料。
在一或更多個實施例中,含錳薄膜進一步包含一或更多種摻雜劑,該一或更多種摻雜劑係選自Co、Mn、Ru、
Ta、Al、Mg、Cr、Nb、Ti及V。在一些實施例中,藉由暴露基板至第二前驅物及反應物來包括摻雜劑,該第二前驅物包含含有摻雜劑元素的化合物。
在一或更多個實施例中,基板實質上同時暴露於第一前驅物及反應物。在一些實施例中,基板依序暴露於第一前驅物及反應物。
在一些實施例中,每一A為氮。在一或更多個實施例中,每一R基團為甲基。在一或更多個實施例中,含錳有機金屬化合物包含錳雙[雙(三甲基矽烷基)醯胺]。
在一些實施例中,反應物為氨及氫中的一或更多者。在一或更多個實施例中,反應物包含氨。
在一些實施例中,含錳薄膜包含MnNx,其中x在約0.1至約3的範圍內。一些實施例進一步包含以下步驟:處理MnNx薄膜以產生矽酸錳。在一些實施例中,矽酸錳形成於介電層上。
一些實施例進一步包含以下步驟:暴露基板至不同於第一前驅物的第二前驅物及可選擇地暴露至不同於反應物的第二反應物。
在一或更多個實施例中,基板包含位於基板上的介電層,該介電層具有溝槽,該溝槽具有開口、側壁及底部,且含錳薄膜沉積在溝槽的側壁及底部中的一或更多者的至少一部分上。在一些實施例中,含錳薄膜選擇性地沉積在介電層或基板中的一者上,該介電層或基板中的一者在該介電層及基板中的另一者的上方。
在一或更多個實施例中,矽酸錳形成在介電層上。在一些實施例中,含錳薄膜以小於約2 nm的厚度連續。
在一些實施例中,含錳薄膜中實質上不存在氧化錳。
本發明的額外實施例針對在微電子裝置中形成互連的方法。提供基板,該基板包含位於該基板上的介電層。介電層具有開口,該開口允許導電至下層。基板暴露於第一前驅物及反應物。第一前驅物包含含錳有機金屬化合物以在至少一部分介電層上沉積含錳薄膜。含錳有機金屬化合物具有以下化學式:
其中每一A為獨立地選自碳或矽,且每一R為獨立地選自氫、甲基、經取代烷類或非經取代烷類、支鏈烷類或非支鏈烷類、經取代烯類或非經取代烯類、支鏈烯類或非支鏈烯類、經取代炔類或非經取代炔類、支鏈炔類或非支鏈炔類或經取代芳香族或非經取代芳香族。導電材料沉積在含錳薄膜上方。導電材料可選擇地可位於開口上方,該開口允許導電至下層。
本發明的額外實施例針對在微電子裝置中形成互連的方法。提供包含介電層的基板。介電層具有溝槽,該溝槽具有開口、側壁及底部。基板暴露於第一前驅物及反應物。第一前驅物包含含錳有機金屬化合物以在溝槽的側壁及/或底部的至少一部分上沉積含錳薄膜。含錳有機金屬化合物具有
以下化學式:
其中每一A為獨立地選自碳或矽,且每一R為獨立地選自氫、甲基、經取代烷類或非經取代烷類、支鏈烷類或非支鏈烷類、經取代烯類或非經取代烯類、支鏈烯類或非支鏈烯類、經取代炔類或非經取代炔類、支鏈炔類或非支鏈炔類或經取代芳香族或非經取代芳香族。包含Cu的導電材料沉積至有襯墊的溝槽中。
在一些實施例中,含錳薄膜包含在介電質過渡至MnNx的表面處的矽酸錳。在一或更多個實施例中,薄膜包含矽酸錳且矽酸錳直接沉積至基板上。
一或更多個實施例進一步包含以下步驟:在沉積導電材料之前暴露第一層至電漿處理。在一些實施例中,電漿包含He、Ar、NH3、H2及N2中的一或更多者。
本發明的進一步實施例針對在微電子裝置中形成互連的方法。提供包含介電質的基板。介電層具有溝槽,該溝槽具有開口、側壁及底部。基板依序暴露於第一前驅物及反應物,第一前驅物包含具有以下化學式的含錳有機金屬化合物:
其中每一A為獨立地選自碳或矽,且每一R為獨立地選自氫、甲基、經取代烷類或非經取代烷類、支鏈烷類或非支鏈烷類、經取代烯類或非經取代烯類、支鏈烯類或非支鏈烯類、經取代炔類或非經取代炔類、支鏈炔類或非支鏈炔類或經取代芳香族或非經取代芳香族,以在溝槽的側壁及/或底部的至少一部分上沉積含錳薄膜。包含Cu的導電材料沉積至有襯墊的溝槽中。
100‧‧‧微電子裝置
105‧‧‧基板
110‧‧‧介電層
115‧‧‧側壁
120‧‧‧溝槽底部
130‧‧‧阻障層
140‧‧‧導電填充材料
150‧‧‧溝槽
160‧‧‧開口
200‧‧‧微電子裝置
205‧‧‧基板
210‧‧‧介電層
215‧‧‧側壁
220‧‧‧溝槽底部
230‧‧‧第一層
235‧‧‧第二層
240‧‧‧導電填充材料
因此,可詳細理解本發明的上述特徵結構的方式,即上文簡要概述的本發明的更特定描述可參照實施例進行,一些實施例圖示於隨附圖式中。然而,應注意,隨附圖式僅圖示本發明的典型實施例,且因此不欲視為本發明範疇的限制,因為本發明可允許其他同等有效的實施例。
第1A圖及第1B圖圖示根據本發明的一或更多個實施例的沉積阻障層及導電填充材料之前及之後的介電層;及第2圖圖示根據本發明的一或更多個實施例的具有第一層、第二層及導電填充材料的介電層。
描述本發明的數個示例性實施例之前,將理解,本發明不限於以下描述中闡明的構造或製程步驟的細節。本發
明能夠具有其他實施例及能夠以各種方式實作或執行。
本發明的實施例係關於由有機金屬前驅物產生錳(Mn)或氮化錳(MnNx)。沉積方法可為原子層沉積(ALD)或化學氣相沉積(CVD)。有機金屬前驅物可包括錳甲矽烷基醯胺基複合物。沉積的錳或MnNx薄膜可用作後端製程銅互連中替代的擴散阻障以替換當前使用的PVD TaN或ALD TaN。沉積方法可與ALD TaN沉積整合以產生摻雜錳的TaN或摻雜有MnNx的鉭。
錳或MnNx為建議用於該等應用的新材料。錳可與介電下層反應以形成矽酸錳作為阻障。在不受限於任何特定的操作原理的情況下,咸信MnNx不僅是擴散阻障而且促進銅及介電質之間的黏附。
存在高品質及高純度的MnNx或錳的CVD/ALD薄膜的少數實例。一些前驅物具有含氧配合基,此舉導致MnOx的形成。在銅表面上形成的氧化錳難以分離開且將增加通孔電阻。一些前驅物具有極低的蒸氣壓力及反應速率,此對腔室設計形成挑戰及導致ALD沉積期間的不良薄膜形態。一些實施例的前驅物可藉由CVD產生高純度錳薄膜及藉由ALD產生高純度MnNx薄膜,該等薄膜具有光滑的形態。
一些實施例的來自三甲基甲矽烷基醯胺基錳複合物的MnNx的ALD已經在標準的ALD腔室上執行。薄膜在所有測試的介電材料中顯示光滑的表面形態,該等介電材料包括摻雜高孔隙度的碳的低k二氧化矽。可獲得來自三甲基甲矽烷基醯胺基錳的純錳的CVD。錳可與下層介電質反應以形成
矽酸錳,該等矽酸錳經證實為用於銅的良好擴散阻障。
本發明的一個態樣係關於一種微電子裝置,該微電子裝置包含基板、介電層、阻障層及導電材料。第1A圖圖示微電子裝置100的實施例,該微電子裝置100包含基板105及介電層110。介電層110位於基板105上,且介電層110具有溝槽150,該溝槽150由溝槽底部120、側壁115及開口160界定。
在一或更多個實施例中,介電層110為低k介電層。在一些實施例中,介電層包含SiOx。進一步實施例規定介電層包含摻雜多孔碳的SiOx。在一或更多個實施例中,介電層為摻雜多孔碳的SiOx層,該層具有小於3的k值。
第1B圖圖示沉積阻障層130之後的同一微電子裝置100,該阻障層130覆蓋側壁115及/或溝槽底部120的至少一部分。如第1B圖中所圖示,阻障層130可覆蓋側壁115及溝槽底部120的全部。阻障層130可包含MnNx及一或更多種摻雜劑,諸如Co、Mn、Ru、Ta、Al、Mg、Cr、Nb、Ti或V。
在一或更多個實施例中,阻障層包含以錳層的重量計的0.1%至10%的摻雜劑。在一些實施例中,阻障層包含0.2重量%至8重量%的摻雜劑。在特定實施例中,阻障層包含0.5重量%至5重量%的摻雜劑。
根據一或更多個實施例,如本文中所使用,「阻障層」指代藉由沉積TaN及一或更多種摻雜劑所形成的不連續的層,且排除第二元素或摻雜劑擴散進入僅一部分阻障層之區域。換言之,摻雜劑存在於貫穿TaN層的全部厚度,而不
僅是出現在TaN層的表面部分處。
導電填充材料140填滿具有阻障層130為襯墊的至少一部分溝槽150。根據一或更多個實施例,導電填充材料包含銅或銅合金。在其他實施例中,導電填充材料進一步包含Al。
儘管第1B圖中的導電填充材料140圖示為直接接觸阻障層130,但中間層可能在導電填充材料140與阻障層130之間,諸如黏附層或晶種層。根據一或更多個實施例,微電子裝置進一步包含黏附層,該黏附層包含Ru及Co、Mn中的一或更多者。除了Ru及/或Co之外,黏附層可包含一或更多種摻雜劑,諸如Ta、Al、Mg、Cr、Nb、Ti或V。在特定實施例中,黏附層包含Ru及Mn。除了傳統的襯墊之外,錳及氮化錳可用作襯墊。舉例而言,當藉由CVD Cu替代PVD Cu時,氮化錳可能為有希望的襯墊。此外,氮化錳可還原至Mn以作為襯墊促進與Cu的黏附。
在一些實施例中,晶種層沉積在阻障層的頂部上。根據一或更多個實施例,晶種層包含銅的合金,諸如Cu-Mn合金。在一些實施例中,晶種層包含小於約5重量%的Mn、小於約4重量%的Mn、小於約3重量%的Mn或小於約2重量%的Mn。在一或更多個實施例中,晶種層包含約1重量%的Mn。含有1重量%的Mn的銅合金的線路電阻可預期與純銅的線路電阻相同或類似。
雖然不希望受限於任何特定原理,但人們認為摻雜劑可選擇性地經由阻障層130擴散至介電層110且可與介電
材料形成複合物,該複合物將抗電子遷移。因此,在一些實施例中,Mn可經由阻障層擴散且可形成MnSiOx。此MnSiOx的自形成阻障層隨後可阻止從導電材料140至介電層110的銅電子遷移。
除了作為銅阻障之外,摻雜的錳亦可為氧從介電層110擴散至導電材料140的阻障。氧從介電層110擴散至導電材料140可導致氧與導電材料及/或晶種層中的成分反應。舉例而言,氧可與阻障層130及導電材料140的界面處的層反應,由此「固定」Mn至阻障層/導電材料界面上。類似地,若存在包含Mn的晶種層,則氧可與晶種層/阻障層界面處的晶種層中的Mn反應且可固定Mn至該界面。
在一些實施例中,基板暴露於第一前驅物及反應物。實質上可同時暴露於該等前驅物,如在CVD反應中,或依序暴露於該等前驅物,如在ALD反應中。如本說明書及隨附申請專利範圍中所使用,術語「實質上同時」意謂前驅物及反應性氣體流入腔室內以彼此反應且一起與基板表面反應。熟習此項技術者將理解可能存在基板區域,該等區域短暫暴露於前驅物及反應性氣體中的一者直到前驅物及反應性氣體中的另一者擴散至相同區域。
在一些實施例中,含錳有機金屬化合物的化學式如下:
其中每一A為獨立地選自碳或矽,且每一R為獨立地選自氫、甲基、經取代烷類或非經取代烷類、支鏈烷類或非支鏈烷類、經取代烯類或非經取代烯類、支鏈烯類或非支鏈烯類、經取代炔類或非經取代炔類、支鏈炔類或非支鏈炔類或經取代芳香族或非經取代芳香族。錳的氧化狀態可處於任何適當的氧化狀態,該氧化狀態能與基板或反應物反應。在一些實施例中,錳為Mn(II)或Mn(III)。
含錳薄膜的沉積可在裸基板表面上執行或在基板表面上已經存在的薄膜上執行。舉例而言,含錳薄膜可沉積在表面上存在的介電薄膜上。介電薄膜可具有形成於該介電薄膜中的多種結構(例如,溝槽),該等結構具有頂部、底部及側壁。在一些實施例中,存在介電薄膜,該介電薄膜具有至少一個溝槽,該溝槽具有側壁及底部。底部可為介電質或介電質下的表面(例如,裸基板或者另一種材料)。對於不同表面,含錳薄膜的沉積可為選擇性的。在一些實施例中,對於介電層或下層,含錳薄膜的沉積為選擇性的。在一些實施例中,每一A為氮原子。在一或更多個實施例中,每一R基團為甲基。在一些實施例中,含錳有機金屬化合物包含錳雙[雙(三甲基矽烷基)醯胺]。在一些實施例中,反應物為氨及氫中的一或更多者。在不受
限於任何特定的操作原理的情況下,咸信Mn-N鍵在薄膜形成期間斷裂。因此,作為實例,若使用氨,則可形成氮化錳薄膜。然而,若氫用作反應物,則可形成錳薄膜。
在一些實施例中,錳薄膜包含MnNx。一些實施例的x在約0.1至約3的範圍內,或在約0.2至約2的範圍內,或在約0.25至約1的範圍內。氮化錳薄膜可經受後沉積製程,藉由該後沉積製程形成矽酸錳。在一些實施例中,薄膜包含矽酸錳且可直接形成在介電層上。在一或更多個實施例中,錳薄膜包含接近介電表面的矽酸錳及離表面較遠的氮化錳。從矽酸鹽至氮化物的過渡可為逐漸的或可為不連續的步驟。
在一些實施例中,含錳薄膜在小於約2 nm的厚度處為連續的。如在本說明書及隨附申請專利範圍中所使用,術語「連續的」意謂大於總薄膜面積的約10%的薄膜中沒有間隙。在一些實施例中,薄膜以小於3 nm、2.5 nm、1.5 nm、1 nm或0.5 nm的厚度連續。
在一些實施例中,含錳薄膜中實質上不存在氧化錳。如在本說明書及隨附申請專利範圍中所使用,術語「實質上不」意謂層中存在小於約5原子百分比的氧化錳。在一些實施例中,存在小於約4原子%、3原子%、2原子%或1原子%的氧化錳。
第2圖圖示具有基板205及介電層210的微電子裝置200。介電層210具有側壁215及溝槽底部220,該等側壁215及溝槽底部220至少部分地被第一層230所覆蓋。第一層230可為包含矽酸錳的阻障層。第二層235安置在第一層230
上,且可包含錳或氮化錳中的一或更多者。第二層可進一步包含一或更多種摻雜劑,諸如Ta、Al、Mg、Cr、Nb、Ti或V。第一層230與第二層235之間的過渡可為平滑的,如在梯度組分中或在不連續階梯中。
導電填充材料240沉積在藉由側壁215及溝槽底部220界定的溝槽的剩餘部分中。根據一或更多個實施例,導電填充材料包含銅或銅合金。在進一步的實施例中,導電填充材料亦包含Mn。導電材料240可直接沉積在第二層235上或可沉積在第二層235的頂部上的晶種層(未圖示)上。根據一或更多個實施例,晶種層包含銅合金,諸如Mn、Co及Ru。在一些實施例中,晶種層包含小於約5%的Mn,或小於約4%的Mn,或小於約3%的Mn,或小於約2%的Mn或小於約1%的Mn。
除了上述薄膜以外,本發明的另一態樣係關於用於在微電子裝置中形成互連的方法,該方法包含以下步驟:提供基板,該基板具有安置在該基板上之介電層;沉積阻障層在介電層上;及沉積導電材料在阻障層上。根據此態樣的一或更多個實施例,阻障層包含氮化錳及摻雜劑,該摻雜劑選自Mn、Co、Ru、Ta、Al、Mg、Cr、Nb、Ti及V。
錳層(金屬的、氮化物或矽化物)可藉由任何適當的沉積製程形成。舉例而言,錳層可藉由交替層沉積(alternating layer deposition;ALD)製程或電漿增強原子層沉積(plasma enhanced atomic layer deposition;PEALD)來沉積。摻雜劑隨後可藉由化學氣相沉積(CVD)、物理氣相沉積(PVD)
或ALD來沉積。摻雜劑隨後擴散至含錳層中以形成整合的含錳摻雜劑層。摻雜劑可經由各種製程擴散至含錳層中,包括藉由電漿處理及藉由加熱。
或者,錳及摻雜劑可沉積在交替層中。根據此實施例,第一含錳層(諸如錳單層)沉積在介電薄膜上。當介電薄膜被稱作下層用於含錳薄膜的沉積時,將理解下層可為任何適當的層,包括(但不限於),金屬層或基底基板。第一摻雜劑層(諸如摻雜劑層、摻雜劑合金層或其他含摻雜劑化合物層)隨後沉積在第一含錳層的頂部上。此第一摻雜劑層亦可為單層。第二含錳層隨後沉積在第一摻雜劑層的頂部上。重複此製程直到產生所需厚度的摻雜的含錳薄膜。含錳層與摻雜劑層的比率可為任何適當的組合且不限於1:1。舉例而言,可存在十個含錳層沉積用於每一個摻雜劑層。在一些實施例中,存在一個以上前驅物氣體同時或分別流入處理腔室內。舉例而言,含錳前驅物及鈷前驅物可一起流入腔室內以與表面反應。使用的反應物可特定用於前驅物物種中的一者或共同用於兩個物種。在一些實施例中,基板或表面暴露於第一前驅物,接著暴露於第一反應物,及暴露於不同於第一前驅物的第二前驅物,隨後暴露於第一反應物或者不同於第一反應物的第二反應物。
對於沉積摻雜劑金屬,可使用適當的含金屬的前驅物。適當的前驅物的實例包括含有所需摻雜劑的金屬複合物,諸如與有機配合基或羰基配合基配位的摻雜劑金屬。適當的摻雜劑前驅物應具有充足的蒸氣壓力以在適當的製程
(諸如ALD、CVD及PVD)中沉積。取決於使用的摻雜劑前驅物,可使用共同反應物來沉積摻雜劑。舉例而言,還原氣體(諸如氫氣及氨氣)可用作沉積一些摻雜劑之共同反應物。
本發明的一些實施例規定在沉積導電材料之前採用電漿處理摻雜的含錳薄膜。根據一或更多個實施例,電漿包含He、Ar、NH3、H2及N2中的一或更多者。導電材料可以各種方式沉積,包括藉由無電的沉積製程、電鍍(electroplating;ECP)製程、CVD製程或PVD製程。在一些實施例中,第一晶種層沉積在阻障層上,且主體導電層隨後形成在晶種層上。
根據本發明的各種實施例的薄膜事實上可沉積在任何基板材料的上方。如本文中所使用的「基板表面」指代形成在基板上的任何基板或材料表面,在製造製程期間,在該表面上執行薄膜處理。舉例而言,根據應用,其上可執行處理的基板表面包括材料,諸如矽、二氧化矽、拉伸矽、絕緣體上矽(silicon on insulator;SOI)、摻雜碳的氧化矽、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。基板表面上的阻障層、金屬或金屬氮化物包括用於裝置製造之鈦、氮化鈦、氮化鎢、鉭及氮化鉭、鋁、銅或任何其他導體或導電或非導電阻障層。基板可具有各種尺寸,諸如200 mm或300 mm直徑晶圓以及矩形的或正方形的窗格。基板上可使用本發明的實施例,基板包括(但不限於)半導體晶圓(諸如晶體矽(例如,Si<100>或Si<111>))、二氧化矽、拉伸矽、鍺化矽、摻雜多晶矽或未摻雜多晶矽、摻雜矽晶圓或未摻雜矽晶
圓、III-V族材料,諸如砷化鎵、氮化鎵、磷化銦及圖案化或非圖案化的晶圓。基板可暴露於預處理製程以研磨、蝕刻、還原、氧化、羥化、退火及/或烘焙基板表面。
當本發明的實施例提供用於沉積或形成摻雜的含錳薄膜的方法時,處理腔室經設置以在氣相沉積製程期間暴露基板至一連串的氣體及/或電漿。處理腔室將包括分離的反應物供給,隨同載氣、淨化氣體及惰性氣體(諸如氬氣及氮氣)的任何供給,該等供給與用於反應物及氣體的每一者的氣體入口流體連通。每一入口可藉由適當的流量控制器(諸如質量流量控制器或容積流量控制器)控制,該控制器與中央處理單元(central processing unit;CPU)通訊,該中央處理單元允許反應物中的每一者流動至基板以執行如本文中所描述的沉積製程。中央處理單元可為任何形式電腦處理器中的一者,該電腦處理器可用於產業設置中用於控制各種腔室及子處理器。CPU可耦合至記憶體且可為易獲得的記憶體中的一或更多者,諸如隨機存取記憶體(random access memory;RAM)、唯讀記憶體(read only memory;ROM)、快閃記憶體、壓縮光碟、軟碟、硬碟或本端或遠端數位儲存器的任何其他形式。支援電路可耦合至CPU以習知方式支援CPU。該等電路包括快取記憶體、電源、時鐘電路、輸入/輸出電路系統、子系統等等。
在原子層沉積類型腔室中,基板可暴露於第一前驅物及反應物空間或時間分離的製程。時間性的ALD,亦被稱為時域ALD,為傳統的製程,在該製程中第一前驅物流入腔
室內以與表面反應(例如,化學吸附)。在將反應物流入腔室內之前,將第一前驅物自腔室淨化。在空間性的ALD中,第一前驅物及反應性氣體兩者同時流至腔室但是空間分離以便在多次流入之間存在區域,防止前驅物的混合。通常,第一前驅物及反應物之間存在氣體幕(例如,淨化氣體、真空埠或所述者的組合)以確保分離。在空間性的ALD中,必須相對於氣體分配板移動基板,反之亦然,以使得每一部分基板暴露於第一前驅物及反應性氣體兩者。
可在單個基板沉積腔室中處理基板,其中在處理另一個基板之前裝載、處理及卸載單個基板。基板亦可以連續的方式處理,像傳送機系統,在該系統中,多個基板分別被載入腔室的第一部分中,移動穿過腔室且從腔室的第二部分卸載。腔室的形狀及相關的傳送機系統可形成直線路徑或曲線路徑。此外,處理腔室可為旋轉料架,在該旋轉料架中多個基板圍繞中心軸移動及暴露於不同位置處的沉積氣體。
共同反應物通常為蒸氣或氣體形式。反應物可使用載氣傳送。載氣、淨化氣體、沉積氣體或其他製程氣體可含有氮、氫、氬、氖、氦或所述者的組合。此處描述的各種電漿,諸如氮電漿或惰性氣體電漿,可從電漿共同反應性氣體點燃及/或含有電漿共同反應性氣體。
在一或更多個實施例中,用於製程的各種氣體可從各種洞或出口,經由氣體通道經脈衝傳輸進入入口,及進入中央通道。在一或更多個實施例中,沉積氣體可依序脈衝傳輸至噴淋頭及經由噴淋頭脈衝傳輸。或者,如上所述,氣體
可經由氣體供應噴嘴或氣體供應頭同時流動,且基板及/或氣體供應頭可經移動,以使得基板依序暴露於氣體。
在另一實施例中,含錳薄膜可在電漿增強原子層沉積(PEALD)製程期間形成,該製程提供連續的前驅物及電漿脈衝。在具體實施例中,共同反應物可涉及電漿。在涉及使用電漿的其他實施例中,在電漿步驟期間,大體在製程期間離子化試劑,雖然此可能僅發生在沉積腔室的上游,以使得離子或其他能量或發光物種不與沉積薄膜直接接觸,此配置經常被稱為遠端電漿。因此,在此類型的PEALD製程中,從處理腔室外部產生電漿,諸如藉由遠端電漿產生器系統產生。在PEALD製程期間,可從微波(microwave;MW)頻率產生器或射頻(radio frequency;RF)產生器產生電漿。儘管可在本文中揭示的沉積製程期間使用電漿,然而應注意到電漿並非必需。確切而言,其他實施例係關於非常溫和的條件下的沉積製程,無需電漿。
本發明的另一個態樣關於用於在基板上沉積薄膜以執行根據上述實施例中的任一者之製程的設備。在一個實施例中,設備包含沉積腔室用於在基板上沉積薄膜。腔室包含處理區域用於支撐基板。設備包括前驅物入口,該前驅物入口與錳前驅物(諸如,錳[雙(雙(三甲基矽烷基)醯胺])的供應流體連通。設備亦包括反應性氣體入口,該反應性氣體入口與含氮前驅物(諸如氨)的供應流體連通。設備亦包括反應性氣體入口,該反應性氣體入口與摻雜劑前驅物(諸如,含摻雜劑的金屬複合物)的供應流體連通。設備進一步包括淨
化氣體入口,該淨化氣體入口與淨化氣體流體連通。設備可進一步包括真空埠用於從沉積腔室移除氣體。設備可進一步包括輔助氣體入口用於供給一或更多個輔助氣體(諸如惰性氣體)至沉積腔室。沉積可進一步包括用於藉由輻射加熱及/或電阻性加熱來加熱基板的手段。
在一些實施例中,可在本文中所描述的方法期間使用的用於沉積或形成薄膜的電漿系統及處理腔室或系統可在PRODUCER®、CENTURA®或ENDURA®系統上執行,所有該等系統可購自位於加利福尼亞州的聖克拉拉的Applied Materials公司。ALD處理腔室的詳細描述可見於共同讓渡的美國專利第6,821,563號、第6,878,206號、第6,916,398號及第7,780,785號。
遍及此說明書的對「一個實施例」、「某些實施例」、「一或更多個實施例」或「實施例」之引用意謂與實施例有關的描述的特定特徵、結構、材料或特點包括在本發明的至少一個實施例中。因此,遍及本發明書各處的諸如「在一或更多個實施例中」、「在某些實施例中」、「在一個實施例中」或「在實施例中」的用語的出現不一定指代本發明的相同實施例。此外,在一或更多個實施例中,特定特徵、結構、材料或特點可以任何適當的方式組合。
儘管本文中已經參閱特定實施例描述本發明,但應理解,該等實施例僅為說明本發明的原理及應用。對於熟習此項技術者將顯而易見的是在不脫離本發明的精神及範圍的情況下可對本發明的方法及設備做出各種修改及變化。因
此,本發明意欲包括在隨附申請專利範圍及申請專利範圍的等效物的範圍內的修改及變化。
200‧‧‧微電子裝置
205‧‧‧基板
210‧‧‧介電層
215‧‧‧側壁
220‧‧‧溝槽底部
230‧‧‧第一層
235‧‧‧第二層
240‧‧‧導電填充材料
Claims (19)
- 一種形成一含錳薄膜的方法,該方法包含以下步驟:提供一基板,及將該基板暴露至一第一前驅物及一反應物,其中該反應物為氨及氫中的一或更多者,該第一前驅物包含一含錳有機金屬化合物以沉積一含錳薄膜,其中該含錳有機金屬化合物的化學式如下:
- 如請求項1所述之方法,其中該含錳薄膜進一步包含一或更多種摻雜劑,該一或更多種摻雜劑選自Co、Mn、Ru、Ta、Al、Mg、Cr、Nb、Ti及V。
- 如請求項2所述之方法,其中藉由暴露該基板至一第二前驅物及一反應物來包括該摻雜劑,該第二前驅物包含一化合物,該化合物含有該摻雜劑元素。
- 如請求項1所述之方法,其中該基板實質上同時暴露於該第一前驅物及反應物。
- 如請求項1所述之方法,其中該基板依序暴露於該第一前驅物及反應物。
- 如請求項1所述之方法,其中每一R基團為甲基。
- 如請求項1所述之方法,其中該含錳有機金屬化合物包含錳雙[雙(三甲基矽烷基)醯胺]。
- 如請求項7所述之方法,其中該反應物包含氨。
- 如請求項1所述之方法,其中該錳薄膜為MnNx且x在約0.1至約3的範圍內。
- 如請求項9所述之方法,該方法進一步包含以下步驟:處理該MnNx薄膜以產生矽酸錳。
- 如請求項1所述之方法,其中矽酸錳沉積在該基板上。
- 如請求項1所述之方法,其中該含錳薄膜在小於約2nm的一厚度處為連續的。
- 如請求項1所述之方法,該方法進一步包含以下步驟:暴露該基板至不同於該第一前驅物的一第二前驅物及可選擇地暴露至不同於該反應物的一第二反應物。
- 如請求項1所述之方法,其中該基板包含一介電層,該介電層安置在該基板上,該介電層具有一溝槽,該溝槽具有一開口、一側壁及一底部,且該含錳薄膜沉積在該溝槽的該側壁及底部中的一或更多者的至少一部分上。
- 如請求項14所述之方法,其中該含錳薄膜選擇性地沉積在該介電層及基板中的一者上,該介電層及基板中的一者在該介電層及該基板中的另一者的上方。
- 一種用於在一微電子裝置中形成互連的方法,該方法包含以下步驟:提供一基板,該基板包含一介電層,該介電層安置在該基板上,該介電層具有一開口,該開口允許導電至一下層,將該基板暴露至一第一前驅物及一反應物,其中該反應物為氨及氫中的一或更多者,該第一前驅物包含一含錳有機金屬化合物以沉積一含錳薄膜在該介電層的至少一部分上,其中該含錳有機金屬化合物的化學式如下:
- 如請求項16所述之方法,其中該含錳薄膜包含位在該介電質過渡至MnNx的一表面處的矽酸錳。
- 如請求項16所述之方法,該方法進一步包含以下步驟:在沉積該導電材料之前將該含錳薄膜暴露至電漿處理。
- 如請求項18所述之方法,其中該電漿包含He、Ar、NH3、H2及N2中的一或更多者。
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