TWI762194B - 在金屬材料表面上沉積阻擋層的方法 - Google Patents
在金屬材料表面上沉積阻擋層的方法 Download PDFInfo
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- TWI762194B TWI762194B TW110105223A TW110105223A TWI762194B TW I762194 B TWI762194 B TW I762194B TW 110105223 A TW110105223 A TW 110105223A TW 110105223 A TW110105223 A TW 110105223A TW I762194 B TWI762194 B TW I762194B
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- Prior art keywords
- substrate
- barrier layer
- metal material
- azide
- oxide
- Prior art date
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- 238000000034 method Methods 0.000 title claims abstract description 90
- 239000007769 metal material Substances 0.000 title claims abstract description 77
- 238000000151 deposition Methods 0.000 title claims description 51
- 230000000903 blocking effect Effects 0.000 title abstract description 9
- 239000000758 substrate Substances 0.000 claims description 113
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 58
- 230000004888 barrier function Effects 0.000 claims description 56
- 150000001345 alkine derivatives Chemical class 0.000 claims description 33
- 150000001875 compounds Chemical class 0.000 claims description 33
- 229910052757 nitrogen Inorganic materials 0.000 claims description 29
- 239000000376 reactant Substances 0.000 claims description 28
- 239000001257 hydrogen Substances 0.000 claims description 27
- 229910052739 hydrogen Inorganic materials 0.000 claims description 27
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 24
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 24
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 24
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 24
- 150000001540 azides Chemical class 0.000 claims description 23
- 229910000077 silane Inorganic materials 0.000 claims description 21
- 125000000217 alkyl group Chemical group 0.000 claims description 17
- 150000002825 nitriles Chemical class 0.000 claims description 16
- 150000002118 epoxides Chemical class 0.000 claims description 15
- 229910052802 copper Inorganic materials 0.000 claims description 14
- 239000010949 copper Substances 0.000 claims description 14
- 125000003118 aryl group Chemical group 0.000 claims description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 11
- 239000010941 cobalt Substances 0.000 claims description 11
- 229910017052 cobalt Inorganic materials 0.000 claims description 11
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 11
- 229910052721 tungsten Inorganic materials 0.000 claims description 11
- 125000000304 alkynyl group Chemical group 0.000 claims description 7
- IVRMZWNICZWHMI-UHFFFAOYSA-N azide group Chemical group [N-]=[N+]=[N-] IVRMZWNICZWHMI-UHFFFAOYSA-N 0.000 claims description 7
- 239000010936 titanium Substances 0.000 claims description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 6
- 239000010937 tungsten Substances 0.000 claims description 6
- 239000004593 Epoxy Substances 0.000 claims description 5
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 5
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 claims description 5
- 229910052707 ruthenium Inorganic materials 0.000 claims description 5
- 125000006702 (C1-C18) alkyl group Chemical group 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 125000003342 alkenyl group Chemical group 0.000 claims description 4
- BBXVGZSHLMEVIP-UHFFFAOYSA-N dodecylsilane Chemical compound CCCCCCCCCCCC[SiH3] BBXVGZSHLMEVIP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052741 iridium Inorganic materials 0.000 claims description 4
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 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
- 229910052715 tantalum Inorganic materials 0.000 claims description 4
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 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
- 238000004140 cleaning Methods 0.000 claims description 3
- 150000004767 nitrides Chemical class 0.000 claims description 3
- 229910001925 ruthenium oxide Inorganic materials 0.000 claims description 3
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 claims description 3
- 238000004132 cross linking Methods 0.000 claims 1
- 230000008021 deposition Effects 0.000 abstract description 26
- 230000009257 reactivity Effects 0.000 abstract description 4
- 230000007423 decrease Effects 0.000 abstract description 2
- 230000002708 enhancing effect Effects 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 69
- 210000002381 plasma Anatomy 0.000 description 44
- 239000007789 gas Substances 0.000 description 40
- 230000008569 process Effects 0.000 description 38
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 24
- 239000012071 phase Substances 0.000 description 18
- 238000012545 processing Methods 0.000 description 18
- 238000000231 atomic layer deposition Methods 0.000 description 17
- 229910052751 metal Inorganic materials 0.000 description 17
- 239000002184 metal Substances 0.000 description 17
- 239000013545 self-assembled monolayer Substances 0.000 description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 15
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 15
- 229910052718 tin Inorganic materials 0.000 description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 12
- 229930195733 hydrocarbon Natural products 0.000 description 12
- 229910052760 oxygen Inorganic materials 0.000 description 12
- 239000001301 oxygen Substances 0.000 description 12
- 239000002094 self assembled monolayer Substances 0.000 description 12
- 150000002430 hydrocarbons Chemical class 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- 239000002243 precursor Substances 0.000 description 11
- 239000004215 Carbon black (E152) Substances 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 10
- 229910021529 ammonia Inorganic materials 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 description 8
- 229910052710 silicon Inorganic materials 0.000 description 8
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 8
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 8
- 239000005052 trichlorosilane Substances 0.000 description 8
- 239000010703 silicon Substances 0.000 description 7
- AIFMYMZGQVTROK-UHFFFAOYSA-N silicon tetrabromide Chemical compound Br[Si](Br)(Br)Br AIFMYMZGQVTROK-UHFFFAOYSA-N 0.000 description 7
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 6
- 229910052681 coesite Inorganic materials 0.000 description 6
- 229910052906 cristobalite Inorganic materials 0.000 description 6
- 239000003989 dielectric material Substances 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- 235000012239 silicon dioxide Nutrition 0.000 description 6
- 229910052814 silicon oxide Inorganic materials 0.000 description 6
- 229910052682 stishovite Inorganic materials 0.000 description 6
- 229910052905 tridymite Inorganic materials 0.000 description 6
- 239000012808 vapor phase Substances 0.000 description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 5
- 229910008051 Si-OH Inorganic materials 0.000 description 5
- 229910006358 Si—OH Inorganic materials 0.000 description 5
- 238000000137 annealing Methods 0.000 description 5
- 238000005530 etching Methods 0.000 description 5
- 229910052731 fluorine Inorganic materials 0.000 description 5
- 239000011737 fluorine Substances 0.000 description 5
- 229910044991 metal oxide Inorganic materials 0.000 description 5
- 150000004706 metal oxides Chemical class 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 238000000682 scanning probe acoustic microscopy Methods 0.000 description 5
- 229910003910 SiCl4 Inorganic materials 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 229910003089 Ti–OH Inorganic materials 0.000 description 4
- 125000003282 alkyl amino group Chemical group 0.000 description 4
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 4
- 150000004820 halides Chemical class 0.000 description 4
- 238000010926 purge Methods 0.000 description 4
- 238000011946 reduction process Methods 0.000 description 4
- 229910021332 silicide Inorganic materials 0.000 description 4
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 4
- -1 silicon halides Chemical class 0.000 description 4
- CFTHARXEQHJSEH-UHFFFAOYSA-N silicon tetraiodide Chemical compound I[Si](I)(I)I CFTHARXEQHJSEH-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- PYJJCSYBSYXGQQ-UHFFFAOYSA-N trichloro(octadecyl)silane Chemical compound CCCCCCCCCCCCCCCCCC[Si](Cl)(Cl)Cl PYJJCSYBSYXGQQ-UHFFFAOYSA-N 0.000 description 4
- 229940126062 Compound A Drugs 0.000 description 3
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 3
- 229910003676 SiBr4 Inorganic materials 0.000 description 3
- 229910004480 SiI4 Inorganic materials 0.000 description 3
- FXMNVBZEWMANSQ-UHFFFAOYSA-N chloro(silyl)silane Chemical compound [SiH3][SiH2]Cl FXMNVBZEWMANSQ-UHFFFAOYSA-N 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 238000011010 flushing procedure Methods 0.000 description 3
- 238000009616 inductively coupled plasma Methods 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 238000006557 surface reaction Methods 0.000 description 3
- 150000003852 triazoles Chemical class 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910003902 SiCl 4 Inorganic materials 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005137 deposition process Methods 0.000 description 2
- 230000008570 general process Effects 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical group 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 238000001459 lithography Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910001092 metal group alloy Inorganic materials 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
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000007363 ring formation reaction Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 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
- 235000012431 wafers Nutrition 0.000 description 2
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 1
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910003691 SiBr Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910003074 TiCl4 Inorganic materials 0.000 description 1
- 150000001335 aliphatic alkanes Chemical group 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000012707 chemical precursor Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000006352 cycloaddition reaction Methods 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
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- VWWMOACCGFHMEV-UHFFFAOYSA-N dicarbide(2-) Chemical compound [C-]#[C-] VWWMOACCGFHMEV-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000002474 experimental method 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
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 239000012761 high-performance material Substances 0.000 description 1
- 230000005661 hydrophobic surface Effects 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- CTAPFRYPJLPFDF-UHFFFAOYSA-N isoxazole Chemical class C=1C=NOC=1 CTAPFRYPJLPFDF-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing 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
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 150000001282 organosilanes Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 239000010980 sapphire Substances 0.000 description 1
- 150000003376 silicon Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000004347 surface barrier Methods 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 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
- SEDZOYHHAIAQIW-UHFFFAOYSA-N trimethylsilyl azide Chemical compound C[Si](C)(C)N=[N+]=[N-] SEDZOYHHAIAQIW-UHFFFAOYSA-N 0.000 description 1
- CWMFRHBXRUITQE-UHFFFAOYSA-N trimethylsilylacetylene Chemical group C[Si](C)(C)C#C CWMFRHBXRUITQE-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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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 at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
- H01L21/321—After treatment
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02205—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition
- H01L21/02208—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si
- H01L21/02219—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 comprising silicon and nitrogen
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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
- C23C16/02—Pretreatment of the material to be coated
- C23C16/0272—Deposition of sub-layers, e.g. to promote the adhesion of the main coating
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
- H01L21/02123—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon
- H01L21/0217—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material being a silicon nitride not containing oxygen, e.g. SixNy or SixByNz
-
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Abstract
描述多種增強選擇性沉積的方法。一些實施例中,在沉積介電質之前,將阻擋層沉積於金屬材料表面上。一些實施例中,金屬材料表面經過官能化而增強或減少其反應性。
Description
本案揭露內容之實施例關於用於在金屬材料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金屬材料表面上沉積阻擋層以助於僅在介電表面上沉積氮化矽的方法。
半導體工業在追求元件微型化時面臨許多挑戰,元件微型化涉及奈米等級的特徵的快速規模縮小。這樣的問題包括,引入複雜的製造步驟,諸如多重微影步驟,以及高性能材料的整合。為了維持元件微型化的步調,選擇性沉積已顯現前景,因為該選擇性沉積有潛力透過簡化整合方案而移除高昂的微影步驟。
能夠以各式各樣的方式完成材料的選擇性沉積。化學前驅物可選擇性與一個表面反應(相對於另一表面而言)(金屬或介電質)。可調控諸如壓力、基板溫度、前驅物分壓、及/或氣體流量之類的製程參數,以調控特定表面反應的化學動力。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以活化或去活化引入的膜沉積前驅物所針對的表面。
本技術中持續需要改善沉積選擇性的方法。
本案揭露內容之一或多個實施例關於選擇性沉積阻擋層之方法。該方法包括,將具有金屬材料表面與介電表面的基板暴露至矽烷,而在該金屬材料表面上選擇性形成阻擋層,該矽烷包括至少一種化合物,該化合物之通式為SiH3
R,其中R是選自C4至C20的烷基、全氟化烷基、烯基、或炔基基團。
本案揭露內容之額外實施例關於選擇性沉積阻擋層的方法。該方法包括,將具有金屬材料表面與介電表面的基板暴露至炔烴及氮反應物,而在該金屬材料表面上選擇性形成阻擋層,該氮反應物包括疊氮化物或腈氧化物。
本案揭露內容之進一步實施例關於選擇性沉積阻擋層的方法。該方法包括,將具有金屬材料表面與介電表面的基板暴露至環氧化物,而在該金屬材料表面上選擇性形成阻擋層。
本案揭露內容之實施例提供用於在金屬材料表面上沉積阻擋層的多種方法。本案揭露內容之實施例驗明可分別使用或協同使用的用於沉積阻擋層的多種方法。
本案揭露內容之實施例提供用於有利地在介電表面上沉積介電材料(例如SiN)的方法,這是藉由下述方式達成:透過沉積在金屬材料表面上的阻擋層阻擋金屬材料表面上介電材料的沉積。
如本文所用的「基板表面」是指,上面執行膜處理的在基板上所形成的材料表面的部分或是基板的任何部分。舉例而言,上面能夠執行處理的基板表面包括下述材料,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,視應用而定。基板包括(而非限制)半導體晶圓。基板可暴露至前處理製程,以研磨、蝕刻、還原、氧化、氫氧化、退火、UV固化、電子束固化、及/或烘烤該基板表面。除了直接在基板本身表面上進行膜處理之外,在本案揭露內容中,所揭露的膜處理步驟之任一者也可在下層上執行,該下層形成於基板上,在下文中會更詳細揭露,且希望術語「基板表面」包括如上下文所指的此類下層。因此,舉例而言,在膜/層或部分的膜/層已沉積於基板表面上時,新沉積的膜/層之暴露表面變成該基板表面。基板可具有各種尺寸,諸如200mm或300mm直徑的晶圓,以及矩形或方形板。一些實施例中,基板包括剛性的分立材料。
如本文所用的「原子層沉積」或「循環式沉積」是指包括將兩種或更多種反應性化合物依序暴露而在基板表面上沉積材料層的製程。如在此說明書及所附之申請專利範圍中所用,術語「反應性化合物」、「反應性氣體」、「反應性物種」、「前驅物」、「處理氣體」、及類似術語可互換地使用,以意味一物質有能夠在表面反應中與基板表面或基板表面上之材料反應的物種,該表面反應例如化學吸附、氧化、還原、環加成。該基板(或該基板的部分)依序暴露至該兩種或更多種反應性化合物,該等反應性化合物被引入處理腔室之反應區域中。
本案揭露內容之實施例有利地提供用於表面前處理之方法,該表面前處理諸如選擇性阻擋金屬材料表面(包括但不限於銅、鈷、鎢、鉭、氮化鉭、氧化鉭、鈦、氧化鈦、氮化鈦、釕、氧化釕和銥等)。一些實施例有利地提供在介電表面上選擇性生長介電材料的方法,該等介電材料諸如SiO2
、SiN、SiCON、SiCO等。一些實施例有利地提供使用環氧化物表面反應選擇性阻擋表面沉積的方法。
一些實施例中,金屬矽化物選擇性形成於金屬材料表面上勝於在介電表面上。如在此說明書中及所附之申請專利範圍中所用,詞彙「選擇性……勝於」或類似詞彙是意味所述材料沉積在所陳述的表面上達到的程度大於另一表面。一些實施例中,「選擇性」意味所述材料以一速率形成於該選擇性表面上,該速率大於或等於約非所選之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。一些實施例中,含有長烷基鏈的三氫化矽烷(trihydridosilane)(RSiH3
,其中R=C4-C20)用作阻擋分子,且在溶液或氣相與金屬材料表面(包括但不限於Cu、Co、W、及TiN)反應。一些實施例中,在與阻擋分子反應前先清潔金屬材料表面。透過矽烷頭部基團,有機矽烷選擇性與金屬材料表面反應勝於介電表面(例如SiO2
)。矽烷的有機部分作為疏水保護層,而阻擋金屬上有後續介電層(例如SiN)生長,而實現在介電表面上選擇性沉積介電質。
本案揭露內容的一或多個實施例涉及在基板之金屬材料表面上選擇性沉積阻擋層的方法,該基板具有金屬材料表面與介電表面。該方法包括,將基板暴露至矽烷,該矽烷包括至少一種化合物,該化合物之通式為SiH3
R,其中R是選自C4至C20的烷基、全氟化烷基、烯基、或炔基基團。如以此方式所用,字母「C」之後跟隨著數值(例如,「C4」)是意味,該取代基包括指定數目的碳原子(例如,C4包括四個碳原子)。一些實施例中,該取代基可為直鏈基團(例如正丁基)、分支基團(例如第三丁基)或環狀基團(例如環己基)。
該基板的介電表面可包括任何適合的介電材料。適合的介電材料包括(但不限於)氧化物(例如矽氧化物)及高k介電質。一些實施例中,該介電表面基本上由氧化矽組成。如以此方式所用,術語「基本上由……組成」意味在面積的基礎上,該表面為具有大於或等於約95%、98%、或99%的所述材料。
該基板之金屬材料表面可包括任何適合的金屬材料。適合的金屬材料包括(但不限於)金屬、金屬氮化物、金屬合金、及其他導電材料。一些實施例中,該金屬材料表面包括鈷、鎢、或氮化鈦之一或多者。一些實施例中,該金屬材料表面基本上由鈷組成。一些實施例中,該金屬材料表面基本上由鎢組成。一些實施例中,該金屬材料表面基本上由氮化鈦組成。
暴露至基板的矽烷可包括任何適合的三氫化矽烷。一些實施例中,該矽烷包括至少一種化合物,該化合物之通式為SiH3
R,其中R是選自C4至C20的烷基、全氟化烷基、烯基、或炔基基團。一些實施例中,C4至C20烷基基團基本上由一個矽碳鍵、多個碳碳單鍵、及多個碳氫鍵所組成。一些實施例中,C4至C20全氟化烷基基團基本上由一個矽碳鍵、多個碳碳單鍵、及多個碳氟鍵所組成。一些實施例中,C4至C20烯基基團基本上由一個矽碳鍵、多個碳碳單鍵、至少一個碳碳雙鍵、及多個碳氫鍵所組成。一些實施例中,C4至C20炔基基團基本上由一個矽碳鍵、多個碳碳單鍵、至少一個碳碳三鍵、及多個碳氫鍵所組成。一些實施例中,該C4至C20基團包括一或多個鹵素原子及/或疏水性部分(hydrophobic moiety)。
一些實施例中,矽烷包括C4至C20烷基基團。一些實施例中,該矽烷包括十二烷基矽烷(C12
H25
SiH3
)。一些實施例中,該矽烷基本上由十二烷基矽烷組成。
一些實施例中,該矽烷基團在沉積後彼此交聯。一些實施例中,該阻擋層實質上不含有矽烷基團之間的交聯。如在這方面所用,術語「實質上不含有……交聯」意味,在表面積的基礎上,有少於或等於約5%、2%、或1%的交聯。
一些實施例中,在將該基板暴露至矽烷之前先清潔該基板。一些實施例中,僅有基板的金屬材料表面在該基板暴露至矽烷之前清潔。一些實施例中,以氫電漿清潔該基板的金屬材料表面或者是該基板。一些實施例中,該氫電漿是傳導耦合電漿(CCP)。一些實施例中,該氫電漿是感應耦合電漿(ICP)。一些實施例中,該氫電漿包括H2
的電漿。
一些實施例中,在沉積該阻擋層之後,介電層選擇性沉積在介電表面上。一些實施例中,該介電層包括氮化矽。沉積氮化矽可透過任何適合的製程執行。適合的製程可包括將該基板暴露至鹵化矽及氨。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
)、及六氯乙矽烷(HCDS)。
一些實施例中,在沉積介電層之後重複將該基板暴露至該矽烷,而再生該阻擋層。一些實施例中,於再生該阻擋層之後,再度沉積該介電層。一些實施例中,重複將該基板暴露至矽烷及沉積氮化矽層,直到該氮化矽層已經達到預定厚度為止。
在一定數目的沉積循環之後,或是形成膜厚度之後,可執行一次或重複對表面阻擋化學條件的暴露,或是阻擋層的再生。一些實施例中,阻擋層再生前,氮化矽層沉積成厚度在約10Å至約50Å的範圍,或是在約12Å至約35Å的範圍,或在約15Å至約20Å的範圍。一些實施例中,重複將該基板暴露至該矽烷且沉積氮化矽,直到氮化矽層具有大於或等於50Å、75Å、100Å、或150Å的厚度為止。範例
使用2至10分鐘、100瓦的氫電漿清潔金屬材料表面,以減少原生氧化物濃度。在200°C之基板溫度沉積矽烷。一開始以水接觸角(WCA)測量法探究金屬矽化物之形成。較高的接觸角指示疏水性表面(即,矽化物形成)。WCA指示,SiO2
並未被十二烷基矽烷(DDS,R=C12)所阻擋,而金屬材料表面(也就是Co、W、及TiN)被阻擋。用於表面清潔的氫電漿處理助於金屬矽化物形成。
熱及化學穩定性測試結果指出,金屬上的DDS阻擋對於W及TiN而言至200°C都是穩定的,且在Co上多達330°C也穩定。DDS自組裝單層(SAM)可耐受鹵化矽(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
))及NH3
,上述兩者皆用於SiN的ALD。
於DDS SAM上沉積的不同厚度的SiN之WCA研究顯示,當15-20Å的SiN生長之後SAM再生時,在Co、W、及TiN表面上多達約50Å的最小厚度都能夠達到選擇性。透過重複SiN形成之間的再生循環數目,而能夠延長選擇性。觀察到,DDS處理過的基板幾乎不具有SiN生長(由於空氣暴露造成該SiN氧化成SiO2
),然而未以DDS處理過的基板具有約40-50Å的SiN生長。
一些實施例中,取代的疊氮化物或腈氧化物及炔烴在銅表面的存在下反應而形成阻擋層。此反應形成表面鍵結物種,該表面鍵結物種能夠具有潛力以使新官能化的銅表面變得惰性,或是促進反應性朝向引入的膜沉積前驅物。舉例而言,疊氮化物或腈氧化物在銅金屬存在下與炔烴反應,而形成三唑(triazole)或是異噁唑(isooxazole)(分別在疊氮化物或腈氧化物的情況中形成)。一些實施例中,三甲基矽基疊氮化物(trimethylsilyl azide)及三甲基矽基乙炔(trimethylsilyl acetylene)在銅金屬材料表面的存在下反應,而形成所得的表面鍵結三唑。一些實施例中,取代的疊氮化物及炔烴前驅物以氣相依序引至基板。
一些實施例中,在金屬材料表面存在下取代的疊氮化物或腈氧化物及取代的炔烴反應。每一分子(疊氮化物、腈氧化物及炔烴)上反應性取代基的數目N可在1至4個反應性基團之範圍。一些實施例中,反應性基團之數目大於1。
參考圖1,針對疊氮化物及炔烴的可能數目或反應性基團顯示一系列的通常結構。將基團保持在一起的波浪線可以是任何將反應性基團保持在一起的分子鏈,該等反應性基團為基於碳、基於矽、或甚至類似硼、磷、氮、氧、及硫之類的其他元素。
不受理論所限制,當這些單體是在金屬材料表面存在下時,相信這些部分會歷經環化反應,而在金屬材料表面(而不會在介電表面)上形成聚合物網絡,如圖2所說明。相信聚合物網絡對金屬材料表面的鍵結的發生是透過聚合物表面上的氮取代基及雜環的π電子與金屬材料表面的交互作用。
圖3顯示根據本案揭露內容之一些實施例的用於實現選擇性沉積的大致製程流程。流程開始於,將基於乙炔化物(例如炔烴)及基於疊氮化物的單體透過溶液相、純液相(neat)、或氣相方法在約20°C至約600°C的範圍的溫度引至基板。一些實施例中,金屬材料表面是純淨金屬材料表面而在該表面上沒有任何氧化物。引入單體後,聚合物網絡開始透過金屬催化的三唑形成而在金屬材料表面上形成。金屬催化的聚合完成之後,可透過以溶劑(若在溶液相進行)清洗該等表面或使用反應器內側的惰性氣體沖洗,移除未反應的單體。之後可沉積僅在介電質上成核的膜。
製程流程完成之後,能夠使用選擇性蝕刻製程移除聚合物層。已知基於氧及基於氟的蝕刻會蝕刻基於碳的膜,類似在此沉積的阻擋層。圖4顯示透過基於氧的遠端電漿移除聚合物的範例。在此範例中,透過基於氧的遠端電漿蝕刻移除聚合物,該蝕刻移除該聚合物但氧化該金屬材料表面。為了回復原始的金屬材料表面,能夠將金屬氧化物還原回到金屬。一些實施例中,還原包括暴露至H2
及NH3
電漿及/或H2
及NH3
熱退火。
一些實施例中,該膜的一些沉積能夠發生在阻擋層上,而可能導致缺陷(如圖5中的瘤所標示)。一或多個實施例中,伴隨缺陷一併移除聚合物,且該聚合反應再度重新開始,而繼續選擇性生長。
本案揭露內容的一或多個實施例涉及在具有金屬材料表面及介電表面的基板的金屬材料表面上選擇性沉積阻擋層的方法。該方法包括,將該基板暴露至炔烴及氮反應物,而在金屬材料表面上選擇性形成阻擋層,該氮反應物包括疊氮化物或腈氧化物。
一些實施例中,該金屬材料表面包括銅。一些實施例中,該金屬材料表面基本上由銅組成。
一些實施例中,炔烴及氮反應物同時暴露至基板。一些實施例中,該暴露是透過基板對溶液的溶液相暴露而執行,該溶液包括炔烴及氮反應物二者。一些實施例中,該暴露是透過基板對氣體的氣相暴露而執行,該氣體包括炔烴及氮反應物二者。
一些實施例中,炔烴及氮反應物依序暴露至基板。一些實施例中,炔烴先暴露至基板。一些實施例中,氮反應物先暴露至基板。一些實施例中,該暴露是透過基板對溶液的溶液相暴露而執行,該溶液包括炔烴或氮反應物。一些實施例中,該暴露是透過基板對氣體的氣相暴露而執行,該氣體包括炔烴或氮反應物。一些實施例中,一個暴露是在溶液相,而另一個暴露是在氣相。一些實施例中,該基板經沖洗(氣相)或清洗(溶液相)去除前一反應物,之後再暴露至另一反應物。
一些實施例中,該炔烴包括兩種或更多種炔烴部分。一些實施例中,該炔烴包括兩個、或三個、或四個、或更多個炔烴部分。一些實施例中,該炔烴包括至少一種化合物,該化合物的通式為SiR4
,其中每一R獨立地選自C1至C18烷基、芳基、或炔基基團,條件是至少一個R是炔基。
一些實施例中,該氮反應物包括疊氮化物。一些實施例中,該氮反應物基本上由疊氮化物組成。如以此方式所用,該術語「基本上由疊氮化物組成」意味該氮反應物的反應性成分(例如,不包括惰性成分)在分子基礎上為大於或等於約95%、98%、或99%的疊氮化物。一些實施例中,該氮反應物包括腈氧化物。一些實施例中,該氮反應物基本上由腈氧化物組成。如以此方式所用,該術語「基本上由腈氧化物組成」意味該氮反應物的反應性成分(例如,不包括惰性成分)在分子基礎上為大於或等於約95%、98%、或99%的腈氧化物。一些實施例中,該氮反應物實質上不包括腈氧化物。如以此方式所用,術語「實質上不包括腈氧化物」意味,在分子基礎上該氮反應物具有小於或等於約5%、2%、或1%的腈氧化物。
一些實施例中,該疊氮化物包括兩種或更多種疊氮化物部分。一些實施例中,該疊氮化物包括兩種、或三種、或四種、或更多種疊氮化物部分。一些實施例中,該疊氮化物包括至少一種化合物,該化合物的通式為SiR4
,其中每一R獨立地選自C1至C18烷基、芳基、或疊氮化物基團,條件是至少一個R是疊氮化物。
一些實施例中,在將該基板暴露至炔烴或氮反應物之前,先清潔該基板。一些實施例中,在將該基板暴露至炔烴或氮反應物之前,僅先清潔該基板之金屬材料表面。一些實施例中,該基板之金屬材料表面或該基板是以氫電漿清潔。一些實施例中,該氫電漿為傳導耦合電漿(CCP)。一些實施例中,該氫電漿為感應耦合電漿(ICP)。一些實施例中,該氫電漿包括H2
之電漿。
一些實施例中,沉積阻擋層後,介電層選擇性沉積在介電表面上。一些實施例中,該介電層包括氮化矽。沉積氮化矽可透過任何適合的製程執行。適合的製程可包括將該基板暴露至鹵化矽及氨。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
)、及六氯乙矽烷(HCDS)。
一些實施例中,從基板移除阻擋層。該阻擋層可透過任何適合的選擇性蝕刻製程移除。適合的選擇性蝕刻製程包括(但不限於)使用氧電漿及氟電漿。一些實施例中,當使用氧電漿移除阻擋層時,金屬氧化物層形成於該金屬材料表面上。一些實施例中,形成於該金屬材料表面上的金屬氧化物透過使用還原製程移除。適合的還原製程包括(但不限於)使用包括氫或氨的電漿及包括氫或氨的熱退火。一些實施例中,可獨立地遠端或內部生成該氧電漿、氟電漿、氫電漿、及氨電漿,且該等電漿可為傳導耦合或感應耦合。
一些實施例中,在氮化矽層沉積之後,藉由將基板依序暴露至氧電漿及氫電漿移除阻擋層,該基板暴露至炔烴及氮反應物以選擇性阻擋金屬材料表面,而氮化矽膜選擇性沉積於介電表面上。可重複阻擋層的移除、基板的暴露、及氮化矽膜的沉積,直到形成預定厚度的氮化矽膜為止。
一些實施例中,鈷表面可具有增強的表面反應性或致使呈惰性。一些實施例中,鈷可在環氧化物的存在下參與催化,而形成新的官能化表面。該新形成的表面可用於進一步的處理。
本案揭露內容之一或多個實施例涉及在具有金屬材料表面及介電表面之基板的金屬材料表面上選擇性沉積阻擋層的方法。該方法包括,將該基板暴露至環氧化物,以選擇性在金屬材料表面上形成阻擋層。一些實施例中,該金屬材料表面包括鈷。一些實施例中,該金屬材料表面基本上由鈷組成。
一些實施例中,該暴露是透過基板對包括環氧化物的溶液的溶液相暴露而執行。一些實施例中,該暴露是透過基板對包括環氧化物的氣體的氣相暴露而執行。
一些實施例中,該環氧化物包括兩種或更多種環氧化物部分。一些實施例中,該環氧化物為經取代。一些實施例中,該環氧化物包括兩種、或三種、或四種、或更多種環氧化物部分。一些實施例中,該環氧化物包括下述化合物的一或多者:
其中R獨立地選自C1至C4烷基基團。
一些實施例中,該環氧化物包括各別與基板表面反應的兩種或更多種環氧化物部分。一些實施例中,該環氧化物包括兩種或更多種環氧化物部分,其中僅一者與基板表面反應。
一些實施例中,在將該基板暴露至環氧化物之前先清潔該基板。一些實施例中,在將該基板暴露至環氧化物之前,僅先清潔該基板的金屬材料表面。一些實施例中,該基板之金屬材料表面或該基板是以氫電漿清潔。一些實施例中,該氫電漿為傳導耦合電漿(CCP)。一些實施例中,該氫電漿為感應耦合電漿(ICP)。一些實施例中,該氫電漿包括H2
之電漿。
一些實施例中,沉積阻擋層後,介電層選擇性沉積在介電表面上。一些實施例中,該介電層包括氮化矽。沉積氮化矽可透過任何適合的製程執行。適合的製程可包括將該基板暴露至鹵化矽及氨。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
)、及六氯乙矽烷(HCDS)。
一些實施例中,從基板移除阻擋層。該阻擋層可透過任何適合的選擇性蝕刻製程移除。適合的選擇性蝕刻製程包括(但不限於)使用氧電漿及氟電漿。一些實施例中,當使用氧電漿移除阻擋層時,金屬氧化物層形成於該金屬材料表面上。一些實施例中,形成於該金屬材料表面上的金屬氧化物層透過使用還原製程移除。適合的還原製程包括(但不限於)使用包括氫或氨的電漿及包括氫或氨的熱退火。一些實施例中,可獨立地遠端或內部生成該氧電漿、氟電漿、氫電漿、及氨電漿,且該等電漿可為傳導耦合或感應耦合。
矽基鹵化物(silyl halide)前驅物通常不會化學吸附於SiO2
表面上,這是因為表面Si-OH基團在氣相ALD條件下不會與Si-Cl反應。例如,ALD SiO2
膜在一般的ALD條件下不會從SiCl4
/H2
O製程形成。然而,發明人已經發現,將鈦前驅物添加至ALD方案(SiCl4
/H2
O/TiCl4
/H2
O)可造成Tix
Siy
Oz
膜形成。
不受理論所限制,相信儘管Si-OH不與Si-Cl反應,但由於Ti比Si有更低的電負度所以Ti-OH與Si-Cl反應,且Ti-OH比起Si-OH對Si-Cl更具反應性。一些實施例中,此反應性差異用於阻擋TiN而不阻擋SiO2
。
TiN表面一旦暴露至空氣即氧化,且該表面會具有Ti-OH基團。當於空氣中脈衝RSiCl3
(SAM)至暴露的TiN及SiO2
表面時,Si-Cl鍵會與表面Ti-OH反應而非與Si-OH反應。
本案揭露內容的一些實施例涉及於氣相及/或溶液相由三氯矽基碳氫化合物阻擋TiN、W、Cu、或Co之方法。一些實施例中,使用多種化合物阻擋TiN、W、Cu、或Co表面,該等化合物之通式為SiX3
R,其中X是鹵素,R是C1至C18烷基、芳基、及烷基胺。
本案揭露內容之一或多個實施例涉及在具有金屬材料表面與介電表面的基板之金屬材料表面上選擇性沉積阻擋層的方法。該方法包括,將基板暴露至三鹵矽基碳氫化物而選擇性在金屬材料表面上形成阻擋層,該三鹵矽基碳氫化物包括至少一種化合物,該化合物之通式為SiX3
R,其中X是鹵素,R是C1至C18烷基、芳基、及烷胺基。
一些實施例中,對三鹵矽基碳氫化物的暴露是透過基板對包括三鹵矽基碳氫化物的溶液的溶液相暴露而執行。一些實施例中,對三鹵矽基碳氫化物的暴露是透過基板對包括三鹵矽基碳氫化物的氣體的氣相暴露而執行。
一些實施例中,R1
是任何C1-C18烷基、芳基、烷胺基、或苄基。
一些實施例中,該三鹵矽基碳氫化物包括至少一種化合物,該化合物之通式為SiX3
R,其中R是C1至C18烷基、芳基、及烷胺基。如在此方面所用,「烷胺基」是表示有烷類取代基的胺基。換言之,烷胺基取代基具有-NR2
之通式,其中每一R獨立地為H、C1至C6烷基、或芳基。例如,-N(CH3
)2
及-N(CH2
CH3
)2
。
一些實施例中,在該基板暴露至三鹵矽基碳氫化物之前,該基板先暴露至空氣。一些實施例中,在該基板暴露至三鹵矽基碳氫化物之前,僅該基板之金屬材料表面暴露至空氣。範例
藉由ODTS(十八烷基三氯矽烷,octadecyltrichlorosilane)阻擋TiN表面
ODTS溶解於甲苯中,且在室溫將試樣浸泡於溶液達一段設定時間。浸泡後,以甲苯清洗樣本,且以氮氣乾燥。藉由測量水接觸角(WCA)監視SAM形成。1秒浸泡中,SAM的形成充滿於TiN上(但不在SiO2
上)。隨著浸泡時間增加,TiN上的WCA維持固定但SiO2
上的WCA增加。
低溫ALD SiON沉積在SAM處理過的基板上,以評估選擇性介電質沉積。基板維持在200°C,且執行六氯乙矽烷(HCDSO)及NH3
的交替脈衝。SiON的膜厚度是透過橢圓儀測量。150個循環後觀察到5倍選擇性。隨著循環數目增加而選擇性降低。
藉由OTS(辛基丙矽烷)阻擋TiN表面
OTS溶解於甲苯中,且在室溫將試樣浸泡於溶液達一段設定時間。浸泡後,以甲苯清洗樣本,且以氮氣乾燥。藉由測量水接觸角(WCA)監視SAM形成。WCA改變顯示與ODTS實驗類似的趨勢。
各種基板表面上沉積的SAM的熱穩定性是透過WCA測量評估。OTS SAM是在溶液相與氣相中沉積。有SAM沉積的試樣在從200°C至350°C的溫度退火達1小時,且WCA是在退火前及退火後測量。發現到TiN及W上的SAM在多達250°C是穩定的,但在超過該溫度則劣化。相反地,到大於350°C於SiO2
上的SAM是穩定的。比起溶液相,氣相SAM沉積給予更多彈性以達成TiN與SiO2
之間更高的WCA改變。
透過在SiON沉積中所用的前驅物(HCDSO及NH3
)中於200°C退火SAM沉積的試樣達一小時,而評估SAM的化學穩定性。儘管SAM在ALD前驅物中於200°C穩定,但仍有一些劣化。
該方法的一或多個實施例使用原子層沉積(ALD)製程提供阻擋層。在時域(time-domain)ALD製程中,對每一反應性化合物的暴露是透過時間延遲而分開,以容許每一化合物於基板表面上附著及/或反應,然後從處理腔室沖洗該等化合物。透過在後續暴露之間將該等反應性氣體從處理腔室沖洗移除,而防止該等反應性氣體混合。
在空間ALD製程中,反應性氣體流進處理腔室內的不同處理區域。該不同的處理區域與相鄰的處理區域分開,使得反應性氣體不會混合。該基板可在該等處理區域之間移動,以分別將該基板暴露至處理氣體。基板移動期間,基板表面的不同部分(或基板表面上的材料)暴露至該兩種或更多種反應性化合物,使得基板上任何給定的點實質上不同時暴露至超過一種反應性化合物。如熟悉本技術之人士所理解,有可能因為氣體在處理腔室內擴散而基板的一小部分可同時暴露至多種反應性氣體,而該同時的暴露並非刻意,除非另有指定。
時域ALD製程的一個態樣中,第一反應性氣體(即,第一前驅物或化合物A)脈衝輸送至反應區,之後跟隨著第一時間延遲。接著,第二前驅物或化合物B脈衝輸送至反應區中,之後跟隨著第二延遲。在每一時間延遲期間,諸如氬氣之類的沖洗氣體引入處理腔室中,以沖洗反應區,或若不然則從反應區移除任何殘餘的反應性化合物或反應產物或副產物。作為替代方案,該沖洗氣體可在整個沉積製程連續流動,使得在反應性化合物的脈衝之間的時間延遲期間僅有沖洗氣體流動。反應性化合物交替脈衝輸送,直到基板表面上形成預定的膜或膜厚度為止。在任一情境中,脈衝輸送化合物A、沖洗氣體、化合物B及沖洗氣體的ALD製程為一循環。循環可開始於化合物A或化合物B,繼續該循環之各別順序,直到達成有預定厚度的膜為止。
空間ALD製程的實施例中,將第一反應性氣體與第二反應性氣體同時遞送至反應區,但由惰性氣簾及/或真空簾所分開。該氣簾可為進入處理腔室的惰性氣流與離開該處理腔室的真空流之流動的組合。基板相對於氣體遞送設備移動,使得基板上任何給定的點暴露至第一反應性氣體與第二反應性氣體。
如本文所用的「脈衝」或「配劑」是指來源氣體量間歇式或不連續地引入處理腔室的量。每一脈衝內的特定化合物的量可隨時間變化,取決於脈衝持續時間。特定的處理氣體可包括單一化合物或兩種或更多種化合物之混合物/組合。
每一脈衝/配劑的持續時間是可變的,且可經調整以適應例如處理腔室之體積容量以及與處理腔室耦接的真空系統的容量。此外,處理氣體的配劑時間可根據下述因子而變化:處理氣體的流速、處理氣體的溫度、控制閥的類型、運用的處理腔室的類型、以及處理氣體之成分吸附至基板表面上的能力。配劑時間也可根據形成的層的類型及形成的元件的幾何而變化。配劑時間應該夠長,以提供足以吸附/化學吸附至實質上基板整體表面上且在上面形成處理氣體成分層的化合物體積。
雖然上文所述之處理方法的實施例僅包括兩個脈衝的反應性氣體,但會了解這僅為示範,且可使用額外脈衝的處理氣體。該等脈衝可用其整體或部分重複。可重複該循環以形成具預定厚度的阻擋層。一些實施例中,重複該循環以形成具下述厚度的阻擋層:在約5 Å至約40 Å的範圍內、或在約10 Å至約30 Å的範圍內、或在約15 Å至約20 Å的範圍內。
一旦已達到預定厚度,該方法可視情況任選地包括進一步處理(例如介電膜的主體沉積)。一些實施例中,該進一步處理可為ALD製程。例如,一些實施例中,可執行ALD製程,以將氮化矽層主體沉積至目標厚度。
儘管在本文已參考特定實施例描述本案揭露內容,但應瞭解這些實施例僅為說明本案揭露內容的原理與應用。對於熟悉此技術者而言,很明顯可對本案揭露內容之方法與設備製作各種修飾形態與變化形態,但不可背離本案揭露內容之精神與範疇。因此,希望本案揭露內容包括落在所附的申請專利範圍之範疇內的修飾形態及變化形態以及他們的等效例。
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透過參考實施例(其中一些實施例示於附圖說明),可得到上文簡要總結的本案揭露內容的更特定的描述,而得以詳細瞭解本案揭露內容的上文所記載之特徵。然而,應注意,附圖僅說明本案揭露內容之典型實施例,因此不應將該等附圖視為限制本案揭露內容之範疇,因為本案揭露內容可容許其他等效實施例。
圖1顯示根據本案揭露內容之一或多個實施例的關於疊氮化物及炔烴阻擋劑所用的可能數目或反應性基團的一系列通常結構;
圖2顯示根據本案揭露內容之一或多個實施例的在金屬材料表面及環化反應存在下在金屬材料表面上產生聚合網絡的單體的反應示意圖;
圖3顯示根據本案揭露內容之一或多個實施例的實現在金屬材料表面上選擇性沉積聚合物阻擋層及在介電表面上選擇性沉積介電膜的大致製程流程;
圖4顯示根據本案揭露內容之一或多個實施例的透過使用基於氧之遠端電漿及基於氫之遠端電漿移除聚合物阻擋層的製程範例;及
圖5顯示根據本案揭露內容之一或多個實施例的用於選擇性沉積製程的製程流程。
國內寄存資訊(請依寄存機構、日期、號碼順序註記)
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國外寄存資訊(請依寄存國家、機構、日期、號碼順序註記)
無
Claims (20)
- 一種選擇性沉積阻擋層之方法,該方法包括:使用一矽烷(silane)在一基板之一金屬材料表面上選擇性(selectively)形成一阻擋層,該基板具有該金屬材料表面與一介電表面,該矽烷包括至少一種化合物,該化合物之通式為SiH3R,其中R是選自C4至C20的烷基、全氟化烷基、烯基、或炔基基團;及在形成該阻擋層之後,在該介電表面上選擇性沉積一氮化矽層;其中該金屬材料表面包括下述一或多者:銅、鈷、鎢、鉭、氮化鉭、氧化鉭、鈦、氮化鈦、氧化鈦、釕、氧化釕或銥。
- 如請求項1所述之方法,其中該矽烷包括十二烷基矽烷(C12H25SiH3)。
- 如請求項1所述之方法,其中該阻擋層實質上不包括交聯。
- 如請求項1所述之方法,進一步包括:在將該基板暴露至該矽烷之前,以一氫電漿清潔該金屬材料表面。
- 如請求項1所述之方法,進一步包括:在沉積該氮化矽層之後,重複將該基板暴露至一矽烷及沉積一氮化矽層,直到該氮化矽層已達到預定厚度為止。
- 如請求項5所述之方法,其中該預定厚度是 在10埃至50埃之範圍。
- 如請求項5所述之方法,其中該預定厚度大於或等於50埃。
- 一種選擇性沉積阻擋層之方法,該方法包括:在一基板之一金屬材料表面上選擇性形成一阻擋層,其是藉由將該基板暴露於一炔烴(alkyne)及一氮反應物而執行,該基板包括該金屬材料表面與一介電表面,該氮反應物包括一疊氮化物(azide)或一腈氧化物(nitrile oxide);及在形成該阻擋層之後,在該介電表面上選擇性沉積一氮化矽層;其中該金屬材料表面包括下述一或多者:銅、鈷、鎢、鉭、氮化鉭、氧化鉭、鈦、氮化鈦、氧化鈦、釕、氧化釕或銥。
- 如請求項8所述之方法,其中該金屬材料表面包括銅。
- 如請求項8所述之方法,進一步包括:在將該基板暴露至該炔烴或該氮反應物之前,以一氫電漿清潔該金屬材料表面。
- 如請求項8所述之方法,其中該炔烴包括兩種或更多種炔烴部分(alkyne moieties)。
- 如請求項8所述之方法,其中該炔烴包括至少一種化合物,該化合物之通式為SiR4,其中每一R 獨立地選自C1至C18烷基、芳基、或炔基基團,條件是至少一個R是炔基。
- 如請求項8所述之方法,其中該疊氮化物包括兩種或更多種疊氮化物部分。
- 如請求項8所述之方法,其中該疊氮化物包括至少一種化合物,該化合物之通式為SiR4,其中每一R獨立地選自C1至C18烷基、芳基、或疊氮化物基團,條件是至少一個R是疊氮化物基團。
- 如請求項8所述之方法,其中該氮反應物實質上不包括腈氧化物。
- 一種選擇性沉積阻擋層之方法,該方法包括:在一金屬材料表面上選擇性形成一阻擋層,其是藉由:將具有該金屬材料表面與一介電表面的一基板暴露至一環氧化物以選擇性形成該阻擋層;及,在形成該阻擋層之後,在該介電表面上選擇性沉積一氮化矽層,其中該金屬材料表面包括下述一或多者:銅、鈷、鎢、鉭、氮化鉭、氧化鉭、鈦、氮化鈦、氧化鈦、釕、氧化釕或銥。
- 如請求項18所述之方法,其中該金屬材料表面包括鈷。
- 如請求項18所述之方法,其中該環氧化物為經取代。
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