WO2018182318A1 - Composition for depositing silicon-containing thin film and method for manufacturing silicon-containing thin film using the same - Google Patents
Composition for depositing silicon-containing thin film and method for manufacturing silicon-containing thin film using the same Download PDFInfo
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- WO2018182318A1 WO2018182318A1 PCT/KR2018/003682 KR2018003682W WO2018182318A1 WO 2018182318 A1 WO2018182318 A1 WO 2018182318A1 KR 2018003682 W KR2018003682 W KR 2018003682W WO 2018182318 A1 WO2018182318 A1 WO 2018182318A1
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- WO
- WIPO (PCT)
- Prior art keywords
- silicon
- thin film
- composition
- containing thin
- independently
- Prior art date
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- 239000010409 thin film Substances 0.000 title claims abstract description 148
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 106
- 239000010703 silicon Substances 0.000 title claims abstract description 103
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 99
- 238000000151 deposition Methods 0.000 title claims abstract description 69
- 238000000034 method Methods 0.000 title claims abstract description 68
- 239000000203 mixture Substances 0.000 title claims abstract description 54
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 34
- -1 silylamine compound Chemical class 0.000 claims abstract description 54
- 239000010408 film Substances 0.000 claims description 52
- 239000000126 substance Substances 0.000 claims description 38
- 239000000758 substrate Substances 0.000 claims description 28
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 27
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 26
- 230000008021 deposition Effects 0.000 claims description 24
- 239000012495 reaction gas Substances 0.000 claims description 24
- 238000000231 atomic layer deposition Methods 0.000 claims description 21
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 19
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 19
- 125000003342 alkenyl group Chemical group 0.000 claims description 11
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 claims description 11
- 238000005229 chemical vapour deposition Methods 0.000 claims description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 8
- 125000006729 (C2-C5) alkenyl group Chemical group 0.000 claims description 7
- 238000004518 low pressure chemical vapour deposition Methods 0.000 claims description 7
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 4
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 2
- 239000002243 precursor Substances 0.000 abstract description 17
- 230000005540 biological transmission Effects 0.000 abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 15
- 239000008393 encapsulating agent Substances 0.000 abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 125000000217 alkyl group Chemical group 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- ZFCVOJYMROHFMX-UHFFFAOYSA-N 1-[(dimethylamino)methylsilylamino]silyl-N,N-dimethylmethanamine Chemical compound CN(C)C[SiH2]N[SiH2]CN(C)C ZFCVOJYMROHFMX-UHFFFAOYSA-N 0.000 description 8
- 238000004566 IR spectroscopy Methods 0.000 description 8
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 8
- BIVNKSDKIFWKFA-UHFFFAOYSA-N N-propan-2-yl-N-silylpropan-2-amine Chemical compound CC(C)N([SiH3])C(C)C BIVNKSDKIFWKFA-UHFFFAOYSA-N 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 125000006701 (C1-C7) alkyl group Chemical group 0.000 description 6
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 6
- 238000002347 injection Methods 0.000 description 6
- 239000007924 injection Substances 0.000 description 6
- 238000010926 purge Methods 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- 239000012686 silicon precursor Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
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- 238000005259 measurement Methods 0.000 description 4
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- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 3
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 3
- 229910003828 SiH3 Inorganic materials 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 3
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 3
- 239000012159 carrier gas Substances 0.000 description 3
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 3
- 239000001272 nitrous oxide Substances 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- OLRJXMHANKMLTD-UHFFFAOYSA-N silyl Chemical compound [SiH3] OLRJXMHANKMLTD-UHFFFAOYSA-N 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 229910000085 borane Inorganic materials 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000005137 deposition process Methods 0.000 description 2
- UWGIJJRGSGDBFJ-UHFFFAOYSA-N dichloromethylsilane Chemical compound [SiH3]C(Cl)Cl UWGIJJRGSGDBFJ-UHFFFAOYSA-N 0.000 description 2
- 238000005538 encapsulation Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000012844 infrared spectroscopy analysis Methods 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- SIAPCJWMELPYOE-UHFFFAOYSA-N lithium hydride Chemical compound [LiH] SIAPCJWMELPYOE-UHFFFAOYSA-N 0.000 description 2
- 229910000103 lithium hydride Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 2
- BIIBYWQGRFWQKM-JVVROLKMSA-N (2S)-N-[4-(cyclopropylamino)-3,4-dioxo-1-[(3S)-2-oxopyrrolidin-3-yl]butan-2-yl]-2-[[(E)-3-(2,4-dichlorophenyl)prop-2-enoyl]amino]-4,4-dimethylpentanamide Chemical compound CC(C)(C)C[C@@H](C(NC(C[C@H](CCN1)C1=O)C(C(NC1CC1)=O)=O)=O)NC(/C=C/C(C=CC(Cl)=C1)=C1Cl)=O BIIBYWQGRFWQKM-JVVROLKMSA-N 0.000 description 1
- NYNZQNWKBKUAII-KBXCAEBGSA-N (3s)-n-[5-[(2r)-2-(2,5-difluorophenyl)pyrrolidin-1-yl]pyrazolo[1,5-a]pyrimidin-3-yl]-3-hydroxypyrrolidine-1-carboxamide Chemical compound C1[C@@H](O)CCN1C(=O)NC1=C2N=C(N3[C@H](CCC3)C=3C(=CC=C(F)C=3)F)C=CN2N=C1 NYNZQNWKBKUAII-KBXCAEBGSA-N 0.000 description 1
- DWKNOLCXIFYNFV-HSZRJFAPSA-N 2-[[(2r)-1-[1-[(4-chloro-3-methylphenyl)methyl]piperidin-4-yl]-5-oxopyrrolidine-2-carbonyl]amino]-n,n,6-trimethylpyridine-4-carboxamide Chemical compound CN(C)C(=O)C1=CC(C)=NC(NC(=O)[C@@H]2N(C(=O)CC2)C2CCN(CC=3C=C(C)C(Cl)=CC=3)CC2)=C1 DWKNOLCXIFYNFV-HSZRJFAPSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- UXHQLGLGLZKHTC-CUNXSJBXSA-N 4-[(3s,3ar)-3-cyclopentyl-7-(4-hydroxypiperidine-1-carbonyl)-3,3a,4,5-tetrahydropyrazolo[3,4-f]quinolin-2-yl]-2-chlorobenzonitrile Chemical compound C1CC(O)CCN1C(=O)C1=CC=C(C=2[C@@H]([C@H](C3CCCC3)N(N=2)C=2C=C(Cl)C(C#N)=CC=2)CC2)C2=N1 UXHQLGLGLZKHTC-CUNXSJBXSA-N 0.000 description 1
- RSIWALKZYXPAGW-NSHDSACASA-N 6-(3-fluorophenyl)-3-methyl-7-[(1s)-1-(7h-purin-6-ylamino)ethyl]-[1,3]thiazolo[3,2-a]pyrimidin-5-one Chemical compound C=1([C@@H](NC=2C=3N=CNC=3N=CN=2)C)N=C2SC=C(C)N2C(=O)C=1C1=CC=CC(F)=C1 RSIWALKZYXPAGW-NSHDSACASA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- 229910005540 GaP Inorganic materials 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910000673 Indium arsenide Inorganic materials 0.000 description 1
- 229910014329 N(SiH3)3 Inorganic materials 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 1
- 229920012266 Poly(ether sulfone) PES Polymers 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- 229910003811 SiGeC Inorganic materials 0.000 description 1
- 229910000577 Silicon-germanium Inorganic materials 0.000 description 1
- MCRWZBYTLVCCJJ-DKALBXGISA-N [(1s,3r)-3-[[(3s,4s)-3-methoxyoxan-4-yl]amino]-1-propan-2-ylcyclopentyl]-[(1s,4s)-5-[6-(trifluoromethyl)pyrimidin-4-yl]-2,5-diazabicyclo[2.2.1]heptan-2-yl]methanone Chemical compound C([C@]1(N(C[C@]2([H])C1)C(=O)[C@@]1(C[C@@H](CC1)N[C@@H]1[C@@H](COCC1)OC)C(C)C)[H])N2C1=CC(C(F)(F)F)=NC=N1 MCRWZBYTLVCCJJ-DKALBXGISA-N 0.000 description 1
- VOSJXMPCFODQAR-UHFFFAOYSA-N ac1l3fa4 Chemical compound [SiH3]N([SiH3])[SiH3] VOSJXMPCFODQAR-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- VGEWCMWUXFWSRN-UHFFFAOYSA-N chloro-(chloromethylsilylamino)silylmethane Chemical compound ClC[SiH2]N[SiH2]CCl VGEWCMWUXFWSRN-UHFFFAOYSA-N 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- ZOCHARZZJNPSEU-UHFFFAOYSA-N diboron Chemical compound B#B ZOCHARZZJNPSEU-UHFFFAOYSA-N 0.000 description 1
- BUMGIEFFCMBQDG-UHFFFAOYSA-N dichlorosilicon Chemical compound Cl[Si]Cl BUMGIEFFCMBQDG-UHFFFAOYSA-N 0.000 description 1
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- 238000009792 diffusion process Methods 0.000 description 1
- 229940043279 diisopropylamine Drugs 0.000 description 1
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 description 1
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- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- RPQDHPTXJYYUPQ-UHFFFAOYSA-N indium arsenide Chemical compound [In]#[As] RPQDHPTXJYYUPQ-UHFFFAOYSA-N 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
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- 239000003446 ligand Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- OWKFQWAGPHVFRF-UHFFFAOYSA-N n-(diethylaminosilyl)-n-ethylethanamine Chemical compound CCN(CC)[SiH2]N(CC)CC OWKFQWAGPHVFRF-UHFFFAOYSA-N 0.000 description 1
- VOVZXURTCKPRDQ-CQSZACIVSA-N n-[4-[chloro(difluoro)methoxy]phenyl]-6-[(3r)-3-hydroxypyrrolidin-1-yl]-5-(1h-pyrazol-5-yl)pyridine-3-carboxamide Chemical compound C1[C@H](O)CCN1C1=NC=C(C(=O)NC=2C=CC(OC(F)(F)Cl)=CC=2)C=C1C1=CC=NN1 VOVZXURTCKPRDQ-CQSZACIVSA-N 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- XULSCZPZVQIMFM-IPZQJPLYSA-N odevixibat Chemical compound C12=CC(SC)=C(OCC(=O)N[C@@H](C(=O)N[C@@H](CC)C(O)=O)C=3C=CC(O)=CC=3)C=C2S(=O)(=O)NC(CCCC)(CCCC)CN1C1=CC=CC=C1 XULSCZPZVQIMFM-IPZQJPLYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 125000001339 silanediyl group Chemical group [H][Si]([H])(*)* 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 238000001577 simple distillation Methods 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
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- LXEXBJXDGVGRAR-UHFFFAOYSA-N trichloro(trichlorosilyl)silane Chemical compound Cl[Si](Cl)(Cl)[Si](Cl)(Cl)Cl LXEXBJXDGVGRAR-UHFFFAOYSA-N 0.000 description 1
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 1
- 239000005052 trichlorosilane Substances 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Images
Classifications
-
- 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
- H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
- H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
- H01L21/02263—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase
- H01L21/02271—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition
- H01L21/0228—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition deposition by cyclic CVD, e.g. ALD, ALE, pulsed CVD
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/10—Compounds having one or more C—Si linkages containing nitrogen having a Si-N linkage
-
- 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
- H01L21/02164—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material being a silicon oxide, e.g. SiO2
-
- 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
-
- 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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- 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
- H01L21/02222—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 the compound being a silazane
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
- H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
- H01L21/02263—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase
- H01L21/02271—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition
- H01L21/02274—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 in the presence of a plasma [PECVD]
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
- H10K50/84—Passivation; Containers; Encapsulations
- H10K50/844—Encapsulations
Definitions
- the present invention relates to a composition for depositing a silicon-containing thin film and a method for manufacturing a silicon-containing thin film using the same, and more particularly, to a composition for depositing a silicon-containing thin film, containing a silylamine compound as a precursor for depositing a thin film, and a method for manufacturing a silicon-containing thin film using the same.
- a silicon-containing thin film is manufactured through various deposition processes in a semiconductor field to thereby be manufactured in various forms such as a silicon film, a silicon oxide film, a silicon nitride film, a silicon carbonitride film, and a silicon oxynitride film, and an application field of the silicon-containing thin film may be wide.
- the silicon oxide film and the silicon nitride film have a significantly excellent barrier property and oxidation resistance
- the silicon oxide film and the silicon nitride film are used as an insulating film, a diffusion barrier, a hard mask, an etch stop layer, a seed layer, a spacer, a trench isolation, an intermetallic dielectric material, and a passivation layer in manufacturing an apparatus.
- TFT thin film transistor
- MOCVD metal-organic chemical vapor deposition
- ALD atomic layer deposition
- LPCVD low-pressure chemical vapor deposition
- PECVD plasma-enhanced chemical vapor deposition
- PEALD plasma-enhanced atomic layer deposition
- a precursor used to form the silicon-containing thin film may include silane, silane compounds, aminosilane, and alkoxysilane compounds.
- Specific examples thereof may include silane chloride compounds such as dichlorosilane (SiH 2 Cl 2 ) and hexachlorodisilane (Cl 3 SiSiCl 3 ), trisilylamine (N(SiH 3 ) 3 ), bis-diethylaminosilane (H 2 Si(N(CH 2 CH 3 ) 2 ) 2 ), di-isopropylaminosilane (H 3 SiN(i-C 3 H 7 ) 2 ), and the like.
- silane chloride compounds such as dichlorosilane (SiH 2 Cl 2 ) and hexachlorodisilane (Cl 3 SiSiCl 3 ), trisilylamine (N(SiH 3 ) 3 ), bis-diethylaminosilane (H 2 Si(N(CH 2 CH 3 ) 2
- An object of the present invention is to provide a composition for depositing a silicon-containing thin film, containing a silylamine compound capable of being used as a precursor of the silicon-containing thin film.
- Another object of the present invention is to provide a method for manufacturing a silicon-containing thin film using the composition for depositing a silicon-containing thin film according to the present invention.
- a composition for depositing a silicon-containing thin film containing a silylamine compound having excellent cohesive force, a high deposition rate, and excellent physical and electrical properties as a precursor for depositing a silicon-containing thin film, the silylamine compound being represented by the following Chemical Formula 1.
- R 1 to R 4 are each independently hydrogen, (C1-C7)alkyl, or (C2-C7)alkenyl, or R 1 and R 2 , and R 3 and R 4 are each independently linked to each other to form a ring; and
- R 5 and R 6 are each independently (C1-C7)alkyl, or (C2-C7)alkenyl.)
- R 5 and R 6 may be each independently (C1-C5)alkyl.
- the silylamine compound represented by Chemical Formula 1 may be represented by the following Chemical Formula 2 or 3.
- R 11 to R 14 are each independently hydrogen, (C1-C5)alkyl, or (C2-C5)alkenyl;
- R 5 and R 6 are each independently (C1-C5)alkyl, or (C2-C5)alkenyl;
- n and m are each independently an integer of 1 to 7.
- R 5 and R 6 may be each independently (C1-C5)alkyl; and n and m may be each independently an integer of 1 to 4.
- the silylamine compound represented by Chemical Formula 1 may be selected from the following compounds but is not limited thereto.
- the silicon-containing thin film may be formed by an atomic layer deposition (ALD) method, a chemical vapor deposition (CVD) method, a metal-organic chemical vapor deposition (MOCVD) method, a low-pressure chemical vapor deposition (LPCVD) method, a plasma-enhanced chemical vapor deposition (PECVD) method, or a plasma-enhanced atomic layer deposition (PEALD) method, and be a silicon oxide (SiO 2 ) film, a silicon oxy carbide (SiOC) film, a silicon nitride (SiN) film, a silicon oxy nitride (SiON) film, a silicon carbonitride (SiCN) film, or a silicon carbide (SiC) film.
- ALD atomic layer deposition
- CVD chemical vapor deposition
- MOCVD metal-organic chemical vapor deposition
- LPCVD low-pressure chemical vapor deposition
- PECVD plasma-enh
- the method for manufacturing a silicon-containing thin film according to the present invention may include:
- composition for depositing a silicon-containing thin film according to the present invention with the substrate to adsorb the composition for depositing a silicon-containing thin film according to the present invention in the substrate;
- the reaction gas may be supplied after being activated by generating plasma at a plasma power of 50 to 1000 W.
- a composition for depositing a silicon-containing thin film contains a silylamine which is a liquid at room temperate and has high volatility and excellent thermal stability as a precursor, such that a high-quality silicon-containing thin film having high purity and durability may be provided under lower plasma power and film formation temperature conditions.
- an excellent deposition rate and excellent stress intensity may be implemented even under a low film formation temperature condition, and in a silicon-containing thin film manufactured thereby, contents of impurities such as carbon, oxygen, and hydrogen are minimized, such that the silicon-containing thin film may have a high purity, excellent physical and electrical properties, and excellent water vapor transmission rate.
- FIG. 1 is a view illustrating a result obtained by measuring a vapor pressure of a bis(dimethylaminomethylsilyl)amine compound prepared in Example 1.
- FIG. 2 is a view illustrating a thermogravimetric analysis result of the bis(dimethylaminomethylsilyl)amine compound prepared in Example 1.
- FIG. 3 is a view illustrating results obtained by performing infrared spectroscopic analysis on deposited films of silicon-containing thin films manufactured in Examples 2 to 8 and Comparative Example 2.
- FIG. 4 is a view illustrating results obtained by performing infrared spectroscopic analysis on deposited films of silicon-containing thin films manufactured in Examples 9 to 15.
- FIG. 5 is a result obtained by measuring a water vapor transmission rate of a silicon-containing thin film prepared in Example 6.
- FIG. 6 is a result obtained by measuring a water vapor transmission rate of a silicon-containing thin film prepared in Example 11.
- the present invention provides a composition for depositing a silicon-containing thin film containing a silylamine compound represented by the following Chemical Formula 1, which is a liquid at room temperature and has high volatility and excellent thermal stability to thereby be used as a significantly useful precursor of forming a silicon-containing thin film, wherein the silylamine compound is represented by the following Chemical Formula 1.
- R 1 to R 4 are each independently hydrogen, (C1-C7)alkyl, or (C2-C7)alkenyl, or R 1 and R 2 , and R 3 and R 4 are each independently linked to each other to form a ring; and
- R 5 and R 7 are each independently (C1-C7)alkyl, or (C2-C7)alkenyl.)
- silylamine compound contained in the composition for depositing a silicon-containing thin film amine has two aminosilyl functional groups as substituents, such that the silylamine compound, which is a liquid at room temperature, has high volatility. Therefore, the silylamine compound may be significantly usefully used to form the silicon-containing thin film.
- the silylamine compound according to the present invention is a compound having a silazane backbone, but necessarily has two aminosilyl functional groups ( and ), and only when each silicon atom of the aminosilyl functional groups necessarily has one hydrogen atom attached thereto, the silylamine compound may have useful effects as a precursor for depositing a thin film.
- R 5 and R 6 may be each independently (C1-C5)alkyl.
- the silylamine compound represented by Chemical Formula 1 may be represented by the following Chemical Formula 2 or 3.
- R 11 to R 14 are each independently hydrogen, (C1-C5)alkyl, or (C2-C5)alkenyl;
- R 5 and R 6 are each independently (C1-C5)alkyl, or (C2-C5)alkenyl;
- n and m are each independently an integer of 1 to 7.
- each silicon atom of two aminosilyl groups in the silazane backbone necessarily has one hydrogen atom attached thereto, such that the silylamine compound has a more excellent effect as the precursor for depositing a silicon-containing thin film.
- R 5 and R 6 may be each independently (C1-C5)alkyl or (C2-C5)alkenyl; and n and m are each independently an integer of 1 to 4. More preferably, R 5 and R 6 may be each independently (C1-C5)alkyl; and n and m are each independently an integer of 1 to 3.
- the silylamine compound represented by Chemical Formula 1 is a compound represented by the following Chemical Formula 4 in which both sides of an NH group are symmetric to each other in order to have more excellent effect as the precursor for depositing a silicon-containing thin film.
- R 1 and R 2 are each independently hydrogen, (C1-C7)alkyl, or (C2-C7)alkenyl, or R 1 and R 2 is linked to each other to form a ring;
- R 5 is (C1-C7)alkyl or (C2-C7)alkenyl.)
- the silylamine compound represented by Chemical Formula 1 may be selected from the following compounds.
- the composition for depositing a silicon-containing thin film according to the present invention contains the silylamine compound represented by Chemical Formula 1 as the precursor for depositing a thin film, and the silylamine compound in the composition for depositing a silicon-containing thin film may be contained in a content range in which the content may be recognized by those skilled in the art in consideration of film formation conditions, a thickness, properties, or the like, of the thin film.
- alkyl means a linear, branched, and cyclic saturated and unsaturated hydrocarbons having 1 to 7 carbon atoms, preferably, 1 to 5 carbon atoms, and more preferably 1 to 3 carbon atoms, and examples thereof may include methyl, ethyl, propyl, butyl, isobutyl, pentyl, and the like.
- halogen refers to a halogen element, and examples thereof include fluoro, chloro, bromo, iodo.
- alkenyl as a single group or a part of another group means a straight-chain, branched-chain, or cyclic hydrocarbon radical having 2 to 7 carbon atoms and one or more carbon-carbon double bonds.
- a more preferable alkenyl radical is a lower alkenyl radical having 2 to 5 carbon atoms.
- the most preferable lower alkenyl radical is a lower alkenyl radical having about 2 to 3 carbon atoms.
- an alkenyl group may be substituted at a random usable attachment point. Examples of the alkenyl radical include ethenyl, propenyl, allyl, butenyl, and 4-methylbutenyl.
- alkenyl and “lower alkenyl” include radicals having cis and trans orientations or alternatively, E and Z orientations.
- R 1 and R 2 , and R 3 and R 4 are each independently linked to each other to form a ring
- the phrase “R 1 and R 2 , and R 3 and R 4 are each independently linked to each other to form a ring” includes the case in which R 1 and R 2 are linked to each other to form a ring but R 3 and R 4 do not form a ring; the case in which on the contrary, R 1 and R 2 do not form a ring but R 3 and R 4 are linked to each other to form a ring; and the case in which R 1 and R 2 are linked to each other to form a ring and R 3 and R 4 are linked to each other to form a ring, wherein the formed ring may be an alicyclic or aromatic ring containing N, and preferably, an alicyclic ring.
- the silylamine compound represented by Chemical Formula 1 may be prepared by a method as long as the method may be recognized by those skilled in the art.
- the present invention provides a method for manufacturing a silicon-containing thin film using the composition for depositing a silicon-containing thin film according to the present invention.
- the composition for depositing a silicon-containing thin film according to the present invention containing the silylamine compound represented by Chemical Formula 1 which is a liquid at room temperature and has high volatility and excellent thermal stability as the precursor is used, such that the handling may be easy, it is possible to manufacture various thin films, and it is possible to manufacture a silicon-containing thin film having a high purity at a high deposition rate even at a low temperature and a low power.
- a silicon-containing thin film manufactured by the method according to the present invention has excellent durability and electric properties, and resistance against hydrogen fluoride and a water vapor transmission rate are also excellent.
- the silicon-containing thin film may be formed by any method as long as it may be recognized by those skilled in the art.
- the silicon-containing thin film may be formed by an atomic layer deposition (ALD) method, a chemical vapor deposition (CVD) method, a metal-organic chemical vapor deposition (MOCVD) method, a low-pressure chemical vapor deposition (LPCVD) method, a plasma enhanced chemical vapor deposition (PECVD) method, or a plasma enhanced atomic layer deposition (PEALD) method, but PECVD, ALD, or PEALD is more preferable in order to allow the thin film to be more easily deposited, and allow the manufactured thin film to have excellent properties.
- ALD atomic layer deposition
- CVD chemical vapor deposition
- MOCVD metal-organic chemical vapor deposition
- LPCVD low-pressure chemical vapor deposition
- PECVD plasma enhanced chemical vapor deposition
- PEALD plasma enhanced atomic layer deposition
- the silicon-containing thin film according to the present invention may be a silicon oxide (SiO2) film, a silicon oxy carbide (SiOC) film, a silicon nitride (SiN) film, a silicon oxy nitride (SiON) film, a silicon carbonitride (SiCN) film, or a silicon carbide (SiC) film, and various thin films having high quality may be manufactured.
- SiO2 silicon oxide
- SiOC silicon oxy carbide
- SiN silicon nitride
- SiON silicon oxy nitride
- SiCN silicon carbonitride
- SiC silicon carbide
- the method for manufacturing a silicon-containing thin film according to the present invention may include:
- composition for depositing a silicon-containing thin film according to the present invention contacting the composition for depositing a silicon-containing thin film according to the present invention with the substrate to adsorb the composition for depositing a silicon-containing thin film in the substrate;
- the method for manufacturing a silicon-containing thin film according to the present invention may include:
- reaction gas in step D) may remove a ligand of the silylamine compound contained in the composition for depositing a silicon-containing thin film to form a Si-O atomic layer.
- the reaction gas according to the exemplary embodiment may be supplied after being activated by generating plasma at a plasma power of 50 to 1000 W.
- deposition conditions may be adjusted depending on a structure or thermal properties of a desired thin film.
- the deposition condition according to the exemplary embodiment of the present invention may include an injection flow rate of the composition for depositing a silicon-containing thin film containing the silylamine compound, injection flow rates of the reaction gas and a carrier gas, pressure, RF power, the temperature of the substrate, and the like.
- the injection flow rate of the composition for depositing a silicon-containing thin film may be adjusted in a range of 10 to 1000 cc/min
- the injection flow rate of the carrier gas may be adjusted in a range of 10 to 1000 cc/min
- the injection flow rate of the reaction gas may be adjusted in a range of 1 to 1500 cc/min
- the pressure may be adjusted in a range of 0.5 to 10 torr
- the RF power may be adjusted in a range of 50 to 1000 W, preferably 400 to 800 W
- the temperature of the substrate may be adjusted in a range of 30 to 500 °C, preferably 50 to 200 °C, and more preferably 50 to 100°C, but the deposition conditions are not limited thereto.
- the reaction gas used in the method for manufacturing a silicon-containing thin film according to the present invention is not limited, but may be one selected from hydrogen (H 2 ), hydrazine (N 2 H 4 ), ozone (O 3 ), oxygen (O 2 ), nitrous oxide (N 2 O) ammonia (NH 3 ), nitrogen (N 2 ), silane (SiH 4 ), borane (BH 3 ), diborane (B 2 H 6 ), and phosphine (PH 3 ), or a mixed gas of one or more thereof, and the carrier gas may be one selected from nitrogen (N 2 ), argon (Ar), and helium (He), or a mixed gas of two or more thereof.
- the substrate used in the method for manufacturing a silicon-containing thin film according to the present invention may be a substrate containing one or more semiconductor materials selected from Si, Ge, SiGe, GaP, GaAs, SiC, SiGeC, InAs, and InP; a silicon-on-insulator (SOI) substrate; a quartz substrate; a glass substrate for a display; or a flexible plastic substrate made of polyimide, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polymethylmethacrylate (PMMA), polycarbonate (PC), polyethersulfone(PES), polyester, and the like, but is not limited thereto.
- SOI silicon-on-insulator
- the silicon-containing thin film may be directly formed on the substrate.
- a large number of conductive layers, dielectric layers, insulating layers, or the like, may also be formed between the substrate and the silicon-containing thin film.
- the composition for depositing a silicon-containing thin film according to the exemplary embodiment of the present invention may be used as an encapsulant of an organic light emitting diode (OLED).
- OLED organic light emitting diode
- deposition was performed by a plasma enhanced atomic layer deposition (PEALD) method known in the art using a commercialized 200 mm single wafer shower head type ALD apparatus (CN1, Atomic Premium).
- PEALD plasma enhanced atomic layer deposition
- PECVD plasma enhanced chemical vapor deposition
- CN1, Atomic Premium a commercialized 200 mm single wafer shower head type CVD apparatus
- a thickness of a deposited silicon-containing thin film was measured using an ellipsometer (OPTI-PROBE 2600, THERMA-WAVE), and properties of the thin film were analyzed using infrared spectroscopy (IFS66V/S & Hyperion 3000, Bruker Optics), X-ray photoelectron spectroscopy. Further, a water vapor transmission rate (WVTR) was measured using a WVTR analyzer (MOCON, Aquatran 2), an amount of nitrogen used in measurement was 20ml/min ⁇ Air, and a WVTR measurement area was set to 50 cm 2 . Stress was measured using a Frontier semiconductor (FSM500TC), a measurement area was set to 160 mm, and a thickness of a silicon wafer was set to 0.725 ⁇ m, such that properties of the thin film were analyzed.
- FSM500TC Frontier semiconductor
- a measurement area was set to 160 mm
- a thickness of a silicon wafer was set to 0.725 ⁇ m, such that properties of
- This mixture reaction solution was stirred for 3 hours, aluminum chloride (AlCl 3 ) was removed therefrom by filtration, and the formed chlorotrimethylsilane ((CH 3 ) 3 SiCl) and excessively added dichloro methylsilane (CH 3 SiHCl 2 ) were removed by simple distillation or distillation under reduced pressure. While stirring a recovered bis(chloromethylsilyl)amine ((CH 3 SiHCl) 2 NH)) solution and maintaining a temperature at -15°C, dimethylamine ((CH 3 ) 2 NH, 293.47 g (4.2 mol)) was slowly added thereto. After the addition was completed, the reaction solution was slowly heated to room temperature and stirred at room temperature for 6 hours.
- the formed white solid was removed by filtration, thereby obtaining a filtrate.
- a solvent was removed from this filtrate under reduced pressure, followed by distillation under reduced pressure, thereby obtaining bis(dimethylaminomethylsilyl)amine (CH 3 SiHN(CH 3 ) 2 ) 2 NH, 222.54 g (1.16 mol), yield: 75 %).
- Diisopropylamine 280.3 g (2.77 mol) was put into a 3 L of flame-dried Schlenk flask, and pentane was added thereto and stirred therewith. While stirring this solution and maintaining a temperature at -20°C, trichlorosilane (187.60 g (1.38 mol)) was slowly added thereto, and a reaction solution was slowly heated to room temperature. This mixture reaction solution was stirred at room temperature for 4 hours, and when a white solid was formed, the white solid was removed by filtration, thereby obtaining a filtrate.
- a solvent was removed from this filtrate under reduced pressure, and dimethoxymethane (895.89 g (11.77 mol)) was added thereto as a solvent, and lithium hydride (LiH, 27.53 g (3.46 mol)) was slowly added thereto. After addition, the mixture was refluxed for about 6 hours while maintaining a temperature of the flask at 50°C. After reflux, the flask was cooled to room temperature, and a white solid was removed by filtration, thereby obtaining a filtrate. A solvent was removed from the filtrate under reduced pressure, followed by distillation under reduced pressure, thereby obtaining diisopropylaminosilane (136.5 g, yield: 75 %).
- Film formation was evaluated using the silylamine compound prepared in Example 1 according to the present invention as a composition for forming a silicon oxide film in a general plasma enhanced atomic layer deposition (PEALD) apparatus using a plasma enhanced atomic layer deposition (PEALD) method known in the art.
- PEALD plasma enhanced atomic layer deposition
- As a reaction gas nitrous oxide was used together with plasma, and nitrogen corresponding to an inert gas was used for purging.
- the film was formed at reaction gas and plasma time of 0.5 seconds.
- a specific method for depositing a silicon oxide thin film was illustrated in Table 1.
- a thickness of a deposited thin film was measured using the Ellipsometer, formation of the silicon oxide thin film was analyzed using infrared spectroscopy, and a composition of the silicon oxide thin film was analyzed using X-ray photoelectron spectroscopy. Further, stress of the silicon oxide thin film was analyzed using a stress meter, and in order to measure a water vapor transmission rate (WVTR) of the thin film, the WVTR analyzer was used, thereby measuring the WVTR. Specific analysis results of the silicon oxide thin film were illustrated in Table 2, and a result obtained by analyzing the deposited film using infrared spectroscopy was illustrated in FIG. 3.
- a deposition rate of the silicon oxide thin film deposited so as to have a thickness of 700 ⁇ at a low temperature using the composition for depositing a silicon-containing thin film, containing bis(dimethylaminomethylsilyl)amine prepared according to the present invention was 1.87 to 1.97 ⁇ /cycle, such that the deposition rate was significantly excellent.
- the water vapor transmission rates of the silicon oxide films formed in Examples 6 were 4.5E-3 (g/[m 2 -day]), such that the silicon oxide films have excellent moisture proof properties. Therefore, it is judged that the silicon oxide thin films may be usefully used in entire application fields of the silicon oxide thin film, particularly, as an encapsulant of an organic light emitting diode (OLED).
- OLED organic light emitting diode
- FIG. 5 A result obtained by measuring a water vapor transmission rate of a silicon-containing thin film prepared in Example 6 was illustrated in FIG. 5.
- the water vapor transmission rate was constantly maintained for a long period of time as illustrated in FIG. 5. Therefore, it is judged that the compound suggested in the present invention may be significantly useful in an OLED device in which an encapsulation technology of blocking oxygen and moisture is important.
- Film formation was evaluated using the plasma enhanced atomic layer deposition (PEALD) method known in the art under the same deposition conditions as in Example 2 except that diisopropylaminosilane prepared in Comparative Example 1 was used, a heating temperature of the precursor was 20°C, and the number of deposition was 590 cycles as illustrated in the following Table 1.
- the deposited thin film was analyzed by the same analysis method as in Example 2 under the same conditions as in Example 2, such that analysis results were secured. In order to perform measurement at the same thickness as those of the thin films formed in Examples 2 to 8, the number of deposition was changed.
- a specific method for depositing a silicon oxide thin film was illustrated in the following Table 1, and properties of the deposited thin films were illustrated in Table 2.
- a deposition rate was 1.19 ⁇ /cycle, and a water vapor transmission rate (WVTR) was 8.0E-2 (g/[m 2 -day]), which were lower than those of the bis(dimethylaminomethylsilyl)amine in Example 2.
- Example 2 Film formation was evaluated using the silylamine compound prepared in Example 1 according to the present invention as a composition for forming a silicon nitride film in a general plasma enhanced atomic layer deposition (PEALD) apparatus using a plasma enhanced atomic layer deposition (PEALD) method known in the art.
- PEALD plasma enhanced atomic layer deposition
- As a reaction gas nitrogen and ammonia were used together with plasma as first reaction gas, and nitrogen was used as a second reaction gas. The nitrogen corresponding to an inert gas was used for purging.
- a specific method for depositing a silicon nitride thin film was illustrated in Table 3.
- a thickness of a deposited thin film was measured using the Ellipsometer, formation of the silicon nitride thin film was analyzed using infrared spectroscopy, and a composition of the silicon nitride thin film was analyzed using X-ray photoelectron spectroscopy. Further, in order to measure a water vapor transmission rate (WVTR) of the thin film, the WVTR analyzer was used, thereby measuring the WVTR. Specific analysis results of the silicon nitride thin film were illustrated in the following Table 4, and results obtained by analyzing the deposited film using infrared spectroscopy were illustrated in FIG. 4.
- Example 9 Film formation was evaluated using a plasma enhanced atomic layer deposition (PEALD) method known in the art in the same manner as in Example 9 except for changing deposition conditions as in Table 3, and the deposited thin film was analyzed by the same analysis method as in Example 9 under the same conditions as in Example 9, such that analysis results were secured.
- PEALD plasma enhanced atomic layer deposition
- a specific method for depositing a silicon nitride thin film and analysis results were illustrated in the following Tables 3 and 4. Further, the deposited films were analyzed using infrared spectroscopy, and the result was illustrated in FIG. 4. As a result, it may be appreciated that the thin film manufactured in Examples 10 to 15 were silicon nitride thin films.
- Example 11 a result obtained by measuring a water vapor transmission rate of a silicon-containing thin film prepared in Example 11 was illustrated in FIG. 6.
- the water vapor transmission rate was constantly maintained for a long period of time as illustrated in FIG. 6. Therefore, it is judged that the compound suggested in the present invention may be significantly usefully used in an OLED device in which an encapsulation technology of blocking oxygen and moisture is important.
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Abstract
Provided are a composition containing a silylamine compound and a method for manufacturing a silicon-containing thin film using the same, and more particularly, a composition for depositing a silicon-containing thin film, containing a silylamine compound capable of forming a silicon-containing thin film having a significantly excellent water vapor transmission rate to thereby be usefully used as a precursor of the silicon-containing thin film and an encapsulant of a display, and a method for manufacturing a silicon-containing thin film using the same.
Description
The present invention relates to a composition for depositing a silicon-containing thin film and a method for manufacturing a silicon-containing thin film using the same, and more particularly, to a composition for depositing a silicon-containing thin film, containing a silylamine compound as a precursor for depositing a thin film, and a method for manufacturing a silicon-containing thin film using the same.
A silicon-containing thin film is manufactured through various deposition processes in a semiconductor field to thereby be manufactured in various forms such as a silicon film, a silicon oxide film, a silicon nitride film, a silicon carbonitride film, and a silicon oxynitride film, and an application field of the silicon-containing thin film may be wide.
Particularly, since the silicon oxide film and the silicon nitride film have a significantly excellent barrier property and oxidation resistance, the silicon oxide film and the silicon nitride film are used as an insulating film, a diffusion barrier, a hard mask, an etch stop layer, a seed layer, a spacer, a trench isolation, an intermetallic dielectric material, and a passivation layer in manufacturing an apparatus.
Recently, a polycrystalline silicon thin film has been used in a thin film transistor (TFT), a solar cell, and the like, and an application field thereof has been gradually diversified.
As a representative technology for manufacturing a silicon-containing thin film known in the art, there are a metal-organic chemical vapor deposition (MOCVD) method for reacting a gas-type silicon precursor and a reaction gas with each other to form a film on a surface of a substrate or directly reacting the gas-type silicon precursor and the reaction gas with each other on the surface to form a film and an atomic layer deposition (ALD) method for physically or chemically adsorbing a gas-type silicon precursor and sequentially injecting a reaction gas to form a film. Various technologies for manufacturing a thin film such as a low-pressure chemical vapor deposition (LPCVD) method applying the above-mentioned method, a plasma-enhanced chemical vapor deposition (PECVD) method and a plasma-enhanced atomic layer deposition (PEALD) method capable of performing deposition at a low temperature, and the like, are applied to processes for manufacturing next-generation semiconductors and display devices to thereby be used to form a ultra-fine pattern and deposit an ultra-thin film having uniform and excellent properties at a nano-scale thickness.
Representative examples of a precursor used to form the silicon-containing thin film may include silane, silane compounds, aminosilane, and alkoxysilane compounds. Specific examples thereof may include silane chloride compounds such as dichlorosilane (SiH2Cl2) and hexachlorodisilane (Cl3SiSiCl3), trisilylamine (N(SiH3)3), bis-diethylaminosilane (H2Si(N(CH2CH3)2)2), di-isopropylaminosilane (H3SiN(i-C3H7)2), and the like. These precursors have been used in mass-production processes for manufacturing semiconductors and displays.
However, due to fineness of devices caused by ultra-high integration of the devices and an increase in aspect ratio, and diversification of materials of the devices, a technology of forming an ultra-fin thin film having a uniform and thin thickness and excellent electrical properties at a low temperature to be desired has been required. Therefore, a high-temperature process (600℃ or more) using an existing silicon precursor, a step coverage, etching properties, and physical and electric properties of the thin film have become problems, such that the development of a novel more excellent silicon precursor and a method for forming a thin film have been studied.
An object of the present invention is to provide a composition for depositing a silicon-containing thin film, containing a silylamine compound capable of being used as a precursor of the silicon-containing thin film.
Another object of the present invention is to provide a method for manufacturing a silicon-containing thin film using the composition for depositing a silicon-containing thin film according to the present invention.
In one general aspect, there is provided a composition for depositing a silicon-containing thin film, containing a silylamine compound having excellent cohesive force, a high deposition rate, and excellent physical and electrical properties as a precursor for depositing a silicon-containing thin film, the silylamine compound being represented by the following Chemical Formula 1.
[Chemical Formula 1]
(In Chemical Formula 1,
R1 to R4 are each independently hydrogen, (C1-C7)alkyl, or (C2-C7)alkenyl, or R1 and R2, and R3 and R4 are each independently linked to each other to form a ring; and
R5 and R6 are each independently (C1-C7)alkyl, or (C2-C7)alkenyl.)
Preferably, in the silylamine compound represented by Chemical Formula 1 according to the exemplary embodiment of the present invention, R5 and R6 may be each independently (C1-C5)alkyl.
Preferably, the silylamine compound represented by Chemical Formula 1 according to the exemplary embodiment of the present invention may be represented by the following Chemical Formula 2 or 3.
[Chemical Formula 2]
[Chemical Formula 3]
(In Chemical Formula 2 or 3,
R11 to R14 are each independently hydrogen, (C1-C5)alkyl, or (C2-C5)alkenyl;
R5 and R6 are each independently (C1-C5)alkyl, or (C2-C5)alkenyl; and
n and m are each independently an integer of 1 to 7.)
Preferably, in Chemical Formula 2 or 3 according to the exemplary embodiment of the present invention, R5 and R6 may be each independently (C1-C5)alkyl; and n and m may be each independently an integer of 1 to 4.
The silylamine compound represented by Chemical Formula 1 according to the exemplary embodiment of the present invention may be selected from the following compounds but is not limited thereto.
In another general aspect, there is provided a method for manufacturing a silicon-containing thin film using the composition for depositing a silicon-containing thin film according to the exemplary embodiment of the present invention.
In the method for manufacturing a silicon-containing thin film, the silicon-containing thin film may be formed by an atomic layer deposition (ALD) method, a chemical vapor deposition (CVD) method, a metal-organic chemical vapor deposition (MOCVD) method, a low-pressure chemical vapor deposition (LPCVD) method, a plasma-enhanced chemical vapor deposition (PECVD) method, or a plasma-enhanced atomic layer deposition (PEALD) method, and be a silicon oxide (SiO2) film, a silicon oxy carbide (SiOC) film, a silicon nitride (SiN) film, a silicon oxy nitride (SiON) film, a silicon carbonitride (SiCN) film, or a silicon carbide (SiC) film.
More specifically, the method for manufacturing a silicon-containing thin film according to the present invention may include:
a) maintaining a temperature of a substrate mounted in a chamber at 30 to 500℃;
b) contacting the composition for depositing a silicon-containing thin film according to the present invention with the substrate to adsorb the composition for depositing a silicon-containing thin film according to the present invention in the substrate; and
c) injecting a reaction gas into the substrate in which the composition for depositing a silicon-containing thin film is adsorbed to form a silicon-containing thin film.
In the method for manufacturing a silicon-containing thin film, the reaction gas may be supplied after being activated by generating plasma at a plasma power of 50 to 1000 W.
A composition for depositing a silicon-containing thin film contains a silylamine which is a liquid at room temperate and has high volatility and excellent thermal stability as a precursor, such that a high-quality silicon-containing thin film having high purity and durability may be provided under lower plasma power and film formation temperature conditions.
Further, in a method for manufacturing a silicon-containing thin film using the composition for depositing a silicon-containing thin film according to the present invention, an excellent deposition rate and excellent stress intensity may be implemented even under a low film formation temperature condition, and in a silicon-containing thin film manufactured thereby, contents of impurities such as carbon, oxygen, and hydrogen are minimized, such that the silicon-containing thin film may have a high purity, excellent physical and electrical properties, and excellent water vapor transmission rate.
FIG. 1 is a view illustrating a result obtained by measuring a vapor pressure of a bis(dimethylaminomethylsilyl)amine compound prepared in Example 1.
FIG. 2 is a view illustrating a thermogravimetric analysis result of the bis(dimethylaminomethylsilyl)amine compound prepared in Example 1.
FIG. 3 is a view illustrating results obtained by performing infrared spectroscopic analysis on deposited films of silicon-containing thin films manufactured in Examples 2 to 8 and Comparative Example 2.
FIG. 4 is a view illustrating results obtained by performing infrared spectroscopic analysis on deposited films of silicon-containing thin films manufactured in Examples 9 to 15.
FIG. 5 is a result obtained by measuring a water vapor transmission rate of a silicon-containing thin film prepared in Example 6.
FIG. 6 is a result obtained by measuring a water vapor transmission rate of a silicon-containing thin film prepared in Example 11.
The present invention provides a composition for depositing a silicon-containing thin film containing a silylamine compound represented by the following Chemical Formula 1, which is a liquid at room temperature and has high volatility and excellent thermal stability to thereby be used as a significantly useful precursor of forming a silicon-containing thin film, wherein the silylamine compound is represented by the following Chemical Formula 1.
[Chemical Formula 1]
(In Chemical Formula 1,
R1 to R4 are each independently hydrogen, (C1-C7)alkyl, or (C2-C7)alkenyl, or R1 and R2, and R3 and R4 are each independently linked to each other to form a ring; and
R5 and R7 are each independently (C1-C7)alkyl, or (C2-C7)alkenyl.)
In the silylamine compound contained in the composition for depositing a silicon-containing thin film, amine has two aminosilyl functional groups as substituents, such that the silylamine compound, which is a liquid at room temperature, has high volatility. Therefore, the silylamine compound may be significantly usefully used to form the silicon-containing thin film.
More specifically, the silylamine compound according to the present invention is a compound having a silazane backbone, but necessarily has two aminosilyl functional groups ( and ), and only when each silicon atom of the aminosilyl functional groups necessarily has one hydrogen atom attached thereto, the silylamine compound may have useful effects as a precursor for depositing a thin film.
Preferably, in the silylamine compound represented by Chemical Formula 1 according to the exemplary embodiment of the present invention, R5 and R6 may be each independently (C1-C5)alkyl.
Preferably, the silylamine compound represented by Chemical Formula 1 according to the exemplary embodiment of the present invention may be represented by the following Chemical Formula 2 or 3.
[Chemical Formula 2]
[Chemical Formula 3]
(In Chemical Formulas 2 and 3,
R11 to R14 are each independently hydrogen, (C1-C5)alkyl, or (C2-C5)alkenyl;
R5 and R6 are each independently (C1-C5)alkyl, or (C2-C5)alkenyl; and
n and m are each independently an integer of 1 to 7.)
In the silylamine compound according to the present invention, each silicon atom of two aminosilyl groups in the silazane backbone necessarily has one hydrogen atom attached thereto, such that the silylamine compound has a more excellent effect as the precursor for depositing a silicon-containing thin film.
Preferably, in Chemical Formula 2 or 3 according to the exemplary embodiment of the present invention, R5 and R6 may be each independently (C1-C5)alkyl or (C2-C5)alkenyl; and n and m are each independently an integer of 1 to 4. More preferably, R5 and R6 may be each independently (C1-C5)alkyl; and n and m are each independently an integer of 1 to 3.
It is more preferable that the silylamine compound represented by Chemical Formula 1 is a compound represented by the following Chemical Formula 4 in which both sides of an NH group are symmetric to each other in order to have more excellent effect as the precursor for depositing a silicon-containing thin film.
[Chemical Formula 4]
(In Chemical Formula 4,
R1 and R2 are each independently hydrogen, (C1-C7)alkyl, or (C2-C7)alkenyl, or R1 and R2 is linked to each other to form a ring; and
R5 is (C1-C7)alkyl or (C2-C7)alkenyl.)
The silylamine compound represented by Chemical Formula 1 according to the exemplary embodiment of the present invention may be selected from the following compounds.
The composition for depositing a silicon-containing thin film according to the present invention contains the silylamine compound represented by Chemical Formula 1 as the precursor for depositing a thin film, and the silylamine compound in the composition for depositing a silicon-containing thin film may be contained in a content range in which the content may be recognized by those skilled in the art in consideration of film formation conditions, a thickness, properties, or the like, of the thin film.
As used herein, the term "alkyl" means a linear, branched, and cyclic saturated and unsaturated hydrocarbons having 1 to 7 carbon atoms, preferably, 1 to 5 carbon atoms, and more preferably 1 to 3 carbon atoms, and examples thereof may include methyl, ethyl, propyl, butyl, isobutyl, pentyl, and the like.
As used herein, "halogen" refers to a halogen element, and examples thereof include fluoro, chloro, bromo, iodo.
As disclosed herein, the term "alkenyl" as a single group or a part of another group means a straight-chain, branched-chain, or cyclic hydrocarbon radical having 2 to 7 carbon atoms and one or more carbon-carbon double bonds. A more preferable alkenyl radical is a lower alkenyl radical having 2 to 5 carbon atoms. The most preferable lower alkenyl radical is a lower alkenyl radical having about 2 to 3 carbon atoms. Further, an alkenyl group may be substituted at a random usable attachment point. Examples of the alkenyl radical include ethenyl, propenyl, allyl, butenyl, and 4-methylbutenyl. The terms "alkenyl" and "lower alkenyl" include radicals having cis and trans orientations or alternatively, E and Z orientations.
As used herein, the phrase "R1 and R2, and R3 and R4 are each independently linked to each other to form a ring" includes the case in which R1 and R2 are linked to each other to form a ring but R3 and R4 do not form a ring; the case in which on the contrary, R1 and R2 do not form a ring but R3 and R4 are linked to each other to form a ring; and the case in which R1 and R2 are linked to each other to form a ring and R3 and R4 are linked to each other to form a ring, wherein the formed ring may be an alicyclic or aromatic ring containing N, and preferably, an alicyclic ring.
The silylamine compound represented by Chemical Formula 1 according to the exemplary embodiment of the present invention may be prepared by a method as long as the method may be recognized by those skilled in the art.
In addition, the present invention provides a method for manufacturing a silicon-containing thin film using the composition for depositing a silicon-containing thin film according to the present invention.
In the method for manufacturing a silicon-containing thin film according to the present invention, the composition for depositing a silicon-containing thin film according to the present invention, containing the silylamine compound represented by Chemical Formula 1 which is a liquid at room temperature and has high volatility and excellent thermal stability as the precursor is used, such that the handling may be easy, it is possible to manufacture various thin films, and it is possible to manufacture a silicon-containing thin film having a high purity at a high deposition rate even at a low temperature and a low power.
Further, a silicon-containing thin film manufactured by the method according to the present invention has excellent durability and electric properties, and resistance against hydrogen fluoride and a water vapor transmission rate are also excellent.
In the method for manufacturing a silicon-containing thin film according to the present invention, the silicon-containing thin film may be formed by any method as long as it may be recognized by those skilled in the art. However, preferably, the silicon-containing thin film may be formed by an atomic layer deposition (ALD) method, a chemical vapor deposition (CVD) method, a metal-organic chemical vapor deposition (MOCVD) method, a low-pressure chemical vapor deposition (LPCVD) method, a plasma enhanced chemical vapor deposition (PECVD) method, or a plasma enhanced atomic layer deposition (PEALD) method, but PECVD, ALD, or PEALD is more preferable in order to allow the thin film to be more easily deposited, and allow the manufactured thin film to have excellent properties.
The silicon-containing thin film according to the present invention may be a silicon oxide (SiO2) film, a silicon oxy carbide (SiOC) film, a silicon nitride (SiN) film, a silicon oxy nitride (SiON) film, a silicon carbonitride (SiCN) film, or a silicon carbide (SiC) film, and various thin films having high quality may be manufactured.
More specifically, the method for manufacturing a silicon-containing thin film according to the present invention may include:
a) maintaining a temperature of a substrate mounted in a chamber at 30 to 500℃;
b) contacting the composition for depositing a silicon-containing thin film according to the present invention with the substrate to adsorb the composition for depositing a silicon-containing thin film in the substrate; and
c) injecting a reaction gas into the substrate in which the composition for depositing a silicon-containing thin film is adsorbed to form a silicon-containing thin film.
More specifically, the method for manufacturing a silicon-containing thin film according to the present invention may include:
A) maintaining a temperature of a substrate mounted in a chamber at 30 to 500℃;
B) contacting the composition for depositing a silicon-containing thin film with the substrate to adsorb the composition for depositing a silicon-containing thin film in the substrate;
C) purging the remaining composition for depositing a silicon-containing thin film and by-products;
D) injecting a reaction gas into the substrate in which the composition for depositing a silicon-containing thin film is adsorbed to form a silicon-containing thin film; and
E) purging the remaining reaction gas and by-products, wherein the reaction gas in step D) may remove a ligand of the silylamine compound contained in the composition for depositing a silicon-containing thin film to form a Si-O atomic layer.
Preferably, the reaction gas according to the exemplary embodiment may be supplied after being activated by generating plasma at a plasma power of 50 to 1000 W.
In the method for manufacturing a silicon-containing thin film according to the exemplary embodiment of the present invention, deposition conditions may be adjusted depending on a structure or thermal properties of a desired thin film. Examples of the deposition condition according to the exemplary embodiment of the present invention may include an injection flow rate of the composition for depositing a silicon-containing thin film containing the silylamine compound, injection flow rates of the reaction gas and a carrier gas, pressure, RF power, the temperature of the substrate, and the like. As non-restrictive examples of the deposition conditions, the injection flow rate of the composition for depositing a silicon-containing thin film may be adjusted in a range of 10 to 1000 cc/min, the injection flow rate of the carrier gas may be adjusted in a range of 10 to 1000 cc/min, the injection flow rate of the reaction gas may be adjusted in a range of 1 to 1500 cc/min, the pressure may be adjusted in a range of 0.5 to 10 torr, the RF power may be adjusted in a range of 50 to 1000 W, preferably 400 to 800 W, and the temperature of the substrate may be adjusted in a range of 30 to 500 ℃, preferably 50 to 200 ℃, and more preferably 50 to 100℃, but the deposition conditions are not limited thereto.
The reaction gas used in the method for manufacturing a silicon-containing thin film according to the present invention is not limited, but may be one selected from hydrogen (H2), hydrazine (N2H4), ozone (O3), oxygen (O2), nitrous oxide (N2O) ammonia (NH3), nitrogen (N2), silane (SiH4), borane (BH3), diborane (B2H6), and phosphine (PH3), or a mixed gas of one or more thereof, and the carrier gas may be one selected from nitrogen (N2), argon (Ar), and helium (He), or a mixed gas of two or more thereof.
The substrate used in the method for manufacturing a silicon-containing thin film according to the present invention may be a substrate containing one or more semiconductor materials selected from Si, Ge, SiGe, GaP, GaAs, SiC, SiGeC, InAs, and InP; a silicon-on-insulator (SOI) substrate; a quartz substrate; a glass substrate for a display; or a flexible plastic substrate made of polyimide, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polymethylmethacrylate (PMMA), polycarbonate (PC), polyethersulfone(PES), polyester, and the like, but is not limited thereto.
Further, the silicon-containing thin film may be directly formed on the substrate. Alternatively, a large number of conductive layers, dielectric layers, insulating layers, or the like, may also be formed between the substrate and the silicon-containing thin film.
Preferably, the composition for depositing a silicon-containing thin film according to the exemplary embodiment of the present invention may be used as an encapsulant of an organic light emitting diode (OLED).
The present invention will be described in detail with reference to the following Examples. The terms and words used in the present specification and claims should not be interpreted as being limited to typical meanings or dictionary definitions, but should be interpreted as having meanings and concepts relevant to the technical scope of the present invention based on the rule according to which an inventor can appropriately define the concept of the term to describe most appropriately the best method he or she knows for carrying out the present invention.
Therefore, configurations described in the embodiments and shown in the drawings of the present specification indicate only the most preferred example rather than indicating all the technical ideas of the present invention and therefore, it is to be understood that various equivalents and modifications that can replace the above configurations may be present.
Further, in all the following Examples, deposition was performed by a plasma enhanced atomic layer deposition (PEALD) method known in the art using a commercialized 200 mm single wafer shower head type ALD apparatus (CN1, Atomic Premium). In addition, deposition was performed by a plasma enhanced chemical vapor deposition (PECVD) method known in the art using a commercialized 200 mm single wafer shower head type CVD (PECVD) apparatus (CN1, Atomic Premium).
A thickness of a deposited silicon-containing thin film was measured using an ellipsometer (OPTI-PROBE 2600, THERMA-WAVE), and properties of the thin film were analyzed using infrared spectroscopy (IFS66V/S & Hyperion 3000, Bruker Optics), X-ray photoelectron spectroscopy. Further, a water vapor transmission rate (WVTR) was measured using a WVTR analyzer (MOCON, Aquatran 2), an amount of nitrogen used in measurement was 20ml/minㆍAir, and a WVTR measurement area was set to 50 cm2. Stress was measured using a Frontier semiconductor (FSM500TC), a measurement area was set to 160 mm, and a thickness of a silicon wafer was set to 0.725 ㎛, such that properties of the thin film were analyzed.
[Example 1] Preparation of Bis(dimethylaminomethylsilyl)amine
Under an anhydrous and inert atmosphere, after putting hexamethyl disilazane (((CH3)3Si)2NH, 250 g (1.55 mol)) and aluminum chloride (AlCl3, 10 g (0.075 mol)) into a 2000 mL flame-dried flask, dichloro methylsilane (CH3SiHCl2, 713.19g (6.20 mol)) was slowly added thereto while stirring the mixture and maintaining a temperature at 25℃. Then, a reaction solution was slowly heated to 40℃. This mixture reaction solution was stirred for 3 hours, aluminum chloride (AlCl3) was removed therefrom by filtration, and the formed chlorotrimethylsilane ((CH3)3SiCl) and excessively added dichloro methylsilane (CH3SiHCl2) were removed by simple distillation or distillation under reduced pressure. While stirring a recovered bis(chloromethylsilyl)amine ((CH3SiHCl)2NH)) solution and maintaining a temperature at -15℃, dimethylamine ((CH3)2NH, 293.47 g (4.2 mol)) was slowly added thereto. After the addition was completed, the reaction solution was slowly heated to room temperature and stirred at room temperature for 6 hours. The formed white solid was removed by filtration, thereby obtaining a filtrate. A solvent was removed from this filtrate under reduced pressure, followed by distillation under reduced pressure, thereby obtaining bis(dimethylaminomethylsilyl)amine (CH3SiHN(CH3)2)2NH, 222.54 g (1.16 mol), yield: 75 %).
1H-NMR(inC6D6):δ 0.12(s, 6H, ((CH3SiHN(CH3)2)2NH), 2.47(s, 12H, ((CH3SiHN(CH3)2)2NH), 4.43(m, 2H, ((CH3SiHN(CH3)2)2NH), 2.0(b, 1H, ((CH3SiHN(CH3)2)2NH).
[Comparative Example 1] Preparation of Diisopropylaminosilane
Diisopropylamine (280.3 g (2.77 mol)) was put into a 3 L of flame-dried Schlenk flask, and pentane was added thereto and stirred therewith. While stirring this solution and maintaining a temperature at -20℃, trichlorosilane (187.60 g (1.38 mol)) was slowly added thereto, and a reaction solution was slowly heated to room temperature. This mixture reaction solution was stirred at room temperature for 4 hours, and when a white solid was formed, the white solid was removed by filtration, thereby obtaining a filtrate. A solvent was removed from this filtrate under reduced pressure, and dimethoxymethane (895.89 g (11.77 mol)) was added thereto as a solvent, and lithium hydride (LiH, 27.53 g (3.46 mol)) was slowly added thereto. After addition, the mixture was refluxed for about 6 hours while maintaining a temperature of the flask at 50℃. After reflux, the flask was cooled to room temperature, and a white solid was removed by filtration, thereby obtaining a filtrate. A solvent was removed from the filtrate under reduced pressure, followed by distillation under reduced pressure, thereby obtaining diisopropylaminosilane (136.5 g, yield: 75 %).
1H-NMR(inC6D6):δ 0.93(d, 6H, (SiH3(N(CH(CH3)2)), 2.47(m, 2H, (SiH3(N(CH(CH3)2)), 5.65(s, 3H, (SiH3(NCH(CH3))2)
[Example 2] Manufacturing of Silicon Oxide Thin Film by PEALD Using Bis(dimethylaminomethylsilyl)amine
Film formation was evaluated using the silylamine compound prepared in Example 1 according to the present invention as a composition for forming a silicon oxide film in a general plasma enhanced atomic layer deposition (PEALD) apparatus using a plasma enhanced atomic layer deposition (PEALD) method known in the art. As a reaction gas, nitrous oxide was used together with plasma, and nitrogen corresponding to an inert gas was used for purging. The film was formed at reaction gas and plasma time of 0.5 seconds. A specific method for depositing a silicon oxide thin film was illustrated in Table 1.
A thickness of a deposited thin film was measured using the Ellipsometer, formation of the silicon oxide thin film was analyzed using infrared spectroscopy, and a composition of the silicon oxide thin film was analyzed using X-ray photoelectron spectroscopy. Further, stress of the silicon oxide thin film was analyzed using a stress meter, and in order to measure a water vapor transmission rate (WVTR) of the thin film, the WVTR analyzer was used, thereby measuring the WVTR. Specific analysis results of the silicon oxide thin film were illustrated in Table 2, and a result obtained by analyzing the deposited film using infrared spectroscopy was illustrated in FIG. 3.
[Examples 3 to 8] Manufacturing of Silicon Oxide Thin Films by PEALD Using Bis(dimethylaminomethylsilyl)amine
Film formation was evaluated using the plasma enhanced atomic layer deposition (PEALD) method known in the art in the same manner as in Example 2 except that deposition conditions were changed as illustrated in Table 1 in Example 2. Further, results obtained by analyzing the deposited films using infrared spectroscopy were illustrated in a graph of FIG. 3.
As appreciated in Examples 2 to 8 according to the present invention, a deposition rate of the silicon oxide thin film deposited so as to have a thickness of 700 Å at a low temperature using the composition for depositing a silicon-containing thin film, containing bis(dimethylaminomethylsilyl)amine prepared according to the present invention was 1.87 to 1.97 Å/cycle, such that the deposition rate was significantly excellent.
More specifically, it may be appreciated that as compared to Comparative Example 2 in which a composition for depositing a silicon-containing thin film, containing diisopropylaminosilane as a precursor of a thin film, in Examples 2 to 8 in which the composition for depositing a silicon-containing thin film, containing a silylamine compound according to the present invention as a precursor was used, the deposition rate of the thin film was more excellent, and the water vapor transmission rate was also excellent, which may have a significant influence on increase in productivity in forming the silicon-containing thin film. As the results of analyzing the deposited thin films using the infrared spectroscopy in FIG. 3, it may be appreciated that all the thin films formed in Examples 2 to 8 were silicon oxide films. Further, the water vapor transmission rates of the silicon oxide films formed in Examples 6 were 4.5E-3 (g/[m2-day]), such that the silicon oxide films have excellent moisture proof properties. Therefore, it is judged that the silicon oxide thin films may be usefully used in entire application fields of the silicon oxide thin film, particularly, as an encapsulant of an organic light emitting diode (OLED).
A result obtained by measuring a water vapor transmission rate of a silicon-containing thin film prepared in Example 6 was illustrated in FIG. 5. The water vapor transmission rate was constantly maintained for a long period of time as illustrated in FIG. 5. Therefore, it is judged that the compound suggested in the present invention may be significantly useful in an OLED device in which an encapsulation technology of blocking oxygen and moisture is important.
[Comparative Example 2] Manufacturing of Silicon Oxide Thin Film by PEALD Using Diisopropylaminosilane
Film formation was evaluated using the plasma enhanced atomic layer deposition (PEALD) method known in the art under the same deposition conditions as in Example 2 except that diisopropylaminosilane prepared in Comparative Example 1 was used, a heating temperature of the precursor was 20℃, and the number of deposition was 590 cycles as illustrated in the following Table 1. The deposited thin film was analyzed by the same analysis method as in Example 2 under the same conditions as in Example 2, such that analysis results were secured. In order to perform measurement at the same thickness as those of the thin films formed in Examples 2 to 8, the number of deposition was changed. A specific method for depositing a silicon oxide thin film was illustrated in the following Table 1, and properties of the deposited thin films were illustrated in Table 2. As illustrated in Table 2, a deposition rate was 1.19 Å/cycle, and a water vapor transmission rate (WVTR) was 8.0E-2 (g/[m2-day]), which were lower than those of the bis(dimethylaminomethylsilyl)amine in Example 2.
Temperature of Substrate(℃) | Precursor | Purge | Reaction Gas and Plasma | Reaction Gas Purge | No. of Deposition | Process Time(sec) | ||||||
Heating Temperature(℃) | Injection Time(sec) | Flow Rate (sccm) | Time (sec) | Flow Rate (sccm) | RF Power (W) | Time (sec) | Time (sec) | Flow Rate (sccm) | Cycle | |||
Example 2 | 90 | 70 | 0.1 | 600 | 0.4 | 800 | 400 | 0.5 | 0.1 | 300 | 380 | 418 |
Example 3 | 90 | 70 | 0.1 | 600 | 0.4 | 800 | 400 | 0.7 | 0.1 | 300 | 363 | 471.9 |
Example 4 | 90 | 70 | 0.1 | 600 | 0.4 | 800 | 400 | 0.9 | 0.1 | 300 | 370 | 555 |
Example5 | 90 | 70 | 0.1 | 600 | 0.4 | 800 | 400 | 1.2 | 0.1 | 300 | 370 | 666 |
Example 6 | 90 | 70 | 0.1 | 600 | 0.4 | 400 | 400 | 0.9 | 0.1 | 300 | 370 | 555 |
Example 7 | 90 | 70 | 0.1 | 600 | 0.4 | 1400 | 400 | 0.9 | 0.1 | 300 | 370 | 555 |
Example 8 | 90 | 70 | 0.1 | 600 | 0.4 | 800 | 500 | 0.9 | 0.1 | 300 | 370 | 555 |
Comparative Example 2 | 90 | 20 | 0.1 | 600 | 0.4 | 800 | 400 | 0.5 | 0.1 | 300 | 590 | 649 |
Variable | Deposition Rate | Thickness of Thin Film | Refractive Index | O/Si Composition Ratio | Stress of Film | WVTR | |
(Å/cycle) | (Å) | - | - | (MPa) | (g/[m2-day]) | ||
Example 2 | Plasma Time of 0.5 sec | 1.87 | 710 | 1.46 | 1.73 | -134 | Unmeasured |
Example 3 | Plasma Time of 0.7 sec | 1.95 | 723 | 1.47 | 1.73 | -193 | Unmeasured |
Example 4 | Plasma Time of 0.9 sec | 1.95 | 721 | 1.47 | 1.73 | -149 | 2.0E-2 |
Example 5 | Plasma Time of 1.2 sec | 1.92 | 711 | 1.48 | 1.73 | -293 | 2.5E-2 |
Example 6 | Reaction Gas of400 sccm | 1.97 | 731 | 1.48 | 1.72 | -250 | 4.5E-3 |
Example 7 | Reaction Gas of1400 sccm | 1.92 | 711 | 1.47 | 1.73 | -120 | 5.2E-2 |
Example 8 | RF Power of500W | 1.95 | 720 | 1.48 | 1.73 | -151 | 1.1E-2 |
Comparative Example 2 | Plasma Time of 0.5 sec | 1.19 | 702 | 1.48 | 1.73 | -272 | 8.0E-2 |
[Example 9] Manufacturing of Silicon Nitride Thin film by PEALD Using Bis(dimethylaminomethylsilyl)amine
Film formation was evaluated using the silylamine compound prepared in Example 1 according to the present invention as a composition for forming a silicon nitride film in a general plasma enhanced atomic layer deposition (PEALD) apparatus using a plasma enhanced atomic layer deposition (PEALD) method known in the art. As a reaction gas, nitrogen and ammonia were used together with plasma as first reaction gas, and nitrogen was used as a second reaction gas. The nitrogen corresponding to an inert gas was used for purging. A specific method for depositing a silicon nitride thin film was illustrated in Table 3.
A thickness of a deposited thin film was measured using the Ellipsometer, formation of the silicon nitride thin film was analyzed using infrared spectroscopy, and a composition of the silicon nitride thin film was analyzed using X-ray photoelectron spectroscopy. Further, in order to measure a water vapor transmission rate (WVTR) of the thin film, the WVTR analyzer was used, thereby measuring the WVTR. Specific analysis results of the silicon nitride thin film were illustrated in the following Table 4, and results obtained by analyzing the deposited film using infrared spectroscopy were illustrated in FIG. 4.
[Examples 10 to 15 and Comparative Example 3] Manufacturing of Silicon Nitride Thin films by PEALD Using Bis(dimethylaminomethylsilyl)amine or Diisopropylaminosilane
Film formation was evaluated using a plasma enhanced atomic layer deposition (PEALD) method known in the art in the same manner as in Example 9 except for changing deposition conditions as in Table 3, and the deposited thin film was analyzed by the same analysis method as in Example 9 under the same conditions as in Example 9, such that analysis results were secured. A specific method for depositing a silicon nitride thin film and analysis results were illustrated in the following Tables 3 and 4. Further, the deposited films were analyzed using infrared spectroscopy, and the result was illustrated in FIG. 4. As a result, it may be appreciated that the thin film manufactured in Examples 10 to 15 were silicon nitride thin films.
Further, a result obtained by measuring a water vapor transmission rate of a silicon-containing thin film prepared in Example 11 was illustrated in FIG. 6. The water vapor transmission rate was constantly maintained for a long period of time as illustrated in FIG. 6. Therefore, it is judged that the compound suggested in the present invention may be significantly usefully used in an OLED device in which an encapsulation technology of blocking oxygen and moisture is important.
[Table 3] Deposition Conditions of Silicon Nitride
Variable | Deposition Rate | Thickness of Thin Film | Refractive Index | N/SiComposition Ratio | WVTR | |
(Å/cycle) | (Å) | - | - | (g/[m2-day]) | ||
Example9 | Plasma Time of 0.8sec/2sec | 0.72 | 350 | 1.82 | 1.32 | 1.7E-3 |
Example10 | Plasma Time of 1.5sec/2sec | 0.64 | 350 | 1.87 | 1.22 | 2.2E-2 |
Example11 | Plasma Time of 1.2sec/3sec | 0.7 | 350 | 1.88 | 1.24 | 2.6E-4 |
Example12 | Plasma Time of 0.8sec/4sec | 0.73 | 350 | 1.89 | 1.25 | 1.7E-2 |
Example13 | Plasma Time of 1.5sec/4sec | 0.58 | 350 | 1.93 | 1.17 | 3.1E-2 |
Example14 | Plasma Time of1sec/2sec | 0.71 | 350 | 1.83 | 1.26 | 4.1E-4 |
Example15 | Plasma Power of 800W Plasma Time of 0.6sec/1.3sec | 0.81 | 350 | 1.84 | 1.18 | 2.7E-3 |
Comparative Example3 | Plasma Power of 800W Plasma Time of 0.6sec/1.3sec | 0.43 | 350 | 1.88 | 1.24 | 7.2E-3 |
Claims (10)
- A composition for depositing a silicon-containing thin film, the composition comprising a silylamine compound represented by the following Chemical Formula 1:[Chemical Formula 1]in Chemical Formula 1,R1 to R4 are each independently hydrogen, C1-C7alkyl, or C2-C7alkenyl, or R1 and R2, and R3 and R4 are each independently linked to each other to form a ring; andR5 and R6 are each independently C1-C7alkyl, or C2-C7)alkenyl.
- The composition of claim 1, wherein R5 and R6 are each independently C1-C5alkyl.
- The composition of claim 1, wherein the silylamine compound represented by Chemical Formula 1 is represented by Chemical Formula 2 or 3:[Chemical Formula 2][Chemical Formula 3]in Chemical Formulas 2 and 3,R11 to R14 are each independently hydrogen, C1-C5alkyl, or C2-C5alkenyl;R5 and R6 are each independently C1-C5alkyl, or C2-C5alkenyl; andn and m are each independently an integer of 1 to 7.
- The composition of claim 3, wherein R5 and R6 are each independently C1-C5alkyl; andn and m are each independently an integer of 1 to 4.
- A method for manufacturing a silicon-containing thin film, using the composition of any one of claims 1 to 5.
- The method of claim 6, wherein deposition is performed by an atomic layer deposition method, a chemical vapor deposition method, a metal-organic chemical vapor deposition method, a low-pressure chemical vapor deposition method, a plasma-enhanced chemical vapor deposition method, or a plasma-enhanced atomic layer deposition method.
- The method of claim 6, wherein the silicon-containing thin film is a silicon oxide film, a silicon oxy carbide film, a silicon nitride film, a silicon oxy nitride film, a silicon carbonitride film, or a silicon carbide film.
- The method of claim 6, comprising:a) maintaining a temperature of a substrate mounted in a chamber at 30 to 500℃;b) contacting the composition of any one of claims 1 to 5 with the substrate to adsorb the composition in the substrate; andc) injecting a reaction gas into the substrate in which the composition is adsorbed to form a silicon-containing thin film.
- The method of claim 9, wherein the reaction gas is supplied after being activated by generating plasma with a plasma power of 50 to 1000 W.
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US16/499,216 US20200111665A1 (en) | 2017-03-29 | 2018-03-29 | Composition for depositing silicon-containing thin film and method for manufacturing silicon-containing thin film using the same |
CN201880019561.2A CN110431192B (en) | 2017-03-29 | 2018-03-29 | Composition for depositing silicon-containing film and method for manufacturing silicon-containing film using the same |
US17/653,217 US20230089296A1 (en) | 2017-03-29 | 2022-03-02 | Composition for depositing silicon-containing thin film and method for manufacturing silicon-containing thin film using the same |
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CN113402542A (en) * | 2021-05-25 | 2021-09-17 | 吉林奥来德光电材料股份有限公司 | Compound for packaging film, ink composition containing compound and film packaging structure |
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