JP6262702B2 - 酸化ケイ素薄膜の高温原子層堆積 - Google Patents
酸化ケイ素薄膜の高温原子層堆積 Download PDFInfo
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- JP6262702B2 JP6262702B2 JP2015210441A JP2015210441A JP6262702B2 JP 6262702 B2 JP6262702 B2 JP 6262702B2 JP 2015210441 A JP2015210441 A JP 2015210441A JP 2015210441 A JP2015210441 A JP 2015210441A JP 6262702 B2 JP6262702 B2 JP 6262702B2
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims description 53
- 229910052814 silicon oxide Inorganic materials 0.000 title claims description 41
- 238000000231 atomic layer deposition Methods 0.000 title description 62
- 239000010409 thin film Substances 0.000 title description 2
- 238000000034 method Methods 0.000 claims description 99
- 238000010926 purge Methods 0.000 claims description 77
- 229910052760 oxygen Inorganic materials 0.000 claims description 59
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 58
- 238000000151 deposition Methods 0.000 claims description 58
- 239000001301 oxygen Substances 0.000 claims description 58
- 239000012686 silicon precursor Substances 0.000 claims description 58
- 239000007789 gas Substances 0.000 claims description 54
- 239000000758 substrate Substances 0.000 claims description 28
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 27
- 125000004122 cyclic group Chemical group 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 125000000524 functional group Chemical group 0.000 claims description 21
- 125000000041 C6-C10 aryl group Chemical group 0.000 claims description 20
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 20
- 125000000217 alkyl group Chemical group 0.000 claims description 20
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 19
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 18
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 18
- 239000001257 hydrogen Substances 0.000 claims description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims description 15
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- 125000005103 alkyl silyl group Chemical group 0.000 claims description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 9
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 8
- 125000003277 amino group Chemical group 0.000 claims description 6
- 238000004873 anchoring Methods 0.000 claims description 6
- 229910052734 helium Inorganic materials 0.000 claims description 6
- 239000001307 helium Substances 0.000 claims description 6
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 6
- 150000002978 peroxides Chemical class 0.000 claims description 5
- 239000001272 nitrous oxide Substances 0.000 claims description 4
- SNOOUWRIMMFWNE-UHFFFAOYSA-M sodium;6-[(3,4,5-trimethoxybenzoyl)amino]hexanoate Chemical compound [Na+].COC1=CC(C(=O)NCCCCCC([O-])=O)=CC(OC)=C1OC SNOOUWRIMMFWNE-UHFFFAOYSA-M 0.000 claims description 2
- 239000010408 film Substances 0.000 description 63
- 230000008021 deposition Effects 0.000 description 49
- 239000002243 precursor Substances 0.000 description 36
- 239000000203 mixture Substances 0.000 description 23
- -1 Siloxanes Chemical class 0.000 description 19
- 238000005229 chemical vapour deposition Methods 0.000 description 16
- 238000005137 deposition process Methods 0.000 description 16
- KAHVZNKZQFSBFW-UHFFFAOYSA-N n-methyl-n-trimethylsilylmethanamine Chemical compound CN(C)[Si](C)(C)C KAHVZNKZQFSBFW-UHFFFAOYSA-N 0.000 description 15
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 14
- 229910004298 SiO 2 Inorganic materials 0.000 description 13
- 229910052710 silicon Inorganic materials 0.000 description 13
- 239000010703 silicon Substances 0.000 description 13
- 150000004820 halides Chemical group 0.000 description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 229910052794 bromium Inorganic materials 0.000 description 10
- 229910052801 chlorine Inorganic materials 0.000 description 10
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 10
- 229910052740 iodine Inorganic materials 0.000 description 10
- JOOMLFKONHCLCJ-UHFFFAOYSA-N N-(trimethylsilyl)diethylamine Chemical compound CCN(CC)[Si](C)(C)C JOOMLFKONHCLCJ-UHFFFAOYSA-N 0.000 description 9
- 125000004432 carbon atom Chemical group C* 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- NFVBAYVEVKKWEE-UHFFFAOYSA-N (2,6-dimethylpiperidin-1-yl)-trimethylsilane Chemical compound CC1CCCC(C)N1[Si](C)(C)C NFVBAYVEVKKWEE-UHFFFAOYSA-N 0.000 description 8
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 6
- 125000003545 alkoxy group Chemical group 0.000 description 6
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- POPACFLNWGUDSR-UHFFFAOYSA-N methoxy(trimethyl)silane Chemical compound CO[Si](C)(C)C POPACFLNWGUDSR-UHFFFAOYSA-N 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 6
- 235000012239 silicon dioxide Nutrition 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- GVHIREZHTRULPT-UHFFFAOYSA-N 2-methyl-n-trimethylsilylpropan-2-amine Chemical compound CC(C)(C)N[Si](C)(C)C GVHIREZHTRULPT-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- RSIHJDGMBDPTIM-UHFFFAOYSA-N ethoxy(trimethyl)silane Chemical compound CCO[Si](C)(C)C RSIHJDGMBDPTIM-UHFFFAOYSA-N 0.000 description 4
- FIRXZHKWFHIBOF-UHFFFAOYSA-N n-(dimethylamino-ethenyl-methylsilyl)-n-methylmethanamine Chemical compound CN(C)[Si](C)(C=C)N(C)C FIRXZHKWFHIBOF-UHFFFAOYSA-N 0.000 description 4
- QULMGWCCKILBTO-UHFFFAOYSA-N n-[dimethylamino(dimethyl)silyl]-n-methylmethanamine Chemical compound CN(C)[Si](C)(C)N(C)C QULMGWCCKILBTO-UHFFFAOYSA-N 0.000 description 4
- WJIJKWCQOIHCCD-UHFFFAOYSA-N n-ethyl-n-triethylsilylethanamine Chemical compound CCN(CC)[Si](CC)(CC)CC WJIJKWCQOIHCCD-UHFFFAOYSA-N 0.000 description 4
- YSPHIXJPYVFLLJ-UHFFFAOYSA-N n-trimethylsilylpropan-2-amine Chemical compound CC(C)N[Si](C)(C)C YSPHIXJPYVFLLJ-UHFFFAOYSA-N 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- NQLVIKZJXFGUET-UHFFFAOYSA-N trimethyl(pyrrolidin-1-yl)silane Chemical compound C[Si](C)(C)N1CCCC1 NQLVIKZJXFGUET-UHFFFAOYSA-N 0.000 description 4
- SZSAVDMNBCBPDP-UHFFFAOYSA-N (2,6-dimethylpiperidin-1-yl)-dimethylsilane Chemical compound CC1CCCC(C)N1[SiH](C)C SZSAVDMNBCBPDP-UHFFFAOYSA-N 0.000 description 3
- IDXCKOANSQIPGX-UHFFFAOYSA-N (acetyloxy-ethenyl-methylsilyl) acetate Chemical compound CC(=O)O[Si](C)(C=C)OC(C)=O IDXCKOANSQIPGX-UHFFFAOYSA-N 0.000 description 3
- AALRHBLMAVGWRR-UHFFFAOYSA-N 1-chlorobutan-2-one Chemical compound CCC(=O)CCl AALRHBLMAVGWRR-UHFFFAOYSA-N 0.000 description 3
- GVPUUBGTKARRHG-UHFFFAOYSA-N 2,2,4,4,5,5-hexamethyl-1,3,2-dioxasilolane Chemical compound CC1(C)O[Si](C)(C)OC1(C)C GVPUUBGTKARRHG-UHFFFAOYSA-N 0.000 description 3
- ZKSILZRWWNJBNJ-UHFFFAOYSA-N 2-methyl-n-triethylsilylpropan-2-amine Chemical compound CC[Si](CC)(CC)NC(C)(C)C ZKSILZRWWNJBNJ-UHFFFAOYSA-N 0.000 description 3
- WGYDXYBQNYQPIU-UHFFFAOYSA-N 3,3-di(propan-2-yloxy)prop-1-enylsilane Chemical compound C(C)(C)OC(OC(C)C)C=C[SiH3] WGYDXYBQNYQPIU-UHFFFAOYSA-N 0.000 description 3
- NZHWWOPEBOADOJ-UHFFFAOYSA-N C(C)(C)(C)N[SiH](C=CC)NC(C)(C)C Chemical compound C(C)(C)(C)N[SiH](C=CC)NC(C)(C)C NZHWWOPEBOADOJ-UHFFFAOYSA-N 0.000 description 3
- QFGKJHGPIVNQPI-UHFFFAOYSA-N C[SiH](C)OC1=CC=CC=C1 Chemical compound C[SiH](C)OC1=CC=CC=C1 QFGKJHGPIVNQPI-UHFFFAOYSA-N 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- YDDZTBQOQUWSJI-UHFFFAOYSA-N N,N-bis(diethylsilyl)ethanamine Chemical compound CC[SiH](CC)N(CC)[SiH](CC)CC YDDZTBQOQUWSJI-UHFFFAOYSA-N 0.000 description 3
- ALDJVDLBZOOSJW-UHFFFAOYSA-N N,N-bis(diethylsilyl)methanamine Chemical compound CC[SiH](CC)N(C)[SiH](CC)CC ALDJVDLBZOOSJW-UHFFFAOYSA-N 0.000 description 3
- YRWHGRDNYIXZIP-UHFFFAOYSA-N N,N-bis(diethylsilyl)propan-2-amine Chemical compound CC[SiH](CC)N(C(C)C)[SiH](CC)CC YRWHGRDNYIXZIP-UHFFFAOYSA-N 0.000 description 3
- HXRPNKYNRBAYOP-UHFFFAOYSA-N N,N-bis(dimethylsilyl)ethanamine Chemical compound CCN([SiH](C)C)[SiH](C)C HXRPNKYNRBAYOP-UHFFFAOYSA-N 0.000 description 3
- YNDNVOKCBWAXLI-UHFFFAOYSA-N N,N-bis(dimethylsilyl)methanamine Chemical compound C[SiH](C)N(C)[SiH](C)C YNDNVOKCBWAXLI-UHFFFAOYSA-N 0.000 description 3
- YGRBRKJLHGOADO-UHFFFAOYSA-N N,N-bis(dimethylsilyl)propan-2-amine Chemical compound CC(C)N([SiH](C)C)[SiH](C)C YGRBRKJLHGOADO-UHFFFAOYSA-N 0.000 description 3
- VOKVWBFNWOQFKH-UHFFFAOYSA-N N-[(propan-2-ylamino)-prop-1-enylsilyl]propan-2-amine Chemical compound C(C)(C)N[SiH](C=CC)NC(C)C VOKVWBFNWOQFKH-UHFFFAOYSA-N 0.000 description 3
- NQKCIEMFVOQKHX-UHFFFAOYSA-N N-[[di(propan-2-yl)amino]-prop-1-enylsilyl]-N-propan-2-ylpropan-2-amine Chemical compound C(C)(C)N(C(C)C)[SiH](C=CC)N(C(C)C)C(C)C NQKCIEMFVOQKHX-UHFFFAOYSA-N 0.000 description 3
- MQWJCFBYOCOAQO-UHFFFAOYSA-N N-[diethylamino(prop-1-enyl)silyl]-N-ethylethanamine Chemical compound C(C)N(CC)[SiH](C=CC)N(CC)CC MQWJCFBYOCOAQO-UHFFFAOYSA-N 0.000 description 3
- NQXWICXWTUBFHT-UHFFFAOYSA-N N-diethylsilyl-2-methylpropan-2-amine Chemical compound CC[SiH](CC)NC(C)(C)C NQXWICXWTUBFHT-UHFFFAOYSA-N 0.000 description 3
- HFFIGVUBWMEZJT-UHFFFAOYSA-N N-diethylsilyl-N-methylmethanamine Chemical compound CC[SiH](CC)N(C)C HFFIGVUBWMEZJT-UHFFFAOYSA-N 0.000 description 3
- ZCNZAWGUQXCNHK-UHFFFAOYSA-N N-diethylsilyl-N-propan-2-ylpropan-2-amine Chemical compound CC[SiH](CC)N(C(C)C)C(C)C ZCNZAWGUQXCNHK-UHFFFAOYSA-N 0.000 description 3
- WJDNXDURVAFUJT-UHFFFAOYSA-N N-diethylsilylpropan-2-amine Chemical compound CC[SiH](CC)NC(C)C WJDNXDURVAFUJT-UHFFFAOYSA-N 0.000 description 3
- SQIKBMFZMZLSMO-UHFFFAOYSA-N N-dimethylsilyl-N-propan-2-ylpropan-2-amine Chemical compound CC(C)N(C(C)C)[SiH](C)C SQIKBMFZMZLSMO-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- PUVVSMFTBVEMTC-UHFFFAOYSA-N [(diethylsilylamino)-ethylsilyl]ethane Chemical compound CC[SiH](CC)N[SiH](CC)CC PUVVSMFTBVEMTC-UHFFFAOYSA-N 0.000 description 3
- GJWAPAVRQYYSTK-UHFFFAOYSA-N [(dimethyl-$l^{3}-silanyl)amino]-dimethylsilicon Chemical compound C[Si](C)N[Si](C)C GJWAPAVRQYYSTK-UHFFFAOYSA-N 0.000 description 3
- JQNJIBYLKBOSCM-UHFFFAOYSA-N [acetyloxy(diethyl)silyl] acetate Chemical compound CC(=O)O[Si](CC)(CC)OC(C)=O JQNJIBYLKBOSCM-UHFFFAOYSA-N 0.000 description 3
- RQVFGTYFBUVGOP-UHFFFAOYSA-N [acetyloxy(dimethyl)silyl] acetate Chemical compound CC(=O)O[Si](C)(C)OC(C)=O RQVFGTYFBUVGOP-UHFFFAOYSA-N 0.000 description 3
- APDDLLVYBXGBRF-UHFFFAOYSA-N [diethyl-(triethylsilylamino)silyl]ethane Chemical compound CC[Si](CC)(CC)N[Si](CC)(CC)CC APDDLLVYBXGBRF-UHFFFAOYSA-N 0.000 description 3
- KEVICWGPAZOCGD-UHFFFAOYSA-N [dimethyl(phenyl)silyl] acetate Chemical compound CC(=O)O[Si](C)(C)C1=CC=CC=C1 KEVICWGPAZOCGD-UHFFFAOYSA-N 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- GEVFICDEOWFKDU-UHFFFAOYSA-N bis[(2-methylpropan-2-yl)oxy]-di(propan-2-yl)silane Chemical compound CC(C)(C)O[Si](C(C)C)(OC(C)(C)C)C(C)C GEVFICDEOWFKDU-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- ZMAPKOCENOWQRE-UHFFFAOYSA-N diethoxy(diethyl)silane Chemical compound CCO[Si](CC)(CC)OCC ZMAPKOCENOWQRE-UHFFFAOYSA-N 0.000 description 3
- VSYLGGHSEIWGJV-UHFFFAOYSA-N diethyl(dimethoxy)silane Chemical compound CC[Si](CC)(OC)OC VSYLGGHSEIWGJV-UHFFFAOYSA-N 0.000 description 3
- BAYBTHPPTMXTLT-UHFFFAOYSA-N diethyl(dipyrrolidin-1-yl)silane Chemical compound C1CCCN1[Si](CC)(CC)N1CCCC1 BAYBTHPPTMXTLT-UHFFFAOYSA-N 0.000 description 3
- HKAGYJNZCWXVCS-UHFFFAOYSA-N diethyl-bis[(2-methylpropan-2-yl)oxy]silane Chemical compound CC(C)(C)O[Si](CC)(CC)OC(C)(C)C HKAGYJNZCWXVCS-UHFFFAOYSA-N 0.000 description 3
- ZWPNXHXXRLYCHZ-UHFFFAOYSA-N diethyl-di(propan-2-yloxy)silane Chemical compound CC(C)O[Si](CC)(CC)OC(C)C ZWPNXHXXRLYCHZ-UHFFFAOYSA-N 0.000 description 3
- ADTGAVILDBXARD-UHFFFAOYSA-N diethylamino(dimethyl)silicon Chemical compound CCN(CC)[Si](C)C ADTGAVILDBXARD-UHFFFAOYSA-N 0.000 description 3
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 3
- VHPUZTHRFWIGAW-UHFFFAOYSA-N dimethoxy-di(propan-2-yl)silane Chemical compound CO[Si](OC)(C(C)C)C(C)C VHPUZTHRFWIGAW-UHFFFAOYSA-N 0.000 description 3
- OFKNHDDXWSOGKH-UHFFFAOYSA-N dimethyl(dipyrrolidin-1-yl)silane Chemical compound C1CCCN1[Si](C)(C)N1CCCC1 OFKNHDDXWSOGKH-UHFFFAOYSA-N 0.000 description 3
- OARYFQYHTWCNQO-UHFFFAOYSA-N dimethyl(propan-2-yloxy)silane Chemical compound CC(C)O[SiH](C)C OARYFQYHTWCNQO-UHFFFAOYSA-N 0.000 description 3
- GWNYFISHEJZWOL-UHFFFAOYSA-N dimethyl(pyrrolidin-1-yl)silane Chemical compound C[SiH](C)N1CCCC1 GWNYFISHEJZWOL-UHFFFAOYSA-N 0.000 description 3
- WTQHTLASFRZLHF-UHFFFAOYSA-N dimethyl-(2-methylbutan-2-yloxy)-phenylsilane Chemical compound CCC(C)(C)O[Si](C)(C)C1=CC=CC=C1 WTQHTLASFRZLHF-UHFFFAOYSA-N 0.000 description 3
- NTFLYZSHQURCGV-UHFFFAOYSA-N dimethyl-[(2-methylpropan-2-yl)oxy]-phenylsilane Chemical compound CC(C)(C)O[Si](C)(C)C1=CC=CC=C1 NTFLYZSHQURCGV-UHFFFAOYSA-N 0.000 description 3
- BFFJBAVNIXLGLQ-UHFFFAOYSA-N dimethyl-[(2-methylpropan-2-yl)oxy]silane Chemical compound C[SiH](C)OC(C)(C)C BFFJBAVNIXLGLQ-UHFFFAOYSA-N 0.000 description 3
- BGPNEHJZZDIFND-UHFFFAOYSA-N dimethyl-bis[(2-methylpropan-2-yl)oxy]silane Chemical compound CC(C)(C)O[Si](C)(C)OC(C)(C)C BGPNEHJZZDIFND-UHFFFAOYSA-N 0.000 description 3
- BPXCAJONOPIXJI-UHFFFAOYSA-N dimethyl-di(propan-2-yloxy)silane Chemical compound CC(C)O[Si](C)(C)OC(C)C BPXCAJONOPIXJI-UHFFFAOYSA-N 0.000 description 3
- SZPIKCAXBLKNNK-UHFFFAOYSA-N dimethyl-phenoxy-phenylsilane Chemical compound C=1C=CC=CC=1[Si](C)(C)OC1=CC=CC=C1 SZPIKCAXBLKNNK-UHFFFAOYSA-N 0.000 description 3
- OUXITSTZXAGCQA-UHFFFAOYSA-N dimethyl-phenyl-propan-2-yloxysilane Chemical compound CC(C)O[Si](C)(C)C1=CC=CC=C1 OUXITSTZXAGCQA-UHFFFAOYSA-N 0.000 description 3
- KZFNONVXCZVHRD-UHFFFAOYSA-N dimethylamino(dimethyl)silicon Chemical compound CN(C)[Si](C)C KZFNONVXCZVHRD-UHFFFAOYSA-N 0.000 description 3
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 description 3
- NYMVBZHJSKIHQK-UHFFFAOYSA-N dimethylsilyl acetate Chemical compound C[SiH](C)OC(C)=O NYMVBZHJSKIHQK-UHFFFAOYSA-N 0.000 description 3
- 230000009977 dual effect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- MBGQQKKTDDNCSG-UHFFFAOYSA-N ethenyl-diethoxy-methylsilane Chemical compound CCO[Si](C)(C=C)OCC MBGQQKKTDDNCSG-UHFFFAOYSA-N 0.000 description 3
- ZLNAFSPCNATQPQ-UHFFFAOYSA-N ethenyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C=C ZLNAFSPCNATQPQ-UHFFFAOYSA-N 0.000 description 3
- DRUOQOFQRYFQGB-UHFFFAOYSA-N ethoxy(dimethyl)silicon Chemical compound CCO[Si](C)C DRUOQOFQRYFQGB-UHFFFAOYSA-N 0.000 description 3
- DFJDZTPFNSXNAX-UHFFFAOYSA-N ethoxy(triethyl)silane Chemical compound CCO[Si](CC)(CC)CC DFJDZTPFNSXNAX-UHFFFAOYSA-N 0.000 description 3
- FIHCECZPYHVEJO-UHFFFAOYSA-N ethoxy-dimethyl-phenylsilane Chemical compound CCO[Si](C)(C)C1=CC=CC=C1 FIHCECZPYHVEJO-UHFFFAOYSA-N 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- VJOOEHFQQLYDJI-UHFFFAOYSA-N methoxy(dimethyl)silane Chemical compound CO[SiH](C)C VJOOEHFQQLYDJI-UHFFFAOYSA-N 0.000 description 3
- REQXNMOSXYEQLM-UHFFFAOYSA-N methoxy-dimethyl-phenylsilane Chemical compound CO[Si](C)(C)C1=CC=CC=C1 REQXNMOSXYEQLM-UHFFFAOYSA-N 0.000 description 3
- VFMNUQLXYDYZTA-UHFFFAOYSA-N n,n-bis(triethylsilyl)propan-2-amine Chemical compound CC[Si](CC)(CC)N(C(C)C)[Si](CC)(CC)CC VFMNUQLXYDYZTA-UHFFFAOYSA-N 0.000 description 3
- OGWVYCFORNDBRE-UHFFFAOYSA-N n,n-bis(trimethylsilyl)ethanamine Chemical compound CCN([Si](C)(C)C)[Si](C)(C)C OGWVYCFORNDBRE-UHFFFAOYSA-N 0.000 description 3
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- FTCHSXVKVGGWCW-UHFFFAOYSA-N trimethyl(1h-pyrrol-2-yl)silane Chemical compound C[Si](C)(C)C1=CC=CN1 FTCHSXVKVGGWCW-UHFFFAOYSA-N 0.000 description 1
- WLADIVUISABQHN-UHFFFAOYSA-N trimethyl(piperidin-1-yl)silane Chemical compound C[Si](C)(C)N1CCCCC1 WLADIVUISABQHN-UHFFFAOYSA-N 0.000 description 1
- HDAHNNLOAPEEMC-UHFFFAOYSA-N trimethyl-(2-methylpyrrolidin-1-yl)silane Chemical compound CC1CCCN1[Si](C)(C)C HDAHNNLOAPEEMC-UHFFFAOYSA-N 0.000 description 1
- PQDJYEQOELDLCP-UHFFFAOYSA-N trimethylsilane Chemical compound C[SiH](C)C PQDJYEQOELDLCP-UHFFFAOYSA-N 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 239000006200 vaporizer Substances 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—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
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/448—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials
-
- 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 System
- 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
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/40—Oxides
- C23C16/401—Oxides containing silicon
- C23C16/402—Silicon dioxide
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
- C23C16/45527—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
- C23C16/45553—Atomic layer deposition [ALD] characterized by the use of precursors specially adapted for ALD
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/52—Controlling or regulating the coating process
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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
- 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
Description
この特許出願は、2012年4月12日付で出願された米国仮特許出願第61/623,217号の優先権の利益を主張する。
a.基材を反応器内に用意する工程、
b.少なくとも1つのケイ素前駆体を前記反応器内に導入する工程、
c.前記反応器をパージガスでパージする工程、
d.酸素源を前記反応器内に導入する工程、及び
e.前記反応器をパージガスでパージする工程
を含み、所望の厚さの酸化ケイ素が堆積するまで工程bから工程eが繰り返され、500〜800℃の1又は複数の温度及び50ミリトール(mT)〜760トールの1又は複数の圧力で実施される、酸化ケイ素を堆積させる方法が提供される。
a.基材を反応器内に用意する工程、
b.少なくとも1つのケイ素前駆体を前記反応器内に導入する工程、
c.前記反応器をパージガスでパージする工程、
d.酸素源を前記反応器内に導入する工程、
e.前記反応器をパージガスでパージする工程、
f.水蒸気又はヒドロキシル源を前記反応器内に導入する工程、及び
g.前記反応器をパージガスでパージする工程
を含み、所望の厚さの酸化ケイ素が堆積するまで工程bから工程gが繰り返され、500〜800℃の1又は複数の温度及び50ミリトール(mT)〜760トールの1又は複数の圧力で実施される、酸化ケイ素を堆積させる方法が提供される。この又は他の実施形態では、酸素源は、酸素、酸素プラズマ、水蒸気、水蒸気プラズマ、過酸化水素、酸化窒素、及びオゾンからなる群より選択される。
I.R1R2 mSi(NR3R4)nXp
(式中、R1、R2及びR3は、それぞれ独立に、水素、直鎖又は分岐鎖のC1〜C10アルキル基、及びC6〜C10アリール基から選択され、R4は、直鎖又は分岐鎖のC1〜C10アルキル基、C6〜C10アリール基、及びC3〜C10アルキルシリル基から選択され、ここで、R3とR4は環式環構造を形成するために連結するか又はR3とR4は環式環構造を形成するために連結せず、XはCl、Br及びIからなる群より選択されるハライドであり、mは0〜3であり、nは0〜2であり、pは0〜2であり、m+n+p=3である)並びに
II.R1R2 mSi(OR3)n(OR4)qXp
(式中、R1及びR2は、それぞれ独立に、水素、直鎖又は分岐鎖のC1〜C10アルキル基、及びC6〜C10アリール基から選択され、R3及びR4は、それぞれ独立に、直鎖又は分岐鎖のC1〜C10アルキル基、及びC6〜C10アリール基から選択され、ここで、R3とR4は環式環構造を形成するために連結するか又はR3とR4は環式環構造を形成するために連結せず、XはCl、Br及びIからなる群より選択されるハライド原子であり、mは0〜3であり、nは0〜2であり、pは0〜2であり、m+n+p=3である)
からなる群より選択される。
a.基材を反応器内に用意する工程、
b.ケイ素前駆体を前記反応器内に導入する工程、
c.前記反応器をパージガスでパージする工程、
d.酸素源を前記反応器内に導入する工程、及び
e.前記反応器をパージガスでパージする工程
を含む。従来技術の方法では、所望の膜厚が堆積するまで工程bから工程eが繰り返される。
I.R1R2 mSi(NR3R4)nXp
(式中、R1、R2及びR3は、それぞれ独立に、水素、直鎖又は分岐鎖のC1〜C10アルキル基、及びC6〜C10アリール基から選択され、R4は、直鎖又は分岐鎖のC1〜C10アルキル基、C6〜C10アリール基、及びC3〜C10アルキルシリル基から選択され、ここで、R3とR4は環式環構造を形成するために連結するか又はR3とR4は環式環構造を形成するために連結せず、XはCl、Br及びIからなる群より選択されるハライドであり、mは0〜3であり、nは0〜2であり、pは0〜2であり、m+n+p=3である)を有する化合物である。式Iを有する前駆体の例としては、これだけに限定されるものではないが、以下のものが挙げられる:ジエチルアミノトリメチルシラン、ジメチルアミノトリメチルシラン、エチルメチルアミノトリメチルシラン、ジエチルアミノトリエチルシラン、ジメチルアミノトリエチルシラン、エチルメチルアミノトリエチルシラン、t‐ブチルアミノトリエチルシラン、イソ‐プロピルアミノトリエチルシラン、ジイソプロピルアミノトリエチルシラン、ピロリジノトリエチルシラン、t‐ブチルアミノトリメチルシラン、イソ‐プロピルアミノトリメチルシラン、ジ‐イソプロピルアミノトリメチルシラン、ピロリジノトリメチルシラン、ジエチルアミノジメチルシラン、ジメチルアミノジメチルシラン、エチルメチルアミノジメチルシラン、t‐ブチルアミノジメチルシラン、イソ‐プロピルアミノジメチルシラン、ジイソプロピルアミノジメチルシラン、ピロリジノジメチルシラン、ジエチルアミノジエチルシラン、ジメチルアミノジエチルシラン、エチルメチルアミノジエチルシラン、t‐ブチルアミノジエチルシラン、イソ‐プロピルアミノジエチルシラン、ジ‐イソプロピルアミノジエチルシラン、ピロリジノジエチルシラン、ビス(ジエチルアミノ)ジメチルシラン、ビス(ジメチルアミノ)ジメチルシラン、ビス(エチルメチルアミノ)ジメチルシラン、ビス(ジ‐イソプロピルアミノ)ジメチルシラン、ビス(イソ‐プロピルアミノ)ジメチルシラン、ビス(tert‐ブチルアミノ)ジメチルシラン、ジピロリジノジメチルシラン、ビス(ジエチルアミノ)ジエチルシラン、ビス(ジメチルアミノ)ジエチルシラン、ビス(エチルメチルアミノ)ジエチルシラン、ビス(ジイソプロピルアミノ)ジエチルシラン、ビス(イソ‐プロピルアミノ)ジエチルシラン、ビス(tert‐ブチルアミノ)ジエチルシラン、ジピロリジノジエチルシラン、ビス(ジエチルアミノ)メチルビニルシラン、ビス(ジメチルアミノ)メチルビニルシラン、ビス(ジメチルアミノ)メチルビニルシラン、ビス(ジ‐イソプロピルアミノ)メチルビニルシラン、ビス(イソ‐プロピルアミノ)メチルビニルシラン、ビス(tert‐ブチルアミノ)メチルビニルシラン、ジピロリジノメチルビニルシラン、2,6‐ジメチルピペリジノメチルシラン、2,6‐ジメチルピペリジノジメチルシラン、2,6‐ジメチルピペリジノトリメチルシラン、トリス(ジメチルアミノ)フェニルシラン、トリス(ジメチルアミノ)メチルシラン、トリス(ジメチルアミノ)エチルシラン、及びトリス(ジメチルアミノ)クロロシラン。
II.R1R2 mSi(OR3)n(OR4)qXp
(式中、R1及びR2は、それぞれ独立に、水素、直鎖又は分岐鎖のC1〜C10アルキル基、及びC6〜C10アリール基から選択され、R3及びR4は、それぞれ独立に、直鎖又は分岐鎖のC1〜C10アルキル基、及びC6〜C10アリール基から選択され、ここで、R3とR4は環式環構造を形成するために連結するか又はR3とR4は環式環構造を形成するために連結せず、XはCl、Br及びIからなる群より選択されるハライド原子であり、mは0〜3であり、nは0〜2であり、qは0〜2であり、pは0〜2であり、m+n+q+p=3である)を有する化合物である。このようなグループIIのケイ素前駆体の例としては、これだけに限定されるものではないが、以下のものが挙げられる:メトキシトリメチルシラン、エトキシトリメチルシラン、イソ‐プロポキシトリメチルシラン、tert‐ブトキシトリメチルシラン、tert‐ペントキシトリメチルシラン、フェノキシトリメチルシラン、アセトキシトリメチルシラン、メトキシトリエチルシラン、エトキシトリエチルシラン、イソ‐プロポキシトリエチルシラン、tert‐ブトキシトリエチルシラン、tert‐ペントキシトリエチルシラン、フェノキシトリエチルシラン、アセトキシトリエチルシラン、メトキシジメチルシラン、エトキシジメチルシラン、イソ‐プロポキシジメチルシラン、tert‐ブトキシジメチルシラン、tert‐ペントキシジメチルシラン、フェノキシジメチルシラン、アセトキシジメチルシラン、メトキシジメチルフェニルシラン、エトキシジメチルフェニルシラン、イソ‐プロポキシジメチルフェニルシラン、tert‐ブトキシジメチルフェニルシラン、tert‐ペントキシジメチルフェニルシラン、フェノキシジメチルフェニルシラン、アセトキシジメチルフェニルシラン、ジメトキシジメチルシラン、ジエトキシジメチルシラン、ジ‐イソプロポキシジメチルシラン、ジ‐t‐ブトキシジメチルシラン、ジアセトキシジメチルシラン、ジメトキシジエチルシラン、ジエトキシジエチルシラン、ジ‐イソプロポキシジエチルシラン、ジ‐t‐ブトキシジエチルシラン、ジアセトキシジエチルシラン、ジメトキシジ‐イソプロピルシラン、ジエトキシジ‐イソプロピルシラン、ジ‐イソプロポキシジ‐イソプロピルシラン、ジ‐t‐ブトキシジ‐イソプロピルシラン、ジアセトキシジ‐イソプロピルシラン、ジメトキシメチルビニルシラン、ジエトキシメチルビニルシラン、ジ‐イソプロポキシメチルビニルシラン、ジ‐t‐ブトキシメチルビニルシラン、ジアセトキシメチルビニルシラン、1,1,3,4‐テトラメチル‐1‐シラ‐2,5‐ジオキサシクロペンタン、及び1,1,3,3,4,4‐ヘキサメチル‐1‐シラ‐2,5‐ジオキサシクロペンタン。
a.基材を反応器内に用意する工程、
b.式I、II又はその両方を有する本明細書で記載される少なくとも1つのケイ素前駆体を前記反応器内に導入する工程、
c.前記反応器をパージガスでパージする工程、
d.酸素源を前記反応器内に導入する工程、及び
e.前記反応器をパージガスでパージする工程
を含み、所望の厚さの酸化ケイ素膜が堆積するまで工程bから工程eが繰り返される。
I.R1R2 mSi(NR3R4)nXp
(式中、R1はメチル(Me)基であり、R2はMe基であり、m=2、n=1、p=0、R3は、水素、直鎖又は分岐鎖のC1〜C10アルキル基、及びC6〜C10アリール基から選択され、R4は、直鎖又は分岐鎖のC1〜C10アルキル基、C6〜C10アリール基、C3〜C10アルキルシリル基から選択され、ここで、R3とR4は環式環構造を形成するために連結するか又はR3とR4は環式環構造を形成するために連結しない)を有する化合物である。以下の表1は、ハライド原子、アミン基、又はアルコキシ基から選択される固着官能基を持ち、且つ、好ましくはメチル又はMe基であるアルキル基から選択される不動態化機能を有する典型的なケイ素前駆体と持つ構造物を示す。理論に縛られるものではないが、Si‐Me基が、500℃超の温度にて安定しているので、更なる表面反応を予防する不動態化官能基を提供し、そして自己制限的ALP又はALD型プロセスにつながる。
a.基材を反応器内に用意する工程、
b.上記の1つのケイ素前駆体を前記反応器内に導入する工程、
c.前記反応器をパージガスでパージする工程、
d.酸化剤を前記反応器内に導入する工程、
e.前記反応器をパージガスでパージする工程、
f.水蒸気又はヒドロキシル源を前記反応器内に導入する工程、及び
g.前記反応器をパージガスでパージする工程
を含み、所望の厚さが堆積するまで工程bから工程gが繰り返される。
a.基材を反応器内に用意する工程、
b.上記の1つのケイ素前駆体を前記反応器内に導入する工程、
c.前記反応器をパージガスでパージする工程、
d.酸素源を前記反応器内に導入する工程、
e.前記反応器をパージガスでパージする工程、
f.水蒸気又はOH源を前記反応器内に導入する工程、及び
g.前記反応器をパージガスでパージする工程
を含み、所望の厚さが堆積するまで工程bから工程gが繰り返される。
a.基材を反応器内に用意する工程、
b.上記の1つのケイ素前駆体を前記反応器内に導入する工程、
c.前記反応器をパージガスでパージする工程、
d.オゾン、過酸化水素又は酸素プラズマを前記反応器内に導入する工程、及び
e.前記反応器をパージガスでパージする工程
を含み、所望の厚さが堆積するまで工程bから工程eが繰り返される。
酸化ケイ素膜の原子層堆積を、次の前駆体を用いて行った:ジメチルアミノトリメチルシラン(DMATMS)。堆積を、実験室スケールのALDプロセスツールで行った。ケイ素前駆体を、蒸気ドローによってチャンバーに供給した。全てのガス(例えば、パージガス、反応ガス又は前駆体及び酸素源)を、堆積ゾーンに入る前に100℃に余熱した。ガス及び前駆体の流量を、高速作動するALDダイアフラムバルブで制御した。堆積に用いた基材は、12インチの長さのシリコンストリップであった。基材の温度を確認するために、熱電対をサンプルホルダーに取り付けた。酸素源ガスとしてオゾンを用いて、堆積を行った。堆積パラメーターを表7に与える。
酸化ケイ素膜の原子層堆積は、実施例1の表Iに挙げたジエチルアミノトリメチルシラン(DEATMS)使用工程である。500〜650℃にて一定の前駆体投与(8秒)でDEATMSを用いて堆積させたSiO2膜の堆積速度と膜不均質性を、表IVに示した。
SiO2膜を、DMATMSを用いてパターンシリコンウェハー上に堆積させた。堆積プロセスを、650℃にて8秒の、酸素源ガスとしてのオゾンと前駆体の二連パルスを使用して実施した。基材上に堆積した膜を、電界放射型走査電子顕微鏡(FESEM)Hitachi S‐4800SEMを使用して計測した。サンプルを、断面ホルダーに乗せ、そして2kVの加速電圧で稼働したSEMを使用して調べられた。サンプル断面のSiO2厚の測定を、溝の上部、側壁、及び底部で行なった。SiO2膜のSEM断面の精査で、素晴らしい段差被覆率(>96%)を示したので、そのプロセスが確かにALDプロセスであると確認した。
酸化ケイ素膜の堆積を、ケイ素前駆体であるジエチルアミノトリエチルシラン(DEATES)とオゾンを使用して行なった。使用した堆積工程は、実施例1の表Iに挙げてある。表VIIには、500〜650℃のウェハー温度にてDEATESを使用して堆積させたSiO2膜の堆積速度と不均質性をまとめてある。
酸化ケイ素膜の原子層堆積を、ケイ素前駆体であるメトキシトリメチルシランを使用して行なった。堆積は、実施例1の表Iで列挙したプロセス工程を用いて650℃にてオゾンを使用することで実施した。基材温度を650℃に設定した。堆積速度は、約0.3Å/サイクルであった。
酸化ケイ素膜の原子層堆積を、ケイ素前駆体であるクロロトリメチルシランを使用して行なった。堆積を、酸素源ガスとしてオゾンを使用して実施し、堆積プロセスパラメーターは、実施例1の表Iと同じである。基材温度を650℃に設定した。堆積速度は0.5Å/サイクルであった。
酸化ケイ素膜の原子層堆積を、ケイ素前駆体であるヘキサメチルジシランを使用して行なった。堆積を、実施例1の表Iに挙げたプロセス工程を用いて、650℃にてオゾンを使用して実施した。堆積速度は、約1.3Å/サイクルであった。
ビスジメチルアミノジメチルシラン(BDMADMS)を、ケイ素前駆体として使用した。BDMADMSは、R1R2 mSi(NR3R4)n(式中、R1、R2、R3、R4は、メチルであり、n=2、そしてm=1。)の一般構造を有する。
添加漏斗、冷却管、及び機械式スターラーを備えた1000ml容の三つ口丸底フラスコの中に、113g(1.0mol)の2,6‐ジメチルピペリジン及び500mlのヘキサンを加えた。撹拌しながら、50.5g(0.5mol)のクロロトリメチルシランを、添加漏斗を通して滴下して加えた。添加が完了した後、反応混合物を6時間還流した。室温まで冷まし、混合物は濾過した。固体をヘキサンで洗浄し、そして、そのヘキサン溶液を濾液と合わせた。溶媒であるヘキサンを蒸留によって取り除いた。分別蒸留によって134gの2,6‐ジメチルピペリジノトリメチルシランを得た。収率は75%であった。図2に提供したマススペクトルで、それが185(M)、170(M‐15)にフラグメントを有するジメチルピペリジノトリメチルシランであることを確認した。
(1)a.基材を反応器内に用意する工程、
b.少なくとも1つのケイ素前駆体を前記反応器内に導入する工程、
c.前記反応器をパージガスでパージする工程、
d.酸素源を前記反応器内に導入する工程、及び
e.前記反応器をパージガスでパージする工程
を含み、所望の厚さの酸化ケイ素が堆積するまで工程bから工程eが繰り返され、
500〜800℃の1又は複数の温度及び50ミリトール(mT)〜760トールの1又は複数の圧力で実施される、基材上に酸化ケイ素膜を堆積させる方法。
I.R1R2 mSi(NR3R4)nXp
(式中、R1、R2及びR3は、それぞれ独立に、水素、直鎖又は分岐鎖のC1〜C10アルキル基、及びC6〜C10アリール基から選択され、R4は、直鎖又は分岐鎖のC1〜C10アルキル基、C6〜C10アリール基、及びC3〜C10アルキルシリル基から選択され、ここで、R3とR4は環式環構造を形成するために連結するか又はR3とR4は環式環構造を形成するために連結せず、XはCl、Br及びIからなる群より選択されるハライドであり、mは0〜3であり、nは0〜2であり、pは0〜2であり、m+n+p=3である)並びに
II.R1R2 mSi(OR3)n(OR4)qXp
(式中、R1及びR2は、それぞれ独立に、水素、直鎖又は分岐鎖のC1〜C10アルキル基、及びC6〜C10アリール基から選択され、R3及びR4は、それぞれ独立に、直鎖又は分岐鎖のC1〜C10アルキル基、及びC6〜C10アリール基から選択され、ここで、R3とR4は環式環構造を形成するために連結するか又はR3とR4は環式環構造を形成するために連結せず、XはCl、Br及びIからなる群より選択されるハライド原子であり、mは0〜3であり、nは0〜2であり、qは0〜2であり、pは0〜2であり、m+n+q+p=3である)
からなる群より選択される式を有する、(1)に記載の方法。
(7)前記酸素源が、酸素、過酸化物、酸素プラズマ、水蒸気、水蒸気プラズマ、過酸化水素、及びオゾン源からなる群より選択される、(1)に記載の方法。
(8)f.水蒸気又はヒドロキシル源を前記反応器内に導入する工程、及び
g.前記反応器をパージガスでパージする工程
を工程eの後にさらに含む、(1)に記載の方法。
b.少なくとも1つのケイ素前駆体を前記反応器内に導入する工程、
c.前記反応器をパージガスでパージする工程、
d.酸素源を前記反応器内に導入する工程、
e.前記反応器をパージガスでパージする工程、
f.水蒸気又はOH源を前記反応器内に導入する工程、及び
g.前記反応器をパージガスでパージする工程
を含み、所望の厚さが堆積するまで工程bから工程gが繰り返され、
プロセス温度が500〜800℃であり、圧力が50ミリトール(mT)〜760トールである、酸化ケイ素を堆積させる方法。
I.R1R2 mSi(NR3R4)nXp
(式中、R1、R2及びR3は、それぞれ独立に、水素、直鎖又は分岐鎖のC1〜C10アルキル基、及びC6〜C10アリール基から選択され、R4は、直鎖又は分岐鎖のC1〜C10アルキル基、C6〜C10アリール基、及びC3〜C10アルキルシリル基から選択され、ここで、R3とR4は環式環構造を形成するために連結するか又はR3とR4は環式環構造を形成するために連結せず、XはCl、Br及びIからなる群より選択されるハライドであり、mは0〜3であり、nは0〜2であり、pは0〜2であり、m+n+p=3である)並びに
II.R1R2 mSi(OR3)n(OR4)qXp
(式中、R1及びR2は、それぞれ独立に、水素、直鎖又は分岐鎖のC1〜C10アルキル基、及びC6〜C10アリール基から選択され、R3及びR4は、それぞれ独立に、直鎖又は分岐鎖のC1〜C10アルキル基、及びC6〜C10アリール基から選択され、ここで、R3とR4は環式環構造を形成するために連結するか又はR3とR4は環式環構造を形成するために連結せず、XはCl、Br及びIからなる群より選択されるハライド原子であり、mは0〜3であり、nは0〜2であり、qは0〜2であり、pは0〜2であり、m+n+q+p=3である)
からなる群より選択される式を有する、(9)に記載の方法。
(15)前記酸素源が、酸素、酸素プラズマ、亜酸化窒素、水蒸気、水蒸気プラズマ、過酸化水素、及びオゾン源からなる群より選択される、(9)に記載の方法。
(16)a.基材を反応器内に用意する工程、
b.少なくとも1つのケイ素前駆体を前記反応器内に導入する工程、
c.前記反応器をパージガスでパージする工程、
d.酸素源を前記反応器内に導入する工程、及び
e.前記反応器をパージガスでパージする工程
を含み、所望の厚さが堆積するまで工程bから工程eが繰り返され、
プロセス温度が500〜800℃であり、圧力が50ミリトール(mT)〜760トールであり、前記ケイ素前駆体がSi‐Me基を含む少なくとも1つの固着官能基及び不動態化官能基を有する、酸化ケイ素を堆積させる方法。
(18)前記プロセス温度が550〜750℃である、(16)に記載の方法。
(19)前記圧力が50ミリトール(mT)〜100トールである、(16)に記載の方法。
(20)前記固着官能基がアミノ基である、(16)に記載の方法。
(21)前記固着官能基がCl、Br及びIからなる群より選択されるハライドである、(16)に記載の方法。
(22)前記固着官能基がアルコキシ基である、(16)に記載の方法。
(24)2,6‐ジメチルピペリジノトリメチルシラン、2,5‐ジメチルピロリジノトリメチルシラン、及び2‐メチルピロリジノトリメチルシランからなる群より選択されるケイ素含有前駆体。
Claims (5)
- a.基材を反応器内に用意する工程、
b.少なくとも1つのケイ素前駆体を前記反応器内に導入する工程、
c.前記反応器をパージガスでパージする工程、
d.酸素源を前記反応器内に導入する工程、及び
e.前記反応器をパージガスでパージする工程
を含み、所望の厚さの酸化ケイ素が堆積するまで工程bから工程eが繰り返され、
550〜800℃の1又は複数の温度及び7.6Pa〜100kPa(50ミリトール(mT)〜760トール)の1又は複数の圧力で実施される、酸化ケイ素を堆積させる方法であって、該ケイ素前駆体が、アミノ基から選択された固着官能基ならびにSi−Me基を含む不動態化官能基を含み、
前記少なくとも1つのケイ素前駆体が、以下の式I
式I. R1R2 mSi(NR3R4)n
式中、R1はメチルであり、R2はメチルであり、R3は、水素、直鎖又は分岐鎖のC1〜C10アルキル基、及びC6〜C10アリール基から選択され、R4は、直鎖又は分岐鎖のC1〜C10アルキル基、C6〜C10アリール基、及びC3〜C10アルキルシリル基から選択され、ここで、R3とR4は環式環構造を形成するために連結するか又はR3とR4は環式環構造を形成するために連結せず、nは1であり、m+n=3である、
を有し、
前記温度が550〜750℃である、
方法。 - 前記圧力が、6.7Pa〜13kPa(50ミリトール(mT)〜100トール)である、請求項1に記載の方法。
- 前記パージガスが、窒素、ヘリウム、及びアルゴンからなる群より選択される、請求項1または2に記載の方法。
- 前記酸素源が、酸素、過酸化物、酸素プラズマ、水蒸気、水蒸気プラズマ、過酸化水素、亜酸化窒素、及びオゾン源からなる群より選択される、請求項1〜3のいずれか1項に記載の方法。
- f.水蒸気又はヒドロキシル源を前記反応器内に導入する工程、及び
g.前記反応器をパージガスでパージする工程
を工程eの後に更に含み、工程b〜gが、所望の厚さの酸化ケイ素が堆積されるまで繰り返される、請求項1〜4のいずれか1項に記載の方法。
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JP2020038978A (ja) | 2020-03-12 |
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