JP5650589B2 - 有機アミノシラン前駆体及びこれを含む膜の堆積方法 - Google Patents
有機アミノシラン前駆体及びこれを含む膜の堆積方法 Download PDFInfo
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- JP5650589B2 JP5650589B2 JP2011124074A JP2011124074A JP5650589B2 JP 5650589 B2 JP5650589 B2 JP 5650589B2 JP 2011124074 A JP2011124074 A JP 2011124074A JP 2011124074 A JP2011124074 A JP 2011124074A JP 5650589 B2 JP5650589 B2 JP 5650589B2
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- 239000002243 precursor Substances 0.000 title claims description 201
- 238000000034 method Methods 0.000 title claims description 127
- 238000000151 deposition Methods 0.000 title claims description 54
- 125000004191 (C1-C6) alkoxy group Chemical group 0.000 claims description 63
- 238000000231 atomic layer deposition Methods 0.000 claims description 63
- 230000008569 process Effects 0.000 claims description 63
- 239000000758 substrate Substances 0.000 claims description 54
- 229910052710 silicon Inorganic materials 0.000 claims description 52
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 51
- 239000010703 silicon Substances 0.000 claims description 51
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 50
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 49
- 125000000217 alkyl group Chemical group 0.000 claims description 49
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 44
- DMSPFACBWOXIBX-UHFFFAOYSA-N 1-phenyl-N-silylmethanamine Chemical compound [SiH3]NCC1=CC=CC=C1 DMSPFACBWOXIBX-UHFFFAOYSA-N 0.000 claims description 42
- 125000000882 C2-C6 alkenyl group Chemical group 0.000 claims description 42
- 230000008021 deposition Effects 0.000 claims description 42
- 125000003601 C2-C6 alkynyl group Chemical group 0.000 claims description 41
- 238000006243 chemical reaction Methods 0.000 claims description 39
- 238000005229 chemical vapour deposition Methods 0.000 claims description 37
- 238000010926 purge Methods 0.000 claims description 36
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 35
- 229910052760 oxygen Inorganic materials 0.000 claims description 35
- 239000001301 oxygen Substances 0.000 claims description 35
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 34
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 31
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 28
- 229910052757 nitrogen Inorganic materials 0.000 claims description 26
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 24
- 125000003118 aryl group Chemical group 0.000 claims description 24
- 239000007789 gas Substances 0.000 claims description 24
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 24
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 23
- 125000006165 cyclic alkyl group Chemical group 0.000 claims description 23
- 125000004122 cyclic group Chemical group 0.000 claims description 23
- 125000006619 (C1-C6) dialkylamino group Chemical group 0.000 claims description 21
- 229910052739 hydrogen Inorganic materials 0.000 claims description 19
- 239000001257 hydrogen Substances 0.000 claims description 19
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 14
- 229910052801 chlorine Inorganic materials 0.000 claims description 13
- 229910052740 iodine Inorganic materials 0.000 claims description 13
- 229910021529 ammonia Inorganic materials 0.000 claims description 12
- 229910052794 bromium Inorganic materials 0.000 claims description 12
- 229910052731 fluorine Inorganic materials 0.000 claims description 12
- 238000005137 deposition process Methods 0.000 claims description 11
- 125000004663 dialkyl amino group Chemical group 0.000 claims description 11
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 11
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 10
- OQWBSXTWPDAPPV-UHFFFAOYSA-N 2-phenyl-N-silylethanamine Chemical compound [SiH3]NCCC1=CC=CC=C1 OQWBSXTWPDAPPV-UHFFFAOYSA-N 0.000 claims description 10
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims description 10
- 239000011261 inert gas Substances 0.000 claims description 8
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 claims description 8
- XOVJJNMNAPZVRJ-UHFFFAOYSA-N (2-methyl-2,3-dihydroindol-1-yl)silane Chemical compound C1=CC=C2N([SiH3])C(C)CC2=C1 XOVJJNMNAPZVRJ-UHFFFAOYSA-N 0.000 claims description 7
- UCDBDBSGNPSTBN-UHFFFAOYSA-N N-phenylsilylcyclohexanamine Chemical compound C1(=CC=CC=C1)[SiH2]NC1CCCCC1 UCDBDBSGNPSTBN-UHFFFAOYSA-N 0.000 claims description 7
- 238000007740 vapor deposition Methods 0.000 claims description 6
- 239000007800 oxidant agent Substances 0.000 claims description 5
- 229910001220 stainless steel Inorganic materials 0.000 claims description 5
- 239000010935 stainless steel Substances 0.000 claims description 5
- 238000003682 fluorination reaction Methods 0.000 claims 8
- XDYSZJWYKJEHOU-UHFFFAOYSA-N 2-(3-methylphenyl)-N-silylethanamine Chemical compound CC1=CC=CC(CCN[SiH3])=C1 XDYSZJWYKJEHOU-UHFFFAOYSA-N 0.000 claims 6
- SMUQFGGVLNAIOZ-UHFFFAOYSA-N quinaldine Chemical compound C1=CC=CC2=NC(C)=CC=C21 SMUQFGGVLNAIOZ-UHFFFAOYSA-N 0.000 claims 4
- QJILMVAZWDJDCY-UHFFFAOYSA-N 1-(3-methylphenyl)-N-silylmethanamine Chemical compound CC1=CC=CC(CN[SiH3])=C1 QJILMVAZWDJDCY-UHFFFAOYSA-N 0.000 claims 3
- RDAPLJSCPBSLCH-UHFFFAOYSA-N 3,4,4a,5-tetrahydro-2H-quinolin-1-ylsilane Chemical compound C1C=CC=C2N([SiH3])CCCC21 RDAPLJSCPBSLCH-UHFFFAOYSA-N 0.000 claims 3
- NDBBZBQLUDGEDQ-UHFFFAOYSA-N C1=CC=C2C(C)=CN([SiH3])C2=C1 Chemical compound C1=CC=C2C(C)=CN([SiH3])C2=C1 NDBBZBQLUDGEDQ-UHFFFAOYSA-N 0.000 claims 3
- XXLADWVIQZCPFB-UHFFFAOYSA-N C1=CC=C2N([SiH3])C(C)=CC2=C1 Chemical compound C1=CC=C2N([SiH3])C(C)=CC2=C1 XXLADWVIQZCPFB-UHFFFAOYSA-N 0.000 claims 3
- PCFJQWUWYALMQK-UHFFFAOYSA-N C1=CC=C2N([SiH3])C3=CC=CC=C3C2=C1 Chemical compound C1=CC=C2N([SiH3])C3=CC=CC=C3C2=C1 PCFJQWUWYALMQK-UHFFFAOYSA-N 0.000 claims 3
- FKCZQNIXGBYXIN-UHFFFAOYSA-N C1=CC=C2N([SiH3])C=CC2=C1 Chemical compound C1=CC=C2N([SiH3])C=CC2=C1 FKCZQNIXGBYXIN-UHFFFAOYSA-N 0.000 claims 3
- ZKUBSEYEIQWQSW-UHFFFAOYSA-N C1=CC=C2N([SiH3])CCOC2=C1 Chemical compound C1=CC=C2N([SiH3])CCOC2=C1 ZKUBSEYEIQWQSW-UHFFFAOYSA-N 0.000 claims 3
- ABIHSJKBVVGBBY-UHFFFAOYSA-N CC1=CC=C(CCN[SiH3])C=C1 Chemical compound CC1=CC=C(CCN[SiH3])C=C1 ABIHSJKBVVGBBY-UHFFFAOYSA-N 0.000 claims 3
- CAYRWRYVJCNDFL-UHFFFAOYSA-N CC1=CC=CC=C1CCN[SiH3] Chemical compound CC1=CC=CC=C1CCN[SiH3] CAYRWRYVJCNDFL-UHFFFAOYSA-N 0.000 claims 3
- BBRCBCVDYRGCNT-UHFFFAOYSA-N N-phenylsilylpropan-2-amine Chemical compound CC(C)N[SiH2]C1=CC=CC=C1 BBRCBCVDYRGCNT-UHFFFAOYSA-N 0.000 claims 3
- JAXJVLDDUIEPQY-UHFFFAOYSA-N C1=CC=C2N([SiH3])C(C)CCC2=C1 Chemical compound C1=CC=C2N([SiH3])C(C)CCC2=C1 JAXJVLDDUIEPQY-UHFFFAOYSA-N 0.000 claims 1
- 150000002431 hydrogen Chemical class 0.000 claims 1
- 238000001947 vapour-phase growth Methods 0.000 claims 1
- 239000010408 film Substances 0.000 description 133
- 238000004949 mass spectrometry Methods 0.000 description 23
- 229910052751 metal Inorganic materials 0.000 description 22
- 239000002184 metal Substances 0.000 description 22
- 125000006575 electron-withdrawing group Chemical group 0.000 description 15
- 229910004298 SiO 2 Inorganic materials 0.000 description 13
- 239000006227 byproduct Substances 0.000 description 13
- 125000001424 substituent group Chemical group 0.000 description 13
- AWFPGKLDLMAPMK-UHFFFAOYSA-N dimethylaminosilicon Chemical group CN(C)[Si] AWFPGKLDLMAPMK-UHFFFAOYSA-N 0.000 description 12
- 239000000463 material Substances 0.000 description 12
- 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 11
- 238000009835 boiling Methods 0.000 description 11
- -1 but not limited to Substances 0.000 description 11
- 239000003153 chemical reaction reagent Substances 0.000 description 11
- 229910000077 silane Inorganic materials 0.000 description 11
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 10
- 230000004888 barrier function Effects 0.000 description 10
- 239000012467 final product Substances 0.000 description 10
- 239000010410 layer Substances 0.000 description 10
- 125000003545 alkoxy group Chemical group 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 9
- 239000003446 ligand Substances 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 239000004065 semiconductor Substances 0.000 description 9
- 230000004913 activation Effects 0.000 description 8
- 125000004432 carbon atom Chemical group C* 0.000 description 8
- 238000004518 low pressure chemical vapour deposition Methods 0.000 description 8
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical class [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 8
- 238000005094 computer simulation Methods 0.000 description 7
- WZUCGJVWOLJJAN-UHFFFAOYSA-N diethylaminosilicon Chemical compound CCN([Si])CC WZUCGJVWOLJJAN-UHFFFAOYSA-N 0.000 description 7
- 125000004430 oxygen atom Chemical group O* 0.000 description 7
- 239000011541 reaction mixture Substances 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methylaniline Chemical compound CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 238000005292 vacuum distillation Methods 0.000 description 6
- 235000012431 wafers Nutrition 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 125000004429 atom Chemical group 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- LBUJPTNKIBCYBY-UHFFFAOYSA-N 1,2,3,4-tetrahydroquinoline Chemical compound C1=CC=C2CCCNC2=C1 LBUJPTNKIBCYBY-UHFFFAOYSA-N 0.000 description 4
- 238000003775 Density Functional Theory Methods 0.000 description 4
- OJGMBLNIHDZDGS-UHFFFAOYSA-N N-Ethylaniline Chemical compound CCNC1=CC=CC=C1 OJGMBLNIHDZDGS-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 125000000304 alkynyl group Chemical group 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 4
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 description 4
- 238000007323 disproportionation reaction Methods 0.000 description 4
- 239000002019 doping agent Substances 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 239000012686 silicon precursor Substances 0.000 description 4
- 229910052715 tantalum Inorganic materials 0.000 description 4
- 238000002230 thermal chemical vapour deposition Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- 150000004703 alkoxides Chemical class 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 230000005587 bubbling Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 239000012159 carrier gas Substances 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 150000003961 organosilicon compounds Chemical class 0.000 description 3
- 150000004756 silanes Chemical class 0.000 description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 3
- 238000004088 simulation Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- LISDBLOKKWTHNH-UHFFFAOYSA-N 1,3,5-Trisilacyclohexan Natural products C1[SiH2]C[SiH2]C[SiH2]1 LISDBLOKKWTHNH-UHFFFAOYSA-N 0.000 description 2
- QRWRJDVVXAXGBT-UHFFFAOYSA-N 2-Methylindoline Chemical compound C1=CC=C2NC(C)CC2=C1 QRWRJDVVXAXGBT-UHFFFAOYSA-N 0.000 description 2
- BHNHHSOHWZKFOX-UHFFFAOYSA-N 2-methyl-1H-indole Chemical compound C1=CC=C2NC(C)=CC2=C1 BHNHHSOHWZKFOX-UHFFFAOYSA-N 0.000 description 2
- FIHILUSWISKVSR-UHFFFAOYSA-N 3,6-dibromo-9h-carbazole Chemical compound C1=C(Br)C=C2C3=CC(Br)=CC=C3NC2=C1 FIHILUSWISKVSR-UHFFFAOYSA-N 0.000 description 2
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000005046 Chlorosilane Substances 0.000 description 2
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 229910052729 chemical element Inorganic materials 0.000 description 2
- VBCSQFQVDXIOJL-UHFFFAOYSA-N diethylazanide;hafnium(4+) Chemical compound [Hf+4].CC[N-]CC.CC[N-]CC.CC[N-]CC.CC[N-]CC VBCSQFQVDXIOJL-UHFFFAOYSA-N 0.000 description 2
- VJDVOZLYDLHLSM-UHFFFAOYSA-N diethylazanide;titanium(4+) Chemical compound [Ti+4].CC[N-]CC.CC[N-]CC.CC[N-]CC.CC[N-]CC VJDVOZLYDLHLSM-UHFFFAOYSA-N 0.000 description 2
- ZYLGGWPMIDHSEZ-UHFFFAOYSA-N dimethylazanide;hafnium(4+) Chemical compound [Hf+4].C[N-]C.C[N-]C.C[N-]C.C[N-]C ZYLGGWPMIDHSEZ-UHFFFAOYSA-N 0.000 description 2
- DWCMDRNGBIZOQL-UHFFFAOYSA-N dimethylazanide;zirconium(4+) Chemical compound [Zr+4].C[N-]C.C[N-]C.C[N-]C.C[N-]C DWCMDRNGBIZOQL-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- NPEOKFBCHNGLJD-UHFFFAOYSA-N ethyl(methyl)azanide;hafnium(4+) Chemical compound [Hf+4].CC[N-]C.CC[N-]C.CC[N-]C.CC[N-]C NPEOKFBCHNGLJD-UHFFFAOYSA-N 0.000 description 2
- LNKYFCABELSPAN-UHFFFAOYSA-N ethyl(methyl)azanide;titanium(4+) Chemical compound [Ti+4].CC[N-]C.CC[N-]C.CC[N-]C.CC[N-]C LNKYFCABELSPAN-UHFFFAOYSA-N 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 description 2
- DMCPFOBLJMLSNX-UHFFFAOYSA-N indole-3-acetonitrile Chemical compound C1=CC=C2C(CC#N)=CNC2=C1 DMCPFOBLJMLSNX-UHFFFAOYSA-N 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- LQFLWKPCQITJIH-UHFFFAOYSA-N n-allyl-aniline Chemical compound C=CCNC1=CC=CC=C1 LQFLWKPCQITJIH-UHFFFAOYSA-N 0.000 description 2
- TXTHKGMZDDTZFD-UHFFFAOYSA-N n-cyclohexylaniline Chemical compound C1CCCCC1NC1=CC=CC=C1 TXTHKGMZDDTZFD-UHFFFAOYSA-N 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- ZFRKQXVRDFCRJG-UHFFFAOYSA-N skatole Chemical compound C1=CC=C2C(C)=CNC2=C1 ZFRKQXVRDFCRJG-UHFFFAOYSA-N 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- MNWRORMXBIWXCI-UHFFFAOYSA-N tetrakis(dimethylamido)titanium Chemical compound CN(C)[Ti](N(C)C)(N(C)C)N(C)C MNWRORMXBIWXCI-UHFFFAOYSA-N 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000006200 vaporizer Substances 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- 125000004890 (C1-C6) alkylamino group Chemical group 0.000 description 1
- KWEKXPWNFQBJAY-UHFFFAOYSA-N (dimethyl-$l^{3}-silanyl)oxy-dimethylsilicon Chemical compound C[Si](C)O[Si](C)C KWEKXPWNFQBJAY-UHFFFAOYSA-N 0.000 description 1
- PUNGSQUVTIDKNU-UHFFFAOYSA-N 2,4,6,8,10-pentamethyl-1,3,5,7,9,2$l^{3},4$l^{3},6$l^{3},8$l^{3},10$l^{3}-pentaoxapentasilecane Chemical compound C[Si]1O[Si](C)O[Si](C)O[Si](C)O[Si](C)O1 PUNGSQUVTIDKNU-UHFFFAOYSA-N 0.000 description 1
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- 238000011282 treatment Methods 0.000 description 1
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 description 1
- XOAJIYVOSJHEQB-UHFFFAOYSA-N trimethyl trimethoxysilyl silicate Chemical compound CO[Si](OC)(OC)O[Si](OC)(OC)OC XOAJIYVOSJHEQB-UHFFFAOYSA-N 0.000 description 1
- PQDJYEQOELDLCP-UHFFFAOYSA-N trimethylsilane Chemical compound C[SiH](C)C PQDJYEQOELDLCP-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 230000005428 wave function Effects 0.000 description 1
- 238000001039 wet etching Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
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- 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
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- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/025—Silicon compounds without C-silicon linkages
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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
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/34—Nitrides
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- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/34—Nitrides
- C23C16/345—Silicon nitride
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- 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
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- 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
- C23C16/50—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 using electric discharges
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/02—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances
- H01B3/12—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances ceramics
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- Plasma & Fusion (AREA)
- Chemical Vapour Deposition (AREA)
- Formation Of Insulating Films (AREA)
Description
反応チャンバーに上記基材の上記少なくとも1つの表面を与えるステップ;及び
次の式Iによって表される少なくとも1種の有機アミノシラン前駆体から、化学気相成長プロセス及び原子層堆積プロセスから選択される堆積プロセスによって、上記少なくとも1つの表面に上記ケイ素含有膜を形成するステップ:
a.基材を反応器に与えるステップ;
b.上記反応器に、次の式Iによって表される少なくとも1種の有機アミノシラン前駆体から選択される少なくとも1種のケイ素前駆体を導入するステップ:
c.上記反応器を、パージガスでパージするステップ;
d.上記反応器に、酸素源を導入するステップ;
e.上記反応器を、パージガスでパージするステップ;及び
f.上記膜の所望の厚みが得られるまで、b〜eのステップを繰り返すステップ。
a.基材を反応器に与えるステップ;
b.上記反応器に、次の式Iによって表される少なくとも1種の有機アミノシラン前駆体を導入するステップ:
c.酸素源を与えて、上記少なくとも1つの表面に上記酸化ケイ素膜を堆積させるステップ。
a.基材を反応器に与えるステップ;
b.上記反応器に、次の式Iによって表される少なくとも1種のケイ素前駆体を導入するステップ:
c.上記反応器を、パージガスでパージするステップ;
d.上記反応器に、窒素含有源を導入するステップ;
e.上記反応器を、パージガスでパージするステップ;及び
f.上記窒化ケイ素膜の所望の厚みが得られるまで、b〜eのステップを繰り返すステップ。
a.基材を反応器に与えるステップ;
b.上記反応器に、次の式Iによって表される少なくとも1種の有機アミノシラン前駆体を導入するステップ:
c.窒素含有源を与えるステップであって、上記少なくとも1種の有機アミノシラン前駆体と、上記窒素含有源とを反応させて、ケイ素及び窒素の両方を含有する上記膜を上記少なくとも1つの表面に堆積させるステップ。
基材をALD反応器に与えるステップ;
上記ALD反応器に、次の式Iによって表される前駆体を含む少なくとも1種の有機アミノシラン前駆体を導入するステップ:
上記少なくとも1種の有機アミノシラン前駆体を、基材に化学吸着させるステップ;
未吸着の上記少なくとも1種の有機アミノシラン前駆体を、パージガスを用いてパージするステップ;
窒素含有源を、加熱した上記基材上の上記有機アミノシラン前駆体に与えて、上記吸着した少なくとも1種の有機アミノシラン前駆体と反応させるステップ;及び
随意に、あらゆる未反応の窒素含有源をパージするステップ。
基材を反応器に与えるステップ;
上記反応器に、次の式Iによって表される少なくとも1種の有機アミノシラン前駆体を導入するステップ:
上記少なくとも1種の有機アミノシラン前駆体を、基材に化学吸着させるステップ;
上記未吸着の少なくとも1種の有機アミノシラン前駆体を、パージガスを用いてパージするステップ;
酸素含有源を、加熱した上記基材上の上記有機アミノシラン前駆体に与えて、上記吸着した少なくとも1種の有機アミノシラン前駆体と反応させるステップ;及び
随意に、あらゆる未反応の酸素含有源をパージするステップ。
周囲温度から約700℃までの範囲の温度に加熱し、且つ1Torr以下の圧力で維持した反応器に、1以上の基材を配置するステップ;
次の式Iを有する少なくとも1種の有機アミノシラン前駆体を導入するステップ:
酸素源を、上記反応器に与えて、上記少なくとも1種の有機アミノシラン前駆体と少なくとも部分的に反応させ、そして上記1以上の基材に誘電体膜を堆積させるステップ。
周囲温度から約700℃までの範囲の温度に加熱し、且つ1Torr以下の圧力で維持した反応器に、1以上の基材を配置するステップ;
次の式Iを有する少なくとも1種の有機アミノシラン前駆体を導入するステップ:
窒素含有源を、上記反応器に与えて、上記少なくとも1種の有機アミノシラン前駆体と少なくとも部分的に反応させ、そして上記1以上の基材に誘電体膜を堆積させるステップ。
500mlのシュレンクフラスコで、64.2グラム(g)(0.6mol)のN−メチルアニリン及び131g(1.0mol)のジ−イソプロピルアミノシランを、周囲温度において窒素雰囲気下で24時間攪拌した。比較的低い沸点の副生成物ジ−イソプロピルアミンを、20mmHgの圧力及び室温(25℃)で減圧除去した。反応混合物を、さらに24時間攪拌した。最終生成物のフェニルメチルアミノシラン(73.6g、収率89.5%)を、沸点の60℃で、5mmHgで減圧蒸留によって得た。最終生成物を、質量分光(MS)によって特徴付けた。これを、図1に与える。これは、特に137、122、106、91及び77でピークを示している。フェニルメチルアミノシランの分子量は、137.27であった。
機械的攪拌器、コンデンサー、ガスバブリング注入口を具備する2000mlの三口フラスコで、1000mlのヘキサン、53.5g(0.5mol)のN−メチルアニリン、及び50.5g(0.5mol)のトリエチルアミンを、窒素雰囲気下で攪拌しながら、−20℃まで冷却した。モノクロロシラン(MCS)を反応混合物に通してバブリングした。白い固体の沈殿物を形成した。反応が完了した後、反応混合物の温度を温めて、室温とし、さらに2時間室温で攪拌した。固体のトリエチルアミン塩酸塩を、ろ過によって除去し、溶媒のヘキサンを蒸留によって除去した。生成物のフェニルメチルアミノシラン(51.3g、収率75%)を、沸点の60℃で、5mmHgでの減圧蒸留によって得た。この化合物を、質量分光によって特徴付け、この生成物がフェニルアミノシランであることを確認した。例1と例2の比較は、比較的高い生成収率を与える例1の合成方法が、実験室スケールの合成では、より有利であることを示している。
500mlのシュレンクフラスコで、60.5g(0.5mol)のN−エチルアニリン及び131g(1.0mol)のジ−イソプロピルアミノシランを、周囲温度において窒素雰囲気下で24時間攪拌した。比較的低い沸点の副生成物ジ−イソプロピルアミンを、20mmHgの圧力及び室温(25℃)で減圧除去した。反応混合物を、さらに24時間攪拌した。最終生成物のフェニルエチルアミノシランを減圧蒸留によって得た。最終生成物を、質量分光(MS)によって特徴付けた。これを、図2に与える。これは、特に151、150、136、120、106、93及び77でピークを示している。フェニルエチルアミノシランの分子量は、151.28であった。
500mlのシュレンクフラスコで、62.5g(0.5mol)のN−アリルアニリン及び131g(1.0mol)のジ−イソプロピルアミノシランを、周囲温度において窒素雰囲気下で24時間攪拌した。比較的低い沸点の副生成物ジ−イソプロピルアミンを、20mmHgの圧力及び室温(25℃)で減圧除去した。反応混合物を、さらに24時間攪拌した。最終生成物のフェニルアリルアミノシランを減圧蒸留によって得た。最終生成物を、質量分光(MS)によって特徴付けた。これを、図3に与える。これは、特に163、162、148、136、120、107、93及び77でピークを示している。フェニルアリルアミノシランの分子量は、163.29であった。
500mlのシュレンクフラスコで、62.5g(0.5mol)の2−メチルインドリン及び131g(1.0mol)のジ−イソプロピルアミノシランを、周囲温度において窒素雰囲気下で24時間攪拌した。比較的低い沸点の副生成物ジ−イソプロピルアミンを、20mmHgの圧力及び室温(25℃)で減圧除去した。反応混合物を、さらに24時間攪拌した。最終生成物のN−シリル−2−メチルインドリンを減圧蒸留によって得た。この化合物を、質量分光(MS)によって特徴付けた。最終生成物を、質量分光(MS)によって特徴付けた。これを、図4に与える。これは、特に163、162、148、132、117、105、91及び77でピークを示している。N−シリル−2−メチルインドリンの分子量は、163.29であった。
500mlのシュレンクフラスコで、87.5g(0.6mol)のN−シクロヘキシルアニリン及び131g(1.0mol)のジ−イソプロピルアミノシランを、周囲温度において窒素雰囲気下で24時間攪拌した。比較的低い沸点の副生成物ジ−イソプロピルアミンを、20mmHgの圧力及び室温(25℃)で減圧除去した。反応混合物を、さらに24時間攪拌した。最終生成物のフェニルシクロヘキシルアミノシランを減圧蒸留によって得た。最終生成物を、質量分光(MS)によって特徴付けた。これを、図5に与える。これは、特に205、178、162、132、115、93及び77でピークを示している。フェニルシクロヘキシルアミノシランの分子量は、205.37であった。
SPARTAN06シミュレーションパッケージソフトウェア(Wavefunction社、アーバイン、カリフォルニア州、米国)を用いてPM3に基づく量子力学的な方法を使って、α−H移動(α−H migration)及び不均化反応に対する、複数の前駆体の相対的な化学的安定性について調査した。量子力学的な密度汎関数理論(Density Functional Theory)を用いて、コンピュータモデリングソフトウエアを使用した大規模計算を実行して、様々なSiN前駆体の反応エネルギーを系統的に評価した。この計算を、分極関数によって拡張された二重数値原子基底関数(double numerical atomic basis set)を加味したPerdew−Wangにより提案された交換相関汎関数(PW91)を用いて、一般化勾配近似(GGA:Generalized gradient approximation)の下で行った。全ての分子構造を、エネルギー的に最も好ましい配置を得るように、完全に最適化した。コンピューター解析で用いた前駆体は次の通りである:ジメチルアミノシラン(DMAS)及び本明細書に記載した式Iを有する前駆体又はフェニルメチルアミノシラン(PMAS)。
2(CH3)2NSiH3→(CH3)2NSiH2N(CH3)2+SiH4
この反応に関して計算した熱化学的なエネルギー及び活性化障壁は、それぞれ−0.6kcal/mol及び5.4kcal/molである。この反応は、本質的に熱化学的に中立であるが、非常に低い活性化障壁が、室温で不均化反応を促進し、DMASが安定ではないことを示す。
酸化ケイ素膜の原子層堆積を、有機アミノシラン前駆体のフェニルメチルアミノシラン(PMAS)を用いて実行して、例7のコンピューターシミュレーションの結果を検証した。堆積を、実験室スケールのALDプロセスツールで、150℃から開始して実行し、温度を、室温まで又は前駆体が酸化物膜の生成をしなくなるまで低下させた。SiO2膜を堆積するために用いたこのプロセスステップを、表3に示す。酸素源ガスとしてオゾンを用いた500サイクルを基準として用いて、堆積を行った。また、堆積のプロセスパラメーターを表3に与える。
酸化ケイ素膜の原子層堆積を、表3に記載したALDプロセスを用いて、有機アミノシラン前駆体のフェニルメチルアミノシラン(PMAS)及びジイソプロピルアミノシラン(DIPAS)を使用して行った。堆積を、実験室スケールのALDプロセスツールで、図9のy軸に示す温度で行った(例えば、23℃又は室温、50℃、75℃及び100℃)。生成酸化ケイ素膜を、サイクル当たりの堆積率及び屈折率に関して特徴づけ、そしてまたこの結果を、図9及び図10に与えた。図9では、サイクル当たりの堆積率を、オングストローム(Å)/サイクルとして測定する。図10では、膜の屈折率を、エリプソメーター(FilmTek 2000SE)を用いて、膜からの反射データを所定の物理的モデル(例えば、ローレンツ振動子モデル)にフィッティングすることによって、測定した。上述したように、屈折率に関して、おおよそ1.44〜1.47の値が、通常のCVDの酸化ケイ素膜を反映するであろう。
有機アミノシラン前駆体のフェニルメチルアミノシランを、窒化ケイ素膜を形成するための堆積プロセスについてのケイ素源としての効果、及び堆積した薄膜の特性に関して調査した。薄膜堆積を、LPCVD水平炉又はATVPEO612炉を用いて実行した。堆積のための実施圧力は、約1Torrであり、堆積温度は、570℃及び650℃であった(表6参照)。NH3を窒素源として用いた。PMAS前駆体を、ベーパードロー(vapor draw)及び異なる前駆体材料に関して蒸気圧を変える事に基づいて調節したラインの温度を用いて、その炉に提供した。堆積のためのプロセスパラメーターを、表6に与える。
窒化ケイ素膜を、リモートプラズマシステムを備えた(AE systems)層流反応器(CNT Savannah 100)を用いて、堆積させた。通常のALDサイクルは次のステップからなる。フェニルメチルアミノシランを70℃で保持し、10sccmの窒素をキャリアガスとしてバブリングにより、反応器に提供した。そのN−メチルアニリニルシランの投与時間は、0.05秒〜5秒の範囲であり;不活性ガスでパージをし;基準の真空度までポンプで排出し;0.9KWの出力に設定したプラズマ発生器を通じて、5sccmの流量でアンモニアプラズマを導入し、そしてウェハーの真上にあるスリットバルブを開いて、2〜9秒の範囲でウェハー表面に曝露し;そして、不活性ガスでパージし、基準の真空度に排出した。このサイクルを、所望の厚みが得られるまで繰り返した。
フェニルメチルアミノシラン(PMAS)のサンプルを、55〜60℃での石英バブラー(quartz bubbler)に装填し、約5週間保持した。このサンプルのガスクロマトグラフィ(GC)解析は、この期間の後でも殆ど劣化がないことを示す。フェニルメチルアミノシランの他の1つのサンプルを、ガラスバイアル瓶に装填し、グローブボックス内に室温で115日間保持した。GC解析は、0.5%未満の劣化を示す。同様のグローブボックスの試験を、次の有機アミノシラン前駆体に対して行った:PMAS、ビスtert−ブチルアミノシラン(BTBAS)、ジエチルアミノシラン(DEAS)及びジイソプロピルアミノシラン(DIPAS)。この試験の結果を図11に与える。BTBASは、2000年から半導体産業で窒化ケイ素及び酸化ケイ素を堆積するのに用いられている。図11は、PMASが、BTBAS及びDIPASと同様の安定性を有することを示す。対照的に、DEASは、顕著な劣化を示す。安定性の結果は、フェニルメチルアミノシランが、熱的に安定であり、半導体プロセス用の有機アミノシラン前駆体として適切であることを示唆している。
Claims (34)
- 次の式Iで表される有機アミノシラン前駆体:
- 前記R1及びR2が、共に結合して環を形成している、請求項1に記載の有機アミノシラン前駆体。
- 前記R1及びR2が、同種である、請求項1に記載の有機アミノシラン前駆体。
- 前記R1及びR2が、異種である、請求項1に記載の有機アミノシラン前駆体。
- フェニルメチルアミノシラン、フェニルエチルアミノシラン、フェニル−イソ−プロピルアミノシラン、フェニルアリルアミノシラン、m−トリルメチルアミノシラン、N−シリル−テトラヒドロキノリン、N−シリル−3−アニリノプロピオニトリル、N−シリル−N−フェニルグリシノニトリル、N−シリルカルバゾール、フェニルシクロヘキシルアミノシラン、N−シリル−2−メチルインドリン、N−シリルベンゾモルホリン、N−シリルインドール、N−シリル−2−メチルインドール、N−シリル−3−メチルインドール、o−トリルエチルアミノシラン、p−トリルエチルアミノシラン、m−トリルエチルアミノシラン、及びN−シリル−1,2,3,4−テトラヒドロ−2−メチルキノリンからなる群より選択される、請求項1に記載の有機アミノシラン前駆体。
- フェニルメチルアミノシランである、請求項5に記載の有機アミノシラン前駆体。
- フェニルエチルアミノシランである、請求項5に記載の有機アミノシラン前駆体。
- m−トリルエチルアミノシランである、請求項5に記載の有機アミノシラン前駆体。
- 次のステップを含む、化学気相成長プロセス及び原子層堆積プロセスから選択される堆積プロセスによって、基材の少なくとも1つの表面に誘電体フィルムを形成する方法。
反応チャンバー中に前記基材の前記少なくとも1つの表面を与えるステップ
前記反応チャンバーに、次の式Iを有する少なくとも1種の有機アミノシラン前駆体を導入するステップ:
前記反応チャンバーに窒素含有源を導入するステップであって、前記少なくとも1種の有機アミノシラン前駆体と、前記窒素含有源とを反応させて、前記少なくとも1つの表面上の前記誘電体フィルムとするステップ。 - 次のステップを含む、原子層堆積(ALD)プロセスにより誘電体フィルムを形成する方法:
a.基材をALD反応器に与えるステップ;
b.前記ALD反応器に、次の式Iを有する少なくとも1種の有機アミノシラン前駆体を与えるステップ:
c.前記ALD反応器を、不活性ガスでパージするステップ;
d.前記ALD反応器に、窒素含有源を導入するステップ;
e.前記ALD反応器を、不活性ガスでパージするステップ;及び
f.前記誘電体フィルムの所望の厚みが得られるまで、b〜eのステップを繰り返すステップ。 - 次のステップを含む、プラズマ強化原子層堆積(PEALD)プロセスを用いて基材の少なくとも1つの表面に誘電体フィルムを形成する方法:
a.基材をALD反応器に与えるステップ;
b.前記ALD反応器に、次の式Iを有する少なくとも1種の有機アミノシラン前駆体を与えるステップ:
c.前記ALD反応器を、不活性ガスでパージするステップ;
d.前記ALD反応器に、プラズマ窒素含有源を導入するステップ;
e.前記ALD反応器を、不活性ガスでパージするステップ;及び
f.前記誘電体フィルムの所望の厚みが得られるまで、b〜eのステップを繰り返すステップ。 - 前記少なくとも1種の有機アミノシラン前駆体が、フェニルメチルアミノシラン、フェニルエチルアミノシラン、フェニル−イソ−プロピルアミノシラン、フェニルアリルアミノシラン、m−トリルメチルアミノシラン、N−シリル−テトラヒドロキノリン、N−シリル−3−アニリノプロピオニトリル、N−シリル−N−フェニルグリシノニトリル、N−シリルカルバゾール、フェニルシクロヘキシルアミノシラン、N−シリル−2−メチルインドリン、N−シリルベンゾモルホリン、N−シリルインドール、N−シリル−2−メチルインドール、N−シリル−3−メチルインドール、o−トリルエチルアミノシラン、p−トリルエチルアミノシラン、m−トリルエチルアミノシラン、及びN−シリル−1,2,3,4−テトラヒドロ−2−メチルキノリンからなる群より選択される、請求項9〜11のいずれか一項に記載の方法。
- 前記少なくとも1種の有機アミノシラン前駆体が、フェニルメチルアミノシランである、請求項12に記載の方法。
- 前記少なくとも1種の有機アミノシラン前駆体が、フェニルエチルアミノシランである、請求項12に記載の方法。
- 前記少なくとも1種の有機アミノシラン前駆体が、m−トリルエチルアミノシランである、請求項12に記載の方法。
- 前記窒素含有源が、アンモニア、ヒドラジン、モノアルキルヒドラジン、ジアルキルヒドラジン、窒素、窒素/水素、アンモニアプラズマ、窒素プラズマ、窒素/水素プラズマ及びこれらの混合物からなる群より選択される、請求項9〜15のいずれか一項に記載の方法。
- 前記誘電体フィルムが、窒化ケイ素及び炭化窒化ケイ素からなる群より選択される、請求項9〜16のいずれか一項に記載の方法。
- 次のステップを含む、基材に酸化ケイ素フィルムを形成する方法:
酸化剤と、次の式Iで表される有機アミノシラン前駆体を含む前駆体とを、気相成長で反応させて、前記基材に前記酸化ケイ素フィルムを形成するステップ:
- 前記気相成長が、化学気相成長、低圧気相成長、プラズマ強化化学気相成長、サイクリック化学気相成長、プラズマ強化サイクリック化学気相成長、原子層堆積及びプラズマ強化原子層堆積からなる群より選択される少なくとも1つである、請求項18に記載の方法。
- 次のステップを含む、基材に酸化ケイ素フィルムを形成する方法:
次の式Iで表される少なくとも一種の有機アミノシラン前駆体を含む組成物、及び少なくとも1種の酸化剤から、前記基材に前記酸化ケイ素フィルムを気相成長により形成するステップ:
ここで、前記気相成長は、化学気相成長、低圧気相成長、プラズマ強化化学気相成長、サイクリック化学気相成長、プラズマ強化サイクリック化学気相成長、原子層堆積及びプラズマ強化原子層堆積からなる群より選択される少なくとも1つである。 - 次のステップを含む、基材に酸化ケイ素フィルムを形成する方法:
次の式Iで表される有機アミノシラン前駆体を反応器に導入するステップ:
少なくとも1種の酸化剤を、前記反応器に導入するステップであって、前記少なくとも1種の酸化剤と、前記有機アミノシランを反応させて、前記基材に前記酸化ケイ素を与えるステップ。 - 次のステップを含む、厚みを有する酸化ケイ素フィルムを基材に形成する方法:
a.次の式Iで表される少なくとも1種の有機アミノシランを、堆積チャンバーに導入するステップ:
b.前記少なくとも1種の有機アミノシラン前駆体を、前記基材に化学吸着させるステップ;
c.前記未反応の少なくとも1種の有機アミノシラン前駆体を、パージガスを用いてパージするステップ;
d.酸素源を、加熱した前記基材上の前記有機アミノシラン前駆体に与えて、前記吸着した少なくとも1種の有機アミノシラン前駆体と反応させるステップ;及び
e.随意に、あらゆる未反応の酸素源をパージするステップ。 - 前記フィルムの厚みが定まるまで、ステップa〜d及び随意のステップeを繰り返す、請求項22に記載の方法。
- 前記少なくとも1種の有機アミノシラン前駆体が、フェニルメチルアミノシラン、フェニルエチルアミノシラン、フェニル−イソ−プロピルアミノシラン、フェニルアリルアミノシラン、m−トリルメチルアミノシラン、N−シリル−テトラヒドロキノリン、N−シリル−3−アニリノプロピオニトリル、N−シリル−N−フェニルグリシノニトリル、N−シリルカルバゾール、フェニルシクロヘキシルアミノシラン、N−シリル−2−メチルインドリン、N−シリルベンゾモルホリン、N−シリルインドール、N−シリル−2−メチルインドール、N−シリル−3−メチルインドール、o−トリルエチルアミノシラン、p−トリルエチルアミノシラン、m−トリルエチルアミノシラン、及びN−シリル−1,2,3,4−テトラヒドロ−2−メチルキノリンからなる群より選択される、請求項18〜23のいずれか一項に記載の方法。
- 前記少なくとも1種の有機アミノシラン前駆体が、フェニルメチルアミノシランである、請求項24に記載の方法。
- 前記少なくとも1種の有機アミノシラン前駆体が、フェニルエチルアミノシランである、請求項24に記載の方法。
- 前記少なくとも1種の有機アミノシラン前駆体が、m−トリルエチルアミノシランである、請求項24に記載の方法。
- 前記反応ステップを、200℃以下の温度で実行する、請求項18〜27のいずれか一項に記載の方法。
- 前記反応ステップを、100℃以下の温度で実行する、請求項28に記載の方法。
- 前記反応ステップを、50℃以下で実行する、請求項29に記載の方法。
- 原子層堆積プロセスである、請求項21に記載の方法。
- プラズマ強化サイクリック化学気相成長プロセスである、請求項21に記載の方法。
- 次の式Iにより表される前駆体、及びケイ素含有フィルムの堆積のための前記前駆体を提供するために用いる容器を含む製品:
ここで、前記前駆体の純度は、98%以上である。 - 前記容器が、ステンレス鋼からなる、請求項33に記載の製品。
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2011
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EP2392691B1 (en) | 2014-09-03 |
KR20110132534A (ko) | 2011-12-08 |
CN102295657A (zh) | 2011-12-28 |
KR20130034033A (ko) | 2013-04-04 |
JP2012025733A (ja) | 2012-02-09 |
TW201202466A (en) | 2012-01-16 |
KR101275143B1 (ko) | 2013-06-17 |
EP2392691A1 (en) | 2011-12-07 |
US20120128897A1 (en) | 2012-05-24 |
US8912353B2 (en) | 2014-12-16 |
CN102295657B (zh) | 2015-04-29 |
TWI491760B (zh) | 2015-07-11 |
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