TW202506695A - Novel aminoalkoxysilylamine compound, method for preparing the same, and uses of the same - Google Patents
Novel aminoalkoxysilylamine compound, method for preparing the same, and uses of the same Download PDFInfo
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 116
- 238000000034 method Methods 0.000 title claims abstract description 40
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 81
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 80
- 239000010703 silicon Substances 0.000 claims abstract description 75
- 239000010409 thin film Substances 0.000 claims abstract description 43
- 238000000151 deposition Methods 0.000 claims abstract description 29
- 239000000203 mixture Substances 0.000 claims abstract description 23
- 238000004519 manufacturing process Methods 0.000 claims abstract description 21
- 125000000217 alkyl group Chemical group 0.000 claims description 165
- 239000000126 substance Substances 0.000 claims description 87
- 239000001257 hydrogen Substances 0.000 claims description 79
- 229910052739 hydrogen Inorganic materials 0.000 claims description 79
- 125000003545 alkoxy group Chemical group 0.000 claims description 45
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 43
- 150000002431 hydrogen Chemical class 0.000 claims description 34
- -1 alkyl lithium Chemical compound 0.000 claims description 20
- 229910052736 halogen Inorganic materials 0.000 claims description 18
- 150000002367 halogens Chemical class 0.000 claims description 17
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 15
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 13
- 229910052744 lithium Inorganic materials 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 2
- 239000010408 film Substances 0.000 description 80
- 239000000758 substrate Substances 0.000 description 35
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 24
- 239000002243 precursor Substances 0.000 description 22
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 21
- 229910052814 silicon oxide Inorganic materials 0.000 description 21
- 238000000231 atomic layer deposition Methods 0.000 description 18
- 230000008021 deposition Effects 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 239000007789 gas Substances 0.000 description 10
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 6
- 239000012686 silicon precursor Substances 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000005229 chemical vapour deposition Methods 0.000 description 5
- 125000000524 functional group Chemical group 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000012495 reaction gas Substances 0.000 description 5
- 230000009257 reactivity Effects 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 238000004518 low pressure chemical vapour deposition Methods 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000002411 thermogravimetry Methods 0.000 description 4
- 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
- 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 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- VOSJXMPCFODQAR-UHFFFAOYSA-N ac1l3fa4 Chemical compound [SiH3]N([SiH3])[SiH3] VOSJXMPCFODQAR-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 229910003002 lithium salt Inorganic materials 0.000 description 3
- 159000000002 lithium salts Chemical class 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910010271 silicon carbide Inorganic materials 0.000 description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- JMOKYFFZJXICCP-UHFFFAOYSA-N CN(C)[Si](C)(N)N(C)C Chemical compound CN(C)[Si](C)(N)N(C)C JMOKYFFZJXICCP-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
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 2
- 229910007991 Si-N Inorganic materials 0.000 description 2
- 229910052581 Si3N4 Inorganic materials 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 229910006294 Si—N Inorganic materials 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- GYQKYMDXABOCBE-UHFFFAOYSA-N chloro-dimethoxy-methylsilane Chemical compound CO[Si](C)(Cl)OC GYQKYMDXABOCBE-UHFFFAOYSA-N 0.000 description 2
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- JILPJDVXYVTZDQ-UHFFFAOYSA-N lithium methoxide Chemical class [Li+].[O-]C JILPJDVXYVTZDQ-UHFFFAOYSA-N 0.000 description 2
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 229910021420 polycrystalline silicon Inorganic materials 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
- 238000010926 purge Methods 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 125000000229 (C1-C4)alkoxy group Chemical group 0.000 description 1
- 238000005133 29Si NMR spectroscopy Methods 0.000 description 1
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 229910005540 GaP Inorganic materials 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 229910000673 Indium arsenide Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229920012266 Poly(ether sulfone) PES Polymers 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- 229910003811 SiGeC Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910000577 Silicon-germanium Inorganic materials 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 1
- 239000012346 acetyl chloride Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- BUMGIEFFCMBQDG-UHFFFAOYSA-N dichlorosilicon Chemical compound Cl[Si]Cl BUMGIEFFCMBQDG-UHFFFAOYSA-N 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- PKTOVQRKCNPVKY-UHFFFAOYSA-N dimethoxy(methyl)silicon Chemical compound CO[Si](C)OC PKTOVQRKCNPVKY-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- BLHLJVCOVBYQQS-UHFFFAOYSA-N ethyllithium Chemical compound [Li]CC BLHLJVCOVBYQQS-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229920002457 flexible plastic Polymers 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 229910021482 group 13 metal Inorganic materials 0.000 description 1
- RPQDHPTXJYYUPQ-UHFFFAOYSA-N indium arsenide Chemical compound [In]#[As] RPQDHPTXJYYUPQ-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 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
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- DVSDBMFJEQPWNO-UHFFFAOYSA-N methyllithium Chemical compound C[Li] DVSDBMFJEQPWNO-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 239000001272 nitrous oxide Substances 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 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
- 238000002360 preparation method Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000007261 regionalization Effects 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
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000000427 thin-film deposition Methods 0.000 description 1
- LXEXBJXDGVGRAR-UHFFFAOYSA-N trichloro(trichlorosilyl)silane Chemical compound Cl[Si](Cl)(Cl)[Si](Cl)(Cl)Cl LXEXBJXDGVGRAR-UHFFFAOYSA-N 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
以下揭露內容係關於一種新穎胺基烷氧基矽基胺（aminoalkoxysilylamine）化合物、一種用於製備該新穎胺基烷氧基矽基胺化合物之方法、一種包含該新穎胺基烷氧基矽基胺化合物之用於沈積含矽薄膜之組成物、以及一種使用該新穎胺基烷氧基矽基胺化合物來製造含矽薄膜之方法。The following disclosure relates to a novel aminoalkoxysilylamine compound, a method for preparing the novel aminoalkoxysilylamine compound, a composition for depositing a silicon-containing film comprising the novel aminoalkoxysilylamine compound, and a method for making a silicon-containing film using the novel aminoalkoxysilylamine compound.
在半導體領域中，藉由各種沈積製程將含矽薄膜製造成各種形式之薄膜，例如矽膜、氧化矽膜、氮化矽膜、碳氮化矽膜及氮氧化矽膜，且近來，已將多晶矽薄膜用於薄膜電晶體（thin film transistor，TFT）、太陽能電池等之中且多晶矽薄膜之應用領域正變得日益多樣化。In the semiconductor field, silicon-containing films are manufactured into various forms of films by various deposition processes, such as silicon films, silicon oxide films, silicon nitride films, silicon carbonitride films, and silicon oxynitride films. Recently, polycrystalline silicon films have been used in thin film transistors (TFTs), solar cells, etc., and the application fields of polycrystalline silicon films are becoming increasingly diverse.
已知用於製造含矽薄膜之代表性技術包含化學氣相沈積（chemical vapor deposition，CVD）及原子層沈積（atomic layer deposition，ALD），其中在化學氣相沈積中，混合氣體形式之矽前驅物係與反應氣體進行反應以在一基板表面上形成膜、或者該矽前驅物係直接在表面上反應以形成膜；在原子層沈積中，氣體形式之矽前驅物係以物理或化學方式吸附至一基板表面上，然後藉由隨後添加反應氣體來形成膜；並且使用例如低壓化學氣相沈積（low pressure chemical vapor deposition，LPCVD）、以及容許在低溫下使用電漿進行沈積之電漿增強型化學氣相沈積（plasma-enhanced chemical vapor deposition，PECVD）與電漿增強型原子層沈積（plasma-enhanced atomic layer deposition，PEALD）等技術之各種薄膜製造技術係被應用於次世代半導體及顯示裝置製造製程中，並被使用於在超精細圖案形成及奈米厚度方面具有均勻及優異性質之超薄膜沈積中。Representative techniques known for fabricating silicon-containing thin films include chemical vapor deposition (CVD), in which a silicon precursor in the form of a mixed gas reacts with a reactive gas to form a film on a substrate surface, or the silicon precursor reacts directly on the surface to form a film; in atomic layer deposition, a silicon precursor in the form of a gas is physically or chemically adsorbed onto a substrate surface, and then a film is formed by subsequently adding a reactive gas; and techniques such as low pressure chemical vapor deposition (LPCVD) and plasma-enhanced chemical vapor deposition (ALD) that allows deposition at low temperatures using plasma are used. Various thin film manufacturing technologies such as PECVD and plasma-enhanced atomic layer deposition (PEALD) are applied in the manufacturing process of next-generation semiconductors and display devices, and are used in the deposition of ultra-thin films with uniformity and excellent properties in ultra-fine pattern formation and nanometer thickness.
用於形成含矽薄膜之前驅物係代表性地為矽烷、氯化矽烷、胺基矽烷及烷氧基矽烷等形式之化合物，且作為一具體實例，包含氯化矽烷（例如二氯矽烷（SiH 2Cl 2）及六氯二矽烷（Cl 3SiSiCl 3））、三矽基胺（N(SiH 3) 3）、雙二乙基胺基矽烷（H 2Si(N(CH 2CH 3) 2) 2）、二異丙基胺基矽烷（H 3SiN(i-C 3H 7) 2）等形式之化合物，該等係用於半導體製造及顯示器製造之大規模生產製程中。 The precursor used to form the silicon-containing film is typically a compound in the form of silane, chlorosilane, aminosilane and alkoxysilane, and as a specific example, includes compounds in the form of chlorosilane (e.g., dichlorosilane (SiH 2 Cl 2 ) and hexachlorodisilane (Cl 3 SiSiCl 3 )), trisilylamine (N(SiH 3 ) 3 ), bisdiethylaminosilane (H 2 Si(N(CH 2 CH 3 ) 2 ) 2 ), diisopropylaminosilane (H 3 SiN(iC 3 H 7 ) 2 ), etc., which are used in large-scale production processes for semiconductor manufacturing and display manufacturing.
然而，由於元件之超高集成所導致的元件微型化與長寬比增加、以及元件材料多樣化，需要一種用於形成在期望低溫下具有均勻薄厚度且具有優異的電性能之超精細薄膜之技術，且因此，使用傳統矽前驅物在600°C或更高溫度下之高溫製程、步階覆蓋（step coverage）、蝕刻性質以及薄膜之物理與電學性質的問題正日益顯現，且因此，需要開發一種新穎且改良的矽前驅物。However, due to the miniaturization and increase in aspect ratio of devices caused by ultra-high integration of devices, and the diversification of device materials, a technology for forming an ultra-fine film with a uniform thin thickness and excellent electrical properties at a desired low temperature is required, and therefore, problems with high-temperature processes at 600°C or higher using conventional silicon precursors, step coverage, etching properties, and physical and electrical properties of thin films are becoming increasingly apparent, and therefore, there is a need to develop a novel and improved silicon precursor.
[相關技術文獻][Related technical literature]
[非專利文獻][Non-patent literature]
《Monatshefte fuer Chemie（ 化學月刊）》（1968），99(4)，1372-5 Monatshefte fuer Chemie ( Chemical Monthly ) (1968), 99(4), 1372-5
本發明之一實施態樣旨在提供一種新穎胺基烷氧基矽基胺化合物。One embodiment of the present invention is to provide a novel aminoalkoxysilylamine compound.
具體而言，本發明之一實施態樣旨在提供一種胺基烷氧基矽基胺化合物，其可作為用於形成含矽薄膜之前驅物，且具有熱穩定性及高揮發性。Specifically, one embodiment of the present invention is to provide an aminoalkoxysilylamine compound which can be used as a pre-driver for forming a silicon-containing film and has thermal stability and high volatility.
具體而言，本發明之一實施態樣旨在提供一種新穎胺基烷氧基矽基胺化合物，其可形成在寬的溫度範圍內具有優異反應性的穩定含矽薄膜。Specifically, one embodiment of the present invention is to provide a novel aminoalkoxysilylamine compound that can form a stable silicon-containing film with excellent reactivity over a wide temperature range.
本發明之另一實施態樣旨在提供一種用於製備該胺基烷氧基矽基胺化合物之方法。Another embodiment of the present invention is to provide a method for preparing the aminoalkoxysilylamine compound.
本發明之另一實施態樣旨在提供一種用於沈積含矽薄膜之組成物，其係包含根據本發明之一示例性實施態樣之胺基烷氧基矽基胺化合物。Another embodiment of the present invention is to provide a composition for depositing a silicon-containing film, which comprises an aminoalkoxysilylamine compound according to an exemplary embodiment of the present invention.
本發明之又一實施態樣旨在提供一種用於形成具有優異特性之含矽薄膜的方法，其係使用一用於沈積含矽薄膜之組成物，該組成物包括該胺基烷氧基矽基胺化合物。Another embodiment of the present invention is to provide a method for forming a silicon-containing film with excellent properties, which uses a composition for depositing a silicon-containing film, wherein the composition includes the aminoalkoxysilylamine compound.
在一個一般態樣中，提供一種胺基烷氧基矽基胺化合物，其係由以下化學式1表示： [化學式1] 其中 R 1為C1至C5烷基； R 2、R 3、R 6及R 7各自獨立為氫、C1至C5烷基或C1至C5烷氧基； R 4、R 5及R 8各自獨立為氫或C1至C5烷基； R 9為C1至C5烷基； A為NR 10R 11或OR 12； R 10為氫或C1至C5烷基；以及 R 11及R 12各自獨立為C1至C5烷基； 條件為以下情形除外：當A為OR 12，R 1、R 8、R 9及R 12皆為乙基，且R 2至R 7皆為甲基。 In a general aspect, an aminoalkoxysilylamine compound is provided, which is represented by the following chemical formula 1: [Chemical formula 1] wherein R 1 is C1 to C5 alkyl; R 2 , R 3 , R 6 and R 7 are each independently hydrogen, C1 to C5 alkyl or C1 to C5 alkoxy; R 4 , R 5 and R 8 are each independently hydrogen or C1 to C5 alkyl; R 9 is C1 to C5 alkyl; A is NR 10 R 11 or OR 12 ; R 10 is hydrogen or C1 to C5 alkyl; and R 11 and R 12 are each independently C1 to C5 alkyl; except for the following situation: when A is OR 12 , R 1 , R 8 , R 9 and R 12 are all ethyl, and R 2 to R 7 are all methyl.
在根據一示例性實施態樣之化學式1之化合物中，R 1可為C1至C3烷基；R 2、R 3、R 6及R 7可各自獨立為氫、C1至C3烷基或C1至C3烷氧基；R 4、R 5及R 8可各自獨立為氫或C1至C3烷基；R 9可為C1至C3烷基；A可為NR 10R 11或OR 12；R 10可為氫或C1至C3烷基；且R 11及R 12可各自獨立為C1至C5烷基。 In the compound of Formula 1 according to an exemplary embodiment, R 1 may be a C1 to C3 alkyl group; R 2 , R 3 , R 6 and R 7 may each independently be a hydrogen, a C1 to C3 alkyl group or a C1 to C3 alkoxy group; R 4 , R 5 and R 8 may each independently be a hydrogen or a C1 to C3 alkyl group; R 9 may be a C1 to C3 alkyl group; A may be NR 10 R 11 or OR 12 ; R 10 may be a hydrogen or a C1 to C3 alkyl group; and R 11 and R 12 may each independently be a C1 to C5 alkyl group.
根據一示例性實施態樣之化合物可為由以下化學式2表示之化合物： [化學式2] 其中 R 1為C1至C5烷基； R 2、R 3、R 6及R 7各自獨立為氫、C1至C5烷基或C1至C5烷氧基； R 4、R 5、R 8及R 10各自獨立為氫或C1至C5烷基；以及 R 9及R 11為C1至C5烷基。 According to an exemplary embodiment, the compound may be a compound represented by the following Chemical Formula 2: wherein R 1 is C1 to C5 alkyl; R 2 , R 3 , R 6 and R 7 are each independently hydrogen, C1 to C5 alkyl or C1 to C5 alkoxy; R 4 , R 5 , R 8 and R 10 are each independently hydrogen or C1 to C5 alkyl; and R 9 and R 11 are C1 to C5 alkyl.
在根據一示例性實施態樣之化學式2之化合物中，R 1可為C1至C3烷基；R 2、R 3、R 6及R 7可各自獨立為氫、C1至C3烷基或C1至C3烷氧基；R 4、R 5、R 8及R 10可各自獨立為氫或C1至C3烷基；且R 9及R 11可為C1至C3烷基。 In the compound of Formula 2 according to an exemplary embodiment, R 1 may be a C1 to C3 alkyl group; R 2 , R 3 , R 6 and R 7 may each independently be hydrogen, a C1 to C3 alkyl group or a C1 to C3 alkoxy group; R 4 , R 5 , R 8 and R 10 may each independently be hydrogen or a C1 to C3 alkyl group; and R 9 and R 11 may be C1 to C3 alkyl groups.
根據一示例性實施態樣之化合物可為由以下化學式3表示之化合物： [化學式3] 其中 R 1為C1至C5烷基； R 2、R 3、R 6及R 7各自獨立為氫、C1至C5烷基或C1至C5烷氧基； R 4、R 5及R 8各自獨立為氫或C1至C5烷基；以及 R 9及R 12各自獨立為C1至C5烷基； 條件為以下情形除外：當R 1、R 8、R 9及R 12皆為乙基，且R 2至R 7皆為甲基。 According to an exemplary embodiment, the compound may be a compound represented by the following Chemical Formula 3: wherein R 1 is C1 to C5 alkyl; R 2 , R 3 , R 6 and R 7 are each independently hydrogen, C1 to C5 alkyl or C1 to C5 alkoxy; R 4 , R 5 and R 8 are each independently hydrogen or C1 to C5 alkyl; and R 9 and R 12 are each independently C1 to C5 alkyl; except for the following situation: when R 1 , R 8 , R 9 and R 12 are all ethyl, and R 2 to R 7 are all methyl.
在根據一示例性實施態樣之化合物中，R 1可為C1至C3烷基；R 2、R 3、R 6及R 7可各自獨立為氫、C1至C3烷基或C1至C3烷氧基；R 4、R 5及R 8可各自獨立為氫或C1至C3烷基；且R 9及R 12可各自獨立為C1至C3烷基。 In a compound according to an exemplary embodiment, R 1 may be a C1 to C3 alkyl group; R 2 , R 3 , R 6 and R 7 may each independently be hydrogen, a C1 to C3 alkyl group or a C1 to C3 alkoxy group; R 4 , R 5 and R 8 may each independently be hydrogen or a C1 to C3 alkyl group; and R 9 and R 12 may each independently be a C1 to C3 alkyl group.
根據一示例性實施態樣之化合物可為選自以下結構之至少一者： 。 The compound according to an exemplary embodiment may be at least one selected from the following structures: .
在另一個一般態樣中，一種用於製備以下化學式1之胺基烷氧基矽基胺化合物的方法係包括：使（C1至C5）烷基鋰、以下化學式4之化合物與以下化學式5之化合物進行反應，以製備以下化學式1之胺基烷氧基矽基胺化合物， [化學式1] [化學式4] [化學式5] 其中 R 1為C1至C5烷基； R 2、R 3、R 6及R 7各自獨立為氫、C1至C5烷基或C1至C5烷氧基； R 4、R 5及R 8各自獨立為氫或C1至C5烷基； R 9為C1至C5烷基； R'為C1至C5烷氧基或鹵素； A為NR 10R 11或OR 12； R 10為氫或C1至C5烷基；以及 R 11及R 12各自獨立地C1至C5烷基； 條件為以下情形除外：當A為OR 12，R 1、R 8、R 9及R 12皆為乙基，且R 2至R 7皆為甲基。 In another general aspect, a method for preparing an aminoalkoxysilylamine compound of the following chemical formula 1 comprises: reacting a (C1 to C5) alkyl lithium, a compound of the following chemical formula 4, and a compound of the following chemical formula 5 to prepare an aminoalkoxysilylamine compound of the following chemical formula 1, [Chemical formula 1] [Chemical formula 4] [Chemical formula 5] wherein R 1 is C1 to C5 alkyl; R 2 , R 3 , R 6 and R 7 are each independently hydrogen, C1 to C5 alkyl or C1 to C5 alkoxy; R 4 , R 5 and R 8 are each independently hydrogen or C1 to C5 alkyl; R 9 is C1 to C5 alkyl; R' is C1 to C5 alkoxy or halogen; A is NR 10 R 11 or OR 12 ; R 10 is hydrogen or C1 to C5 alkyl; and R 11 and R 12 are each independently C1 to C5 alkyl; except for the following situation: when A is OR 12 , R 1 , R 8 , R 9 and R 12 are all ethyl, and R 2 to R 7 are all methyl.
根據一示例性實施態樣，用於製備化學式1之胺基烷氧基矽基胺化合物之方法係包括：當化學式4中之R'為鹵素時，使以下化學式6之化合物與一鹵素源進行反應，以製備化學式4之化合物， [化學式6] 其中 R 1為C1至C5烷基； R 2及R 3各自獨立為氫、C1至C5烷基或C1至C5烷氧基；以及 R 21為C1至C5烷氧基。 According to an exemplary embodiment, a method for preparing an aminoalkoxysilylamine compound of Chemical Formula 1 comprises: when R' in Chemical Formula 4 is a halogen, reacting a compound of the following Chemical Formula 6 with a halogen source to prepare a compound of Chemical Formula 4, [Chemical Formula 6] wherein R 1 is C1 to C5 alkyl; R 2 and R 3 are each independently hydrogen, C1 to C5 alkyl or C1 to C5 alkoxy; and R 21 is C1 to C5 alkoxy.
在另一個一般態樣中，一種用於沈積含矽薄膜之組成物係包含由以下化學式11表示之化合物： [化學式11] 其中 R 1為C1至C5烷基； R 2、R 3、R 6及R 7各自獨立為氫、C1至C5烷基或C1至C5烷氧基； R 4、R 5及R 8各自獨立為氫或C1至C5烷基； R 9為C1至C5烷基； A為NR 10R 11或OR 12； R 10為氫或C1至C5烷基；以及 R 11及R 12各自獨立為C1至C5烷基。 In another general aspect, a composition for depositing a silicon-containing film comprises a compound represented by the following Chemical Formula 11: [Chemical Formula 11] wherein R 1 is C1 to C5 alkyl; R 2 , R 3 , R 6 and R 7 are each independently hydrogen, C1 to C5 alkyl or C1 to C5 alkoxy; R 4 , R 5 and R 8 are each independently hydrogen or C1 to C5 alkyl; R 9 is C1 to C5 alkyl; A is NR 10 R 11 or OR 12 ; R 10 is hydrogen or C1 to C5 alkyl; and R 11 and R 12 are each independently C1 to C5 alkyl.
在又一個一般態樣中，提供一種製造含矽薄膜之方法，其係使用由以下化學式11表示之化合物： [化學式11] 其中 R 1為C1至C5烷基； R 2、R 3、R 6及R 7各自獨立為氫、C1至C5烷基或C1至C5烷氧基； R 4、R 5及R 8各自獨立為氫或C1至C5烷基； R 9為C1至C5烷基； A為NR 10R 11或OR 12； R 10為氫或C1至C5烷基；以及 R 11及R 12各自獨立為C1至C5烷基。 In another general aspect, a method for manufacturing a silicon-containing thin film is provided, which uses a compound represented by the following Chemical Formula 11: [Chemical Formula 11] wherein R 1 is C1 to C5 alkyl; R 2 , R 3 , R 6 and R 7 are each independently hydrogen, C1 to C5 alkyl or C1 to C5 alkoxy; R 4 , R 5 and R 8 are each independently hydrogen or C1 to C5 alkyl; R 9 is C1 to C5 alkyl; A is NR 10 R 11 or OR 12 ; R 10 is hydrogen or C1 to C5 alkyl; and R 11 and R 12 are each independently C1 to C5 alkyl.
從以下詳細說明、圖式及申請專利範圍中可明確顯示出其他特徵及態樣。Other features and aspects will become apparent from the following detailed description, drawings and claims.
以下，將詳細描述本發明。本文中所使用的技術術語及科學術語，除非另有定義，否則具有所屬技術領域中具有通常知識者所理解的一般含義，且已知功能與結構的描述若可能不必要地掩蓋本發明的要點則在後續的描述與附圖中將予以省略。The present invention will be described in detail below. Unless otherwise defined, the technical and scientific terms used herein have the general meanings understood by those of ordinary skill in the art, and the description of known functions and structures will be omitted in the subsequent description and drawings if it may unnecessarily cover the main points of the present invention.
本說明書中的用語「C A至C B」係指「具有A個或更多以及B個或更少的碳原子」，而用語「A至B」則指「A個或更多以及B個或更少」。 In the present specification, the term " CA to CB " means "having A or more and B or less carbon atoms", and the term "A to B" means "A or more and B or less".
本說明書之用語「烷基」為單價取代基且包括直鏈或支鏈二種形式。The term "alkyl" used in this specification is a monovalent substituent and includes both straight chain and branched chain forms.
烷基可具有1至5個碳原子，具體係具有1至3個碳原子。The alkyl group may have 1 to 5 carbon atoms, specifically 1 to 3 carbon atoms.
作為一實例，烷基包括甲基、乙基、正丙基、異丙基、正丁基、異丁基、三級丁基、戊基等，但並非僅限於此。As an example, the alkyl group includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, etc., but is not limited thereto.
本說明書之用語「烷氧基」為-O-烷基基團，其中「烷基」係如上定義。其具體實例包括甲氧基、乙氧基、異丙氧基、丁氧基、異丁氧基、三級丁氧基等，但並非僅限於此。The term "alkoxy" used in this specification refers to an -O-alkyl group, wherein "alkyl" is as defined above. Specific examples thereof include methoxy, ethoxy, isopropoxy, butoxy, isobutoxy, tert-butoxy, etc., but are not limited thereto.
本說明書之用語「鹵素」係指第17族元素，且可為選自F、Cl、Br及I之任一者。The term "halogen" used in this specification refers to a Group 17 element and may be any one selected from F, Cl, Br and I.
此外，本說明書中的用語「包含」是一個開放式描述，其含義相當於「被提供」、「含有」、「具有」或「特徵為」等用語，並不排除未進一步列出的元素、材料或過程。In addition, the term "comprising" in this specification is an open description, which means equivalent to terms such as "provided", "containing", "having" or "characterized by", and does not exclude elements, materials or processes that are not further listed.
此外，除非上下文另有指示，本說明書中所使用的單數形式也可能意味著包括複數形式。In addition, unless the context indicates otherwise, the singular forms used in this specification may also be intended to include the plural forms.
本說明書之用語「胺基烷氧基矽基胺化合物」可由化學式1表示，且與「含矽薄膜之前驅物」乙詞具有相同之含義。The term "aminoalkoxysilylamine compound" used in this specification can be represented by Chemical Formula 1 and has the same meaning as the term "silicon-containing film precursor".
本說明書之用語「熱穩定性（thermal stability）」可指即使在連續加熱製程或高溫製程期間亦不會改變之物理性質，且具體而言，係指即使長時間暴露於上述惡劣條件下亦不會引起結構變化。The term "thermal stability" as used in this specification may refer to a physical property that does not change even during a continuous heating process or a high-temperature process, and specifically, means that the structure does not change even if exposed to the above-mentioned harsh conditions for a long time.
本說明書之用語「具有優異特性之含矽薄膜」係指具有高矽含量、優異熱穩定性及優異耐久性之高品質含矽薄膜。The term "silicon-containing film with excellent properties" used in this specification refers to a high-quality silicon-containing film with high silicon content, excellent thermal stability and excellent durability.
在本說明書中，「常溫」可指處於不進行人工溫度調節之狀態下之溫度，且舉例而言，常溫可為20°C至40°C、20°C至30°C或23°C至26°C。In this specification, "normal temperature" may refer to a temperature without artificial temperature regulation, and for example, normal temperature may be 20°C to 40°C, 20°C to 30°C, or 23°C to 26°C.
本發明提供一種新穎胺基烷氧基矽基胺化合物，其可作為用於製造含矽薄膜之一前驅物，且本發明之胺基烷氧基矽基胺化合物係由以下化學式1表示： [化學式1] 其中 R 1為C1至C5烷基； R 2、R 3、R 6及R 7各自獨立為氫、C1至C5烷基或C1至C5烷氧基； R 4、R 5及R 8各自獨立為氫或C1至C5烷基； R 9為C1至C5烷基； A為NR 10R 11或OR 12； R 10為氫或C1至C5烷基；以及 R 11及R 12各自獨立為C1至C5烷基； 條件為以下情形除外：當A為OR 12，R 1、R 8、R 9及R 12皆為乙基，且R 2至R 7皆為甲基。 The present invention provides a novel aminoalkoxysilylamine compound, which can be used as a precursor for manufacturing a silicon-containing thin film. The aminoalkoxysilylamine compound of the present invention is represented by the following chemical formula 1: [Chemical formula 1] wherein R 1 is C1 to C5 alkyl; R 2 , R 3 , R 6 and R 7 are each independently hydrogen, C1 to C5 alkyl or C1 to C5 alkoxy; R 4 , R 5 and R 8 are each independently hydrogen or C1 to C5 alkyl; R 9 is C1 to C5 alkyl; A is NR 10 R 11 or OR 12 ; R 10 is hydrogen or C1 to C5 alkyl; and R 11 and R 12 are each independently C1 to C5 alkyl; except for the following situation: when A is OR 12 , R 1 , R 8 , R 9 and R 12 are all ethyl, and R 2 to R 7 are all methyl.
本發明之胺基烷氧基矽基胺化合物係具有其中至少一或多個烷氧基官能基與一胺官能基被同時引入至一具有三矽基胺結構之矽原子的結構，由於烷氧基官能基被引入至矽原子而具有經改善的反應性及較低的活化能，且不會產生非揮發性副產物，因而容易以高沈積速率形成高純度的含矽薄膜。The aminoalkoxysilylamine compound of the present invention has a structure in which at least one or more alkoxy functional groups and an amine functional group are simultaneously introduced into a silicon atom having a trisilylamine structure. Since the alkoxy functional group is introduced into the silicon atom, the compound has improved reactivity and lower activation energy, and does not generate non-volatile by-products, so that a high-purity silicon-containing thin film can be easily formed at a high deposition rate.
根據本發明一示例性實施態樣之胺基烷氧基矽基胺化合物具體而言可由胺基矽基烷氧基矽基胺（aminosilylalkoxysilylamine）化合物表示。The aminoalkoxysilylamine compound according to an exemplary embodiment of the present invention can be specifically represented by an aminosilylalkoxysilylamine compound.
在根據一具體實例之胺基烷氧基矽基胺化合物中，在化學式1中，R 1可為C1至C3烷基；R 2、R 3、R 6及R 7可各自獨立為氫、C1至C3烷基或C1至C3烷氧基；R 4、R 5及R 8可各自獨立為氫或C1至C3烷基；R 9可為C1至C3烷基；A可為NR 10R 11或OR 12；R 10可為氫或C1至C3烷基；R 11及R 12可各自獨立為C1至C5烷基，且當A為OR 12時以下情形除外：R 1、R 8、R 9及R 12皆為乙基，且R 2至R 7皆為甲基。 In the aminoalkoxysilylamine compound according to a specific example, in Chemical Formula 1, R 1 may be a C1 to C3 alkyl group; R 2 , R 3 , R 6 and R 7 may each independently be a hydrogen, a C1 to C3 alkyl group or a C1 to C3 alkoxy group; R 4 , R 5 and R 8 may each independently be a hydrogen or a C1 to C3 alkyl group; R 9 may be a C1 to C3 alkyl group; A may be NR 10 R 11 or OR 12 ; R 10 may be a hydrogen or a C1 to C3 alkyl group; R 11 and R 12 may each independently be a C1 to C5 alkyl group, and when A is OR 12 , the following situations are excluded: R 1 , R 8 , R 9 and R 12 are all ethyl groups, and R 2 to R 7 are all methyl groups.
具體而言，根據本發明一示例性實施態樣之胺基烷氧基矽基胺化合物係排除以下情形：當A為OR 12，且R 1、R 8、R 9及R 12皆為乙基。 Specifically, the aminoalkoxysilylamine compound according to an exemplary embodiment of the present invention excludes the following situation: when A is OR 12 , and R 1 , R 8 , R 9 and R 12 are all ethyl groups.
作為一具體實例，本發明之胺基烷氧基矽基胺化合物可為由以下化學式2表示之化合物： [化學式2] 其中 R 1為C1至C5烷基； R 2、R 3、R 6及R 7各自獨立為氫、C1至C5烷基或C1至C5烷氧基； R 4、R 5、R 8及R 10各自獨立為氫或C1至C5烷基；以及 R 9及R 11為C1至C5烷基。 As a specific example, the aminoalkoxysilylamine compound of the present invention can be a compound represented by the following Chemical Formula 2: [Chemical Formula 2] wherein R 1 is C1 to C5 alkyl; R 2 , R 3 , R 6 and R 7 are each independently hydrogen, C1 to C5 alkyl or C1 to C5 alkoxy; R 4 , R 5 , R 8 and R 10 are each independently hydrogen or C1 to C5 alkyl; and R 9 and R 11 are C1 to C5 alkyl.
在根據一示例性實施態樣之化學式2之化合物中，R 1可為C1至C4烷基；R 2、R 3、R 6及R 7可各自獨立為氫、C1至C4烷基或C1至C4烷氧基；R 4、R 5、R 8及R 10可各自獨立為氫或C1至C4烷基；且R 9及R 11可為C1至C4烷基。 In the compound of Formula 2 according to an exemplary embodiment, R 1 may be a C1 to C4 alkyl group; R 2 , R 3 , R 6 and R 7 may each independently be hydrogen, a C1 to C4 alkyl group or a C1 to C4 alkoxy group; R 4 , R 5 , R 8 and R 10 may each independently be hydrogen or a C1 to C4 alkyl group; and R 9 and R 11 may be C1 to C4 alkyl groups.
更具體而言，R 1可為C1至C3烷基；R 2、R 3、R 6及R 7可各自獨立為氫、C1至C3烷基或C1至C3烷氧基；R 4、R 5、R 8及R 10可各自獨立為氫或C1至C3烷基；且R 9及R 11可為C1至C3烷基。 More specifically, R 1 may be a C1 to C3 alkyl group; R 2 , R 3 , R 6 and R 7 may each independently be hydrogen, a C1 to C3 alkyl group or a C1 to C3 alkoxy group; R 4 , R 5 , R 8 and R 10 may each independently be hydrogen or a C1 to C3 alkyl group; and R 9 and R 11 may be C1 to C3 alkyl groups.
作為一具體實例，本發明之胺基烷氧基矽基胺化合物可為由以下化學式3表示之化合物： [化學式3] 其中 R 1為C1至C5烷基； R 2、R 3、R 6及R 7各自獨立為氫、C1至C5烷基或C1至C5烷氧基； R 4、R 5及R 8各自獨立為氫或C1至C5烷基；且 R 9及R 12各自獨立為C1至C5烷基； 條件為以下情形除外：當R 1、R 8、R 9及R 12皆為乙基，且R 2至R 7皆為甲基。 As a specific example, the aminoalkoxysilylamine compound of the present invention can be a compound represented by the following Chemical Formula 3: [Chemical Formula 3] wherein R 1 is C1 to C5 alkyl; R 2 , R 3 , R 6 and R 7 are each independently hydrogen, C1 to C5 alkyl or C1 to C5 alkoxy; R 4 , R 5 and R 8 are each independently hydrogen or C1 to C5 alkyl; and R 9 and R 12 are each independently C1 to C5 alkyl; except for the following situation: when R 1 , R 8 , R 9 and R 12 are all ethyl, and R 2 to R 7 are all methyl.
在根據一具體實例之化學式3之化合物中，R 1可為C1至C4烷基；R 2、R 3、R 6及R 7可各自獨立為氫、C1至C4烷基或C1至C4烷氧基；R 4、R 5及R 8可各自獨立為氫或C1至C4烷基；且R 9及R 12可各自獨立為C1至C4烷基；條件為以下情形除外：當R 1、R 8、R 9及R 12皆為乙基，且R 2至R 7皆為甲基。 In the compound of formula 3 according to a specific example, R 1 may be C1 to C4 alkyl; R 2 , R 3 , R 6 and R 7 may each independently be hydrogen, C1 to C4 alkyl or C1 to C4 alkoxy; R 4 , R 5 and R 8 may each independently be hydrogen or C1 to C4 alkyl; and R 9 and R 12 may each independently be C1 to C4 alkyl; except for the following situation: when R 1 , R 8 , R 9 and R 12 are all ethyl, and R 2 to R 7 are all methyl.
更具體而言，R 1可為C1至C3烷基；R 2、R 3、R 6及R 7可各自獨立為氫、C1至C3烷基或C1至C3烷氧基；R 4、R 5及R 8可各自獨立為氫或C1至C3烷基；且R 9及R 12可各自獨立為C1至C3烷基；條件為以下情形除外：當R 1、R 8、R 9及R 12皆為乙基，且R 2至R 7皆為甲基。 More specifically, R 1 may be a C1 to C3 alkyl group; R 2 , R 3 , R 6 and R 7 may each independently be hydrogen, a C1 to C3 alkyl group or a C1 to C3 alkoxy group; R 4 , R 5 and R 8 may each independently be hydrogen or a C1 to C3 alkyl group; and R 9 and R 12 may each independently be a C1 to C3 alkyl group; except for the following situation: when R 1 , R 8 , R 9 and R 12 are all ethyl groups, and R 2 to R 7 are all methyl groups.
根據一具體實例之胺基烷氧基矽基胺化合物可選自以下化合物，但並非僅限於此： 。 According to a specific example, the aminoalkoxysilylamine compound can be selected from the following compounds, but is not limited thereto: .
此外，本發明提供一種用於製備胺基烷氧基矽基胺化合物之方法。In addition, the present invention provides a method for preparing an aminoalkoxysilylamine compound.
作為一示例性實施態樣，提供一種用於製備以下化學式1之胺基烷氧基矽基胺化合物之方法，該方法包括：使（C1至C5）烷基鋰、以下化學式4之化合物與以下化學式5之化合物進行反應，以製備以下化學式1之胺基烷氧基矽基胺化合物， [化學式1] [化學式4] [化學式5] 其中R 1為C1至C5烷基；R 2、R 3、R 6及R 7各自獨立為氫、C1至C5烷基或C1至C5烷氧基；R 4、R 5及R 8各自獨立為氫或C1至C5烷基；R 9為C1至C5烷基；R'為C1至C5烷氧基或鹵素；A為NR 10R 11或OR 12；R 10為氫或C1至C5烷基；且R 11及R 12各自獨立為C1至C5烷基， 條件為以下情形除外：當A為OR 12，R 1、R 8、R 9及R 12皆為乙基，且R 2至R 7皆為甲基。 As an exemplary embodiment, a method for preparing an aminoalkoxysilylamine compound of the following chemical formula 1 is provided, the method comprising: reacting a (C1 to C5) alkyl lithium, a compound of the following chemical formula 4, and a compound of the following chemical formula 5 to prepare an aminoalkoxysilylamine compound of the following chemical formula 1, [Chemical formula 1] [Chemical formula 4] [Chemical formula 5] wherein R 1 is C1 to C5 alkyl; R 2 , R 3 , R 6 and R 7 are each independently hydrogen, C1 to C5 alkyl or C1 to C5 alkoxy; R 4 , R 5 and R 8 are each independently hydrogen or C1 to C5 alkyl; R 9 is C1 to C5 alkyl; R' is C1 to C5 alkoxy or halogen; A is NR 10 R 11 or OR 12 ; R 10 is hydrogen or C1 to C5 alkyl; and R 11 and R 12 are each independently C1 to C5 alkyl, except for the following situation: when A is OR 12 , R 1 , R 8 , R 9 and R 12 are all ethyl, and R 2 to R 7 are all methyl.
具體而言，用於製備化學式1之胺基烷氧基矽基胺化合物之方法可包括：使（C1至C5）烷基鋰與化學式5之化合物進行反應，以製備鋰鹽；以及，使鋰鹽與化學式4之化合物進行反應，以製備化學式1之胺基烷氧基矽基胺化合物。Specifically, the method for preparing the aminoalkoxysilylamine compound of Chemical Formula 1 may include: reacting a (C1 to C5) alkyl lithium with a compound of Chemical Formula 5 to prepare a lithium salt; and reacting the lithium salt with a compound of Chemical Formula 4 to prepare the aminoalkoxysilylamine compound of Chemical Formula 1.
作為一具體實例，鋰鹽可由以下化學式9表示： [化學式9] 其中取代基係如以上化學式5中所定義。 As a specific example, lithium salt can be represented by the following chemical formula 9: [Chemical formula 9] wherein the substituents are as defined in the above chemical formula 5.
在根據本發明一示例性實施態樣之用於製備化學式1之胺基烷氧基矽基胺化合物之方法中，當化學式4中之R'為鹵素時，可藉由包括使化學式6之化合物與一鹵素源進行反應來製備化學式4之化合物， [化學式6] 其中R 1為C1至C5烷基；R 2及R 3各自獨立地為氫、C1至C5烷基或C1至C5烷氧基；R 21為C1至C5烷氧基。 In a method for preparing an aminoalkoxysilylamine compound of Chemical Formula 1 according to an exemplary embodiment of the present invention, when R' in Chemical Formula 4 is a halogen, the compound of Chemical Formula 4 can be prepared by reacting the compound of Chemical Formula 6 with a halogen source, [Chemical Formula 6] wherein R 1 is a C1 to C5 alkyl group; R 2 and R 3 are each independently hydrogen, a C1 to C5 alkyl group or a C1 to C5 alkoxy group; and R 21 is a C1 to C5 alkoxy group.
根據本發明一示例性實施態樣之鹵素源可為任何可提供能與化學式6之官能基進行取代反應之鹵素的化合物，但作為一實例，該鹵素源可為以下化學式8之化合物。The halogen source according to an exemplary embodiment of the present invention may be any compound that can provide a halogen that can undergo a substitution reaction with the functional group of Chemical Formula 6. However, as an example, the halogen source may be a compound of the following Chemical Formula 8.
更具體而言，在根據本發明一示例性實施態樣之化學式4中，當R'為鹵素時，可藉由在存在以下化學式7之觸媒的情況下，使化學式4之化合物與以下化學式8之化合物反應來製備該化合物： [化學式7] MX 1 3[化學式8] 其中R 22為C1至C5烷基；M為B、Al或Sn；且X 1與X 2各自獨立為鹵素。 More specifically, in Chemical Formula 4 according to an exemplary embodiment of the present invention, when R' is a halogen, the compound can be prepared by reacting the compound of Chemical Formula 4 with the compound of Chemical Formula 8 in the presence of a catalyst of Chemical Formula 7: [Chemical Formula 7] MX 1 3 [Chemical Formula 8] wherein R 22 is a C1 to C5 alkyl group; M is B, Al or Sn; and X 1 and X 2 are each independently a halogen.
作為一具體實例，在化學式6至化學式8中，R 1可為C1至C3烷基；R 2與R 3可各自獨立為C1至C3烷基或C1至C3烷氧基；R 21為C1至C3烷氧基；R 22為C1至C3烷基；M為Al；且X 1與X 2可相同地為Cl。 As a specific example, in Chemical Formulae 6 to 8, R1 may be a C1 to C3 alkyl group; R2 and R3 may each independently be a C1 to C3 alkyl group or a C1 to C3 alkoxy group; R21 is a C1 to C3 alkoxy group; R22 is a C1 to C3 alkyl group; M is Al; and X1 and X2 may both be Cl.
在該製備方法中，烷基鋰可為其中鋰鍵結至C1至C5烷基之化合物，具體而言為甲基鋰、乙基鋰或正丁基鋰，較佳為正丁基鋰。In the preparation method, the alkyl lithium may be a compound in which lithium is bonded to a C1 to C5 alkyl group, specifically methyl lithium, ethyl lithium or n-butyl lithium, preferably n-butyl lithium.
在化學式7之鹵化金屬中，M之金屬可為選自第13族金屬之任一種金屬，且較佳地，M可為B、Al或Sn，且鹵素X 1及X 2可為選自F、Cl、Br及I之任一種鹵素。更具體而言，M可為Al，且X 1及X 2可為Cl。 In the metal halides of Chemical Formula 7, the metal of M may be any metal selected from Group 13 metals, and preferably, M may be B, Al or Sn, and the halogens X1 and X2 may be any halogen selected from F, Cl, Br and I. More specifically, M may be Al, and X1 and X2 may be Cl.
根據一示例性實施態樣，所有的反應可在有機溶劑中實行，具體而言係在選自己烷、二乙醚、甲苯、四氫呋喃等之一或二或更多者之混合有機溶劑中實行，但並非僅限於此。According to an exemplary embodiment, all reactions can be carried out in an organic solvent, specifically in a mixed organic solvent of one or two or more selected from hexane, diethyl ether, toluene, tetrahydrofuran, etc., but not limited thereto.
此外，所有的反應中之反應溫度可使用在常見有機合成中所使用之溫度，但該反應溫度可取決於反應時間、反應材料及起始材料（starting material）之量而變化。In addition, the reaction temperature in all the reactions can use a temperature used in common organic synthesis, but the reaction temperature may vary depending on the reaction time, the amount of the reaction materials and the starting material.
在反應之後，可藉由透過過濾、萃取、再結晶、蒸餾、昇華、層析術等移除副產物來提高純度。After the reaction, the purity can be improved by removing by-products through filtration, extraction, recrystallization, distillation, sublimation, chromatography, etc.
由於藉由該方法所製備之胺基烷氧基矽基胺化合物具有熱穩定性及高揮發性，因此其可用於形成具有良好特性之含矽薄膜，且在寬的溫度範圍內亦具有優異的反應性，俾使可穩定地製造出含矽薄膜。Since the aminoalkoxysilylamine compound prepared by the method has thermal stability and high volatility, it can be used to form a silicon-containing film with good properties, and also has excellent reactivity in a wide temperature range, so that the silicon-containing film can be stably manufactured.
此外，本發明提供一種用於沈積含矽薄膜之組成物，其係包含由以下化學式11表示之化合物： [化學式11] 其中R 1為C1至C5烷基；R 2、R 3、R 6及R 7各自獨立為氫、C1至C5烷基或C1至C5烷氧基；R 4、R 5及R 8各自獨立為氫或C1至C5烷基；R 9為C1至C5烷基；A為NR 10R 11或OR 12；R 10為氫或C1至C5烷基；且R 11與R 12各自獨立為C1至C5烷基。 In addition, the present invention provides a composition for depositing a silicon-containing thin film, which comprises a compound represented by the following Chemical Formula 11: [Chemical Formula 11] wherein R 1 is C1 to C5 alkyl; R 2 , R 3 , R 6 and R 7 are each independently hydrogen, C1 to C5 alkyl or C1 to C5 alkoxy; R 4 , R 5 and R 8 are each independently hydrogen or C1 to C5 alkyl; R 9 is C1 to C5 alkyl; A is NR 10 R 11 or OR 12 ; R 10 is hydrogen or C1 to C5 alkyl; and R 11 and R 12 are each independently C1 to C5 alkyl.
本發明之用於沈積含矽薄膜之組成物中所包括的胺基烷氧基矽基胺化合物係具有其中至少一或多個烷氧基官能基與一胺官能基被同時引入至具有三矽基胺結構之各矽原子的結構，且由於烷氧基官能基被引入至矽原子而具有經改善的反應性及較低的活化能，並且不會產生非揮發性副產物，因此容易以高沈積速率形成高純度的含矽薄膜。The aminoalkoxysilylamine compound included in the composition for depositing a silicon-containing thin film of the present invention has a structure in which at least one or more alkoxy functional groups and an amine functional group are simultaneously introduced into each silicon atom having a trisilylamine structure. Since the alkoxy functional group is introduced into the silicon atom, the compound has improved reactivity and lower activation energy, and does not generate non-volatile by-products, so that a high-purity silicon-containing thin film can be easily formed at a high deposition rate.
此外，由於分子中之矽原子含量高，因此包括該化合物之用於沈積含矽薄膜之組成物可容易以高沈積速率沈積高品質的含矽薄膜且具有高的熱穩定性，且因此，可製造出具有高耐久性及優異純度之薄膜。Furthermore, due to the high silicon atom content in the molecule, a composition for depositing a silicon-containing thin film including the compound can easily deposit a high-quality silicon-containing thin film at a high deposition rate and has high thermal stability, and thus, a thin film with high durability and excellent purity can be manufactured.
在本領域技藝人士考量薄膜之成膜條件或薄膜厚度、性質等能認可之含量範圍內可包括本發明之用於沈積含矽薄膜之組成物。The composition for depositing a silicon-containing thin film of the present invention may be included within a content range that is acceptable to those skilled in the art in terms of film forming conditions, film thickness, properties, etc.
此外，本發明提供一種使用由以下化學式11表示之胺基烷氧基矽基胺化合物來製造含矽薄膜之方法： [化學式11] 其中R 1為C1至C5烷基；R 2、R 3、R 6及R 7各自獨立為氫、C1至C5烷基或C1至C5烷氧基；R 4、R 5及R 8各自獨立為氫或C1至C5烷基；R 9為C1至C5烷基；A為NR 10R 11或OR 12；R 10為氫或C1至C5烷基；且R 11與R 12各自獨立為C1至C5烷基。 In addition, the present invention provides a method for manufacturing a silicon-containing thin film using an aminoalkoxysilylamine compound represented by the following chemical formula 11: [Chemical formula 11] wherein R 1 is C1 to C5 alkyl; R 2 , R 3 , R 6 and R 7 are each independently hydrogen, C1 to C5 alkyl or C1 to C5 alkoxy; R 4 , R 5 and R 8 are each independently hydrogen or C1 to C5 alkyl; R 9 is C1 to C5 alkyl; A is NR 10 R 11 or OR 12 ; R 10 is hydrogen or C1 to C5 alkyl; and R 11 and R 12 are each independently C1 to C5 alkyl.
具體而言，根據本發明之一示例性實施態樣之化學式11可由以下化學式12或化學式13表示： [化學式12] 其中 R 1為C1至C5烷基； R 2、R 3、R 6及R 7各自獨立為氫、C1至C5烷基或C1至C5烷氧基； R 4、R 5、R 8及R 10各自獨立為氫或C1至C5烷基；以及 R 9及R 11為C1至C5烷基， [化學式13] 其中 R 1為C1至C5烷基； R 2、R 3、R 6及R 7各自獨立為氫、C1至C5烷基或C1至C5烷氧基； R 4、R 5及R 8各自獨立為氫或C1至C5烷基；以及 R 9與R 12各自獨立為C1至C5烷基。 Specifically, according to an exemplary embodiment of the present invention, Chemical Formula 11 can be represented by the following Chemical Formula 12 or Chemical Formula 13: [Chemical Formula 12] wherein R 1 is C1 to C5 alkyl; R 2 , R 3 , R 6 and R 7 are each independently hydrogen, C1 to C5 alkyl or C1 to C5 alkoxy; R 4 , R 5 , R 8 and R 10 are each independently hydrogen or C1 to C5 alkyl; and R 9 and R 11 are C1 to C5 alkyl, [Chemical Formula 13] wherein R 1 is C1 to C5 alkyl; R 2 , R 3 , R 6 and R 7 are each independently hydrogen, C1 to C5 alkyl or C1 to C5 alkoxy; R 4 , R 5 and R 8 are each independently hydrogen or C1 to C5 alkyl; and R 9 and R 12 are each independently C1 to C5 alkyl.
在根據一具體實例之用於製造含矽薄膜之方法中，係使用用於沈積含矽薄膜之組成物來製造薄膜，該組成物包括具有熱穩定性及高揮發性之胺基烷氧基矽基胺化合物作為一前驅物，從而可製造出具有優異特性之含矽薄膜。In a method for manufacturing a silicon-containing film according to a specific example, a composition for depositing a silicon-containing film is used to manufacture the film, the composition including a thermally stable and highly volatile aminoalkoxysilylamine compound as a precursor, thereby manufacturing a silicon-containing film with excellent characteristics.
根據一具體實例之含矽薄膜可為在本領域技藝人士能認可之範圍內所能製造的任何膜，且具體而言，可為氧化矽膜（SiO 2）、碳氧化矽膜（SiOC）、氮化矽膜（SiN）、氮氧化矽膜（SiON）、碳氮化矽膜（SiCN）、碳化矽膜（SiC）等，並且可製造出矽含量處於本領域技藝人士能認可之範圍內的各種高品質薄膜。 According to a specific example, the silicon-containing film can be any film that can be manufactured within a range recognized by those skilled in the art, and specifically, can be a silicon oxide film (SiO 2 ), a silicon oxycarbide film (SiOC), a silicon nitride film (SiN), a silicon oxynitride film (SiON), a silicon carbonitride film (SiCN), a silicon carbide film (SiC), etc., and various high-quality films with silicon content within a range recognized by those skilled in the art can be manufactured.
根據一具體實例之用於製造含矽薄膜之方法可為本領域技藝人士能認可之範圍內所容許的任何方法，且較佳地，可藉由原子層沈積（ALD）、化學氣相沈積（CVD）、金屬有機化學氣相沈積（MOCVD）、低壓化學氣相沈積（LPCVD）、電漿增強型化學氣相沈積（PECVD）或電漿增強型原子層沈積（PEALD）來實行，且就更容易進行薄膜沈積且使所製造之薄膜具有優異性質而言，電漿增強型化學氣相沈積（PECVD）或電漿增強型原子層沈積（PEALD）係較佳的。According to a specific example, the method for manufacturing a silicon-containing thin film can be any method allowed within the scope recognized by technical personnel in this field, and preferably, it can be implemented by atomic layer deposition (ALD), chemical vapor deposition (CVD), metal organic chemical vapor deposition (MOCVD), low pressure chemical vapor deposition (LPCVD), plasma enhanced chemical vapor deposition (PECVD) or plasma enhanced atomic layer deposition (PEALD), and plasma enhanced chemical vapor deposition (PECVD) or plasma enhanced atomic layer deposition (PEALD) is preferred in terms of easier film deposition and excellent properties of the manufactured film.
根據一具體實例之製造含矽薄膜之方法可具體包括：a）將安裝於腔室中之基板的溫度加熱至30°C至400°C，並維持該溫度；b）使該基板接觸根據一具體實例之胺基烷氧基矽基胺化合物或根據一具體實例之用於沈積含矽薄膜之組成物，以使該化合物或該組成物吸附至該基板上；以及c）注入反應氣體以在基板上沈積含矽薄膜。A method for manufacturing a silicon-containing film according to a specific example may specifically include: a) heating a substrate mounted in a chamber to a temperature of 30°C to 400°C and maintaining the temperature; b) contacting the substrate with an aminoalkoxysilylamine compound according to a specific example or a composition for depositing a silicon-containing film according to a specific example so that the compound or the composition is adsorbed onto the substrate; and c) injecting a reactive gas to deposit a silicon-containing film on the substrate.
較佳地，當藉由電漿增強型原子層沈積（PEALD）或電漿增強型化學氣相沈積（PECVD）來沈積根據本發明之一具體實例之含矽薄膜時，在步驟a）之後可更包含產生電漿。此外，在步驟b）中，可利用輸送氣體（transport gas）來注入根據一具體實例之胺基烷氧基矽基胺化合物或根據一具體實例之用於沈積含矽薄膜之組成物。Preferably, when the silicon-containing film according to an embodiment of the present invention is deposited by plasma enhanced atomic layer deposition (PEALD) or plasma enhanced chemical vapor deposition (PECVD), the step a) may further include generating plasma. In addition, in step b), the aminoalkoxysilylamine compound according to an embodiment or the composition for depositing a silicon-containing film according to an embodiment may be injected by a transport gas.
在根據一具體實例之用於製造含矽薄膜之方法中，可取決於所欲薄膜之結構或熱性質來調節沈積條件，且作為根據一具體實例之沈積條件，可例示：含有胺基烷氧基矽基胺化合物之用於沈積含矽薄膜之組成物的輸入流速；反應氣體及載體氣體的輸入流速；壓力；RF（radio frequency，射頻）功率；基板溫度等，且作為沈積條件之一非限制性實例，該等條件可在以下範圍內調節：用於沈積含矽薄膜之組成物的輸入流速為10毫升／分鐘（cc/min）至1000毫升／分鐘；載體氣體之流速為10毫升／分鐘至1000毫升／分鐘；反應氣體之流速為1毫升／分鐘至1000毫升／分鐘；壓力為0.5托（torr）至10托；RF功率為200瓦（W）至1000瓦；且基板溫度為30°C至400°C、較佳為100°C至350°C，但並非僅限於此。In a method for manufacturing a silicon-containing thin film according to a specific example, the deposition conditions can be adjusted depending on the structure or thermal properties of the desired thin film, and as deposition conditions according to a specific example, there can be exemplified: the input flow rate of the composition for depositing the silicon-containing thin film containing an aminoalkoxysilylamine compound; the input flow rates of the reaction gas and the carrier gas; the pressure; the RF (radio frequency) frequency, radio frequency) power; substrate temperature, etc., and as a non-limiting example of deposition conditions, the conditions can be adjusted within the following ranges: the input flow rate of the composition for depositing the silicon-containing thin film is 10 ml/min (cc/min) to 1000 ml/min; the flow rate of the carrier gas is 10 ml/min to 1000 ml/min; the flow rate of the reactive gas is 1 ml/min to 1000 ml/min; the pressure is 0.5 torr to 10 torr; the RF power is 200 watts (W) to 1000 watts; and the substrate temperature is 30°C to 400°C, preferably 100°C to 350°C, but is not limited thereto.
在根據一具體實例之用於製造含矽薄膜之方法中所使用的反應氣體可為考慮到待製造之含矽薄膜之材料而通常與矽前驅物一起使用的任何氣體，且作為一具體實例，可為選自氧氣（O 2）、臭氧（O 3）、蒸餾水（H 2O）、過氧化氫（H 2O 2）、一氧化氮（NO）、一氧化二氮（N 2O）、二氧化氮（NO 2）、氨（NH 3）、氮氣（N 2）、肼（hydrazine，N 2H 4）、胺、二胺、一氧化碳（CO）、二氧化碳（CO 2）、C1至C12飽和或不飽和烴、氫、氬及氦之任一或二或更多者，並且輸送氣體可為選自氬、氦及氮之一或二或更多者，但本發明並非僅限於此。 The reaction gas used in the method for manufacturing a silicon-containing thin film according to a specific example may be any gas generally used with a silicon precursor in consideration of the material of the silicon-containing thin film to be manufactured, and as a specific example, may be selected from oxygen (O 2 ), ozone (O 3 ), distilled water (H 2 O), hydrogen peroxide (H 2 O 2 ), nitric oxide (NO), nitrous oxide (N 2 O), nitrogen dioxide (NO 2 ), ammonia (NH 3 ), nitrogen (N 2 ), hydrazine (N 2 H 4 ), amines, diamines, carbon monoxide (CO), carbon dioxide (CO 2 ), any one or two or more of C1 to C12 saturated or unsaturated hydrocarbons, hydrogen, argon and helium, and the transport gas may be one or two or more selected from argon, helium and nitrogen, but the present invention is not limited thereto.
在根據一具體實例之用於製造含矽薄膜之方法中所使用的基板可為包括Si、Ge、SiGe、GaP、GaAs、SiC、SiGeC、InAs及InP之一或多種半導體材料的基板；絕緣體上矽（silicon on insulator，SOI）基板；石英基板；用於顯示器之玻璃基板；可撓性塑膠基板，例如聚醯亞胺、聚對苯二甲酸乙二醇酯（polyethylene terephthalate，PET）、聚萘二甲酸乙二醇酯（polyethylene naphthalate，PEN）、聚甲基丙烯酸甲酯（polymethyl methacrylate，PMMA）、聚碳酸酯（polycarbonate，PC）、聚醚碸（polyethersulfone，PES）及聚酯；等等，但並非僅限於此。The substrate used in the method for manufacturing a silicon-containing thin film according to a specific example may be a substrate including one or more semiconductor materials such as 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; a flexible plastic substrate such as polyimide, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polymethyl methacrylate (PMMA), polycarbonate (PC), polyethersulfone (PES) and polyester; etc., but is not limited thereto.
此外，除了直接在基板上形成含矽薄膜以外，亦可在基板與含矽薄膜之間形成複數個導電層、介電層、絕緣層等。In addition to forming the silicon-containing film directly on the substrate, a plurality of conductive layers, dielectric layers, insulating layers, etc. may also be formed between the substrate and the silicon-containing film.
在下文中，將詳細闡述本發明之實施例。然而，提供該等實施例係為了使本領域技藝人士可容易地實施本發明，而本發明可以各種形式實施，且本發明之思想無須限於該等實施例。Hereinafter, embodiments of the present invention will be described in detail. However, these embodiments are provided to enable those skilled in the art to easily implement the present invention, and the present invention can be implemented in various forms, and the concept of the present invention is not necessarily limited to these embodiments.
在下文中，係藉由 1H NMR、 13C NMR及 29Si-NMR光譜來分析根據本發明之示例性實施態樣的胺基烷氧基矽基胺化合物的結構。 Hereinafter, the structure of the aminoalkoxysilylamine compound according to an exemplary embodiment of the present invention is analyzed by 1 H NMR, 13 C NMR and 29 Si-NMR spectroscopy.
此外，係藉由熱重分析（TGA）及微差掃描熱量計（differential scanning calorimeter，DSC）來量測所獲得的胺基烷氧基矽基胺化合物之熱穩定性、揮發性及分解溫度。In addition, the thermal stability, volatility and decomposition temperature of the obtained aminoalkoxysilylamine compound were measured by thermogravimetric analysis (TGA) and differential scanning calorimeter (DSC).
此外，係使用橢圓偏光儀（ellipsometer）（OPTI-PROBE 2600，THERMA-WAVE（光瑟半導體公司））來量測根據實施例之含矽薄膜的厚度。In addition, the thickness of the silicon-containing thin film according to the embodiment was measured using an ellipsometer (OPTI-PROBE 2600, THERMA-WAVE (Glass Semiconductor Corporation)).
[ 實施例 1]（雙（二甲基胺基）（甲基矽基））（甲基二甲氧基矽基）胺之合成 [ Example 1] Synthesis of (bis(dimethylamino)(methylsilyl))(methyldimethoxysilyl)amine
在無水及惰性氣氛下，將514公克（2.68莫耳）之（雙（二甲基胺基）（甲基矽基））胺（C 6H 21N 3Si 2）及1,753毫升（13.43莫耳）之己烷（C 6H 14）添加至一經火焰乾燥的4,000毫升燒瓶中，且在將內部溫度維持於-20°C之情況下緩慢添加1,049毫升（2.68莫耳）之2.56 M正丁基鋰（C 4H 9Li）。在添加完成之後，在常溫下攪拌5小時，藉此製備（雙（二甲基胺基）（甲基矽基））胺鋰鹽（C 6H 21N 3Si 2Li）。在無水及惰性氣氛下，將365.78公克（2.68莫耳）之甲基三甲氧基矽烷（C 4H 12O 3Si）及1,000毫升（11.60莫耳）之己烷（C 6H 14）添加至一經火焰乾燥的5,000毫升燒瓶中，在將內部溫度維持於-20°C之情況下緩慢添加（雙（二甲基胺基）（甲基矽基））胺鋰鹽（C 6H 21N 3Si 2Li），且在常溫下攪拌20小時。在反應完成之後，對反應混合物進行過濾，以移除甲氧基鋰鹽（LiOCH 3），在減壓下自所得濾液中移除溶劑，並在72°C、1托下實行減壓蒸餾，藉此獲得作為標題化合物之348公克（1.17莫耳）的（雙（二甲基胺基）（甲基矽基））（甲基二甲氧基矽基）胺（產率：43.8%）。 1H-NMR（C 6D 6）：δ 0.20 (s, 3H Si( CH 3 )((OCH 3) 2) 0.34 (m, 6H, (SiHN((CH 3) 2 CH 3 ) 2, 2.49(d, 12H (Si-N( (CH 3) 2 ) 2,, 3.35(s, 6H, (Si- OCH 3) 2 ), 4.78(m, 2H, (Si- H) 2 29Si-NMR（C 6D 6）：δ -18.19 ( Si H(CH 3)(N((CH 3) 2) 2, -18.60 ( Si (CH 3)((OCH 3) 2) 13C-NMR（C 6D 6）：δ 49.49 (Si(CH 3)((O C H 3) 2), 38.22 (SiH(CH 3)(N(( C H 3) 2) 2， -0.83 (Si( C H 3)((OCH 3) 2), -4.17 (SiH( C H 3)(N((CH 3) 2) 2。 Under anhydrous and inert atmosphere, 514 g (2.68 mol) of (bis(dimethylamino)(methylsilyl))amine (C 6 H 21 N 3 Si 2 ) and 1,753 ml (13.43 mol) of hexane (C 6 H 14 ) were added to a flame-dried 4,000 ml flask, and 1,049 ml (2.68 mol) of 2.56 M n-butyl lithium (C 4 H 9 Li) was slowly added while maintaining the internal temperature at -20°C. After the addition was completed, stirring was carried out at room temperature for 5 hours to prepare (bis(dimethylamino)(methylsilyl))amine lithium salt (C 6 H 21 N 3 Si 2 Li). In anhydrous and inert atmosphere, 365.78 g (2.68 mol) of methyltrimethoxysilane (C 4 H 12 O 3 Si) and 1,000 ml (11.60 mol) of hexane (C 6 H 14 ) were added to a flame-dried 5,000 ml flask, and (bis(dimethylamino)(methylsilyl))amide lithium salt (C 6 H 21 N 3 Si 2 Li) was slowly added while maintaining the internal temperature at -20°C, and stirred at room temperature for 20 hours. After the reaction was completed, the reaction mixture was filtered to remove methoxy lithium salt (LiOCH 3 ), the solvent was removed from the obtained filtrate under reduced pressure, and reduced pressure distillation was carried out at 72° C. and 1 torr to obtain 348 g (1.17 mol) of (bis(dimethylamino)(methylsilyl))(methyldimethoxysilyl)amine as the title compound (yield: 43.8%). 1 H-NMR (C 6 D 6 ): δ 0.20 (s, 3H Si( CH 3 )((OCH 3 ) 2 ) 0.34 (m, 6H, (SiHN((CH 3 ) 2 CH 3 ) 2 , 2.49(d, 12H (Si-N( (CH 3 ) 2 ) 2, , 3.35(s, 6H, (Si- OCH 3 ) 2 ), 4.78(m, 2H, (Si- H) 2 29 Si-NMR (C 6 D 6 ): δ -18.19 ( Si H(CH 3 )(N((CH 3 ) 2 ) 2 , -18.60 ( Si (CH 3 )((OCH 3 ) 2 ) 13 C-NMR (C 6 D 6 ): δ 49.49 (Si(CH 3 )((O C H 3 ) 2 ), 38.22 (SiH(CH 3 )(N(( C H 3 ) 2 ) 2 , -0.83 (Si( C H 3 )((OCH 3 ) 2 ), -4.17 (SiH( C H 3 )(N((CH 3 ) 2 ) 2 .
[ 實施例 2]（雙（二甲基胺基）（甲基矽基））（甲基甲氧基矽基）胺之合成 [ Example 2] Synthesis of (bis(dimethylamino)(methylsilyl))(methylmethoxysilyl)amine
在無水及惰性氣氛下，將269公克（1.40莫耳）之（雙（二甲基胺基）（甲基矽基））胺（C 6H 21N 3Si 2）及917毫升（7.02莫耳）之己烷（C 6H 14）添加至一經火焰乾燥的4,000毫升燒瓶中，且在將內部溫度維持於-20°C之情況下緩慢添加549毫升（1.40莫耳）之2.56 M正丁基鋰（C 4H 9Li）。在添加完成之後，在常溫下攪拌5小時，藉此製備（雙（二甲基胺基）（甲基矽基））胺鋰鹽（C 6H 21N 3Si 2Li）。在無水及惰性氣氛下，將149.24公克（1.40莫耳）之甲基二甲氧基矽烷（C 3H 10O 2Si）及1,000毫升（11.60莫耳）之己烷（C 6H 14）添加至一經火焰乾燥的5,000毫升燒瓶中，在將內部溫度維持於-20°C之情況下緩慢添加（雙（二甲基胺基）（甲基矽基））胺鋰鹽（C 6H 21N 3Si 2Li），且在常溫下攪拌5小時。在反應完成之後，對反應混合物進行過濾，以移除甲氧基鋰鹽（LiOCH 3），在減壓下自所得濾液中移除溶劑，並在84°C、5.4托下實行減壓蒸餾，藉此獲得作為標題化合物之180公克（0.677莫耳）的（雙（二甲基胺基）（甲基矽基））（甲基甲氧基矽基）胺（產率：48.2%）。 1H-NMR（C 6D 6）：δ 0.22 (d, 3H Si( CH 3 )H((OCH 3)), 0.28 (m, 6H, (SiHN((CH 3) 2 CH 3 ) 2， 2.46(d, 12H (Si-N( (CH 3) 2 ) 2, 3.36(s, 3H, (Si(CH 3)H( (OCH 3 ) ), 4.57 (m, 3H Si(CH 3) H ((OCH 3)), 4.78 (m, 2H, (Si H N((CH 3) 2CH 3) 2 29Si-NMR（C 6D 6）：δ -17.43 ( Si H(CH 3)(N((CH 3) 2) 2, -31.68 ( Si (CH 3)H((OCH 3)) Under anhydrous and inert atmosphere, 269 g (1.40 mol) of (bis(dimethylamino)(methylsilyl))amine (C 6 H 21 N 3 Si 2 ) and 917 ml (7.02 mol) of hexane (C 6 H 14 ) were added to a flame-dried 4,000 ml flask, and 549 ml (1.40 mol) of 2.56 M n-butyl lithium (C 4 H 9 Li) was slowly added while maintaining the internal temperature at -20°C. After the addition was completed, stirring was carried out at room temperature for 5 hours to prepare (bis(dimethylamino)(methylsilyl))amine lithium salt (C 6 H 21 N 3 Si 2 Li). In anhydrous and inert atmosphere, 149.24 g (1.40 mol) of methyldimethoxysilane (C 3 H 10 O 2 Si) and 1,000 ml (11.60 mol) of hexane (C 6 H 14 ) were added to a flame-dried 5,000 ml flask, and (bis(dimethylamino)(methylsilyl))amide lithium salt (C 6 H 21 N 3 Si 2 Li) was slowly added while maintaining the internal temperature at -20°C, and stirred at room temperature for 5 hours. After the reaction was completed, the reaction mixture was filtered to remove methoxy lithium salt (LiOCH 3 ), the solvent was removed from the obtained filtrate under reduced pressure, and reduced pressure distillation was performed at 84° C. and 5.4 torr to obtain 180 g (0.677 mol) of (bis(dimethylamino)(methylsilyl))(methylmethoxysilyl)amine as the title compound (yield: 48.2%). 1 H-NMR (C 6 D 6 ): δ 0.22 (d, 3H Si( CH 3 )H((OCH 3 )), 0.28 (m, 6H, (SiHN((CH 3 ) 2 CH 3 ) 2 , 2.46(d, 12H (Si-N( (CH 3 ) 2 ) 2 , 3.36(s, 3H, (Si(CH 3 )H( (OCH 3 ) ), 4.57 (m, 3H Si(CH 3 ) H ((OCH 3 )), 4.78 (m, 2H, (Si H N((CH 3 ) 2 CH 3 ) 2 29 Si-NMR (C 6 D 6 ): δ -17.43 ( Si H(CH 3 )(N((CH 3 ) 2 ) 2 , -31.68 ( Si (CH 3 )H((OCH 3 ))
[ 實施例 3]（雙（二甲基胺基）（二甲基矽基））（甲基二甲氧基矽基）胺之合成 [ Example 3] Synthesis of (bis(dimethylamino)(dimethylsilyl))(methyldimethoxysilyl)amine
在無水及惰性氣氛下，將50公克（0.36莫耳）之甲基三甲氧基矽烷（C 4H 12O 3Si）及0.1公克（0.005莫耳）之氯化鋁（AlCl 3）添加至一經火焰乾燥的250毫升燒瓶中，在將內部溫度維持於常溫下緩慢添加34.57公克（0.44莫耳）之乙醯氯（CH 3COCl），且然後在55°C下攪拌24小時。在反應完成之後，對反應混合物進行過濾，以移除氯化鋁（AlCl 3），且在減壓下自所得濾液中移除在反應後所產生之乙酸甲酯（CH 3COOCH 3），藉此製備氯二甲氧基甲基矽烷（C 3H 9ClO 2Si）。 In anhydrous and inert atmosphere, 50 g (0.36 mol) of methyltrimethoxysilane (C 4 H 12 O 3 Si) and 0.1 g (0.005 mol) of aluminum chloride (AlCl 3 ) were added to a flame-dried 250 ml flask, 34.57 g (0.44 mol) of acetyl chloride (CH 3 COCl) was slowly added while maintaining the internal temperature at room temperature, and then stirred at 55° C. for 24 hours. After the reaction was completed, the reaction mixture was filtered to remove aluminum chloride (AlCl 3 ), and methyl acetate (CH 3 COOCH 3 ) produced after the reaction was removed from the obtained filtrate under reduced pressure, thereby preparing chlorodimethoxymethylsilane (C 3 H 9 ClO 2 Si).
將30毫升（0.22莫耳）之己烷（C 6H 14）添加至10公克（0.045莫耳）之雙（二甲基胺基）二甲基矽基胺（C 8H 25N 3Si 2），且然後在-20°C下緩慢添加17.7毫升（0.045莫耳）之2.56 M正丁基鋰（C 4H 9Li）。在常溫下攪拌5小時後，製備雙（二甲基胺基）二甲基矽基胺鋰鹽（C 8H 24N 3Si 2Li）。將30毫升（0.22莫耳）之己烷（C 6H 14）添加至以上所製備之氯二甲氧基甲基矽烷（C 3H 9ClO 2Si），在將內部溫度維持於-20°C之情況下緩慢添加雙（二甲基胺基）二甲基矽基胺鋰鹽（C 8H 24N 3Si 2Li），且然後在常溫下攪拌5小時。在反應完成後，對反應混合物進行過濾，以移除氯化鋰（LiCl），在減壓下自所得濾液中移除溶劑，並獲得作為標題化合物之9.5公克（0.029莫耳）的（雙（二甲基胺基）（二甲基矽基））（甲基二甲氧基矽基）胺（CH 3Si (CH 3O) 2N(Si(CH 3) 2(NCH 3) 2) 2）（產率：68%）。 1H-NMR（C 6D 6）：δ 0.20(s, 3H CH 3 Si(CH 3O) 2), δ 0.30(s, 12H N(Si ( CH 3) 2 N(CH 3) 2) 2), 2.44(s, 12H N(Si(CH 3) 2N (CH 3) 2) 2 ), 3.33(s, 6H CH 3Si (CH 3O) 2) 29Si-NMR（C 6D 6）：δ -5.35 (N( Si (CH 3) 2N(CH 3) 2) 2, -27.90 CH 3 Si (CH 3O) 2。 30 ml (0.22 mol) of hexane (C 6 H 14 ) was added to 10 g (0.045 mol) of bis(dimethylamino)dimethylsilylamine (C 8 H 25 N 3 Si 2 ), and then 17.7 ml (0.045 mol) of 2.56 M n-butyllithium (C 4 H 9 Li) was slowly added at -20°C. After stirring at room temperature for 5 hours, bis(dimethylamino)dimethylsilylamine lithium salt (C 8 H 24 N 3 Si 2 Li) was prepared. 30 ml (0.22 mol) of hexane (C 6 H 14 ) was added to the above-prepared chlorodimethoxymethylsilane (C 3 H 9 ClO 2 Si), bis(dimethylamino)dimethylsilylamine lithium salt (C 8 H 24 N 3 Si 2 Li) was slowly added while maintaining the internal temperature at -20°C, and then stirred at room temperature for 5 hours. After completion of the reaction, the reaction mixture was filtered to remove lithium chloride (LiCl), the solvent was removed from the obtained filtrate under reduced pressure, and 9.5 g (0.029 mol) of (bis(dimethylamino)(dimethylsilyl))(methyldimethoxysilyl)amine (CH 3 Si(CH 3 O) 2 N(Si(CH 3 ) 2 (NCH 3 ) 2 ) 2 ) was obtained as the title compound (yield: 68%). 1 H-NMR (C 6 D 6 ): δ 0.20(s, 3H CH 3 Si(CH 3 O) 2 ), δ 0.30(s, 12H N(Si ( CH 3 ) 2 N(CH 3 ) 2 ) 2 ), 2.44(s, 12H N(Si(CH 3 ) 2 N (CH 3 ) 2 ) 2 ), 3.33(s, 6H CH 3 Si (CH 3 O) 2 ) 29 Si-NMR (C 6 D 6 ): δ -5.35 (N( Si (CH 3 ) 2 N(CH 3 ) 2 ) 2 , -27.90 CH 3 Si (CH 3 O) 2 .
[ 實施例 4]藉由電漿增強型原子層沈積（PEALD）來製造氧化矽薄膜 [ Example 4] Fabrication of silicon oxide thin film by plasma enhanced atomic layer deposition (PEALD)
為了使用已知的電漿增強型原子層沈積（PEALD）在常見的電漿增強型原子層沈積（PEALD）裝置中形成氧化矽薄膜，係使用在實施例3中所製備之胺基烷氧基矽基胺化合物作為一前驅物，並對氧化矽膜的形成進行評價。In order to form a silicon oxide film using known plasma enhanced atomic layer deposition (PEALD) in a conventional plasma enhanced atomic layer deposition (PEALD) apparatus, the aminoalkoxysilylamine compound prepared in Example 3 was used as a precursor, and the formation of the silicon oxide film was evaluated.
作為其上欲形成有氧化矽薄膜之基板，係使用一矽基板，且矽基板被傳送至一沈積腔室中，並使矽基板之溫度恆定地維持於表1中所闡述之溫度。As a substrate on which a silicon oxide thin film is to be formed, a silicon substrate is used, and the silicon substrate is transferred to a deposition chamber, and the temperature of the silicon substrate is constantly maintained at the temperature described in Table 1.
使由不鏽鋼製成之填充有該前驅物的起泡器型罐（bubbler type canister）維持於下表1中所闡述之溫度下，俾使該前驅物之蒸氣壓恆定。使用氬氣作為傳送氣體而將氣化前驅物傳送至腔室中並使其在矽基板上形成膜。A bubbler type canister made of stainless steel filled with the precursor was maintained at the temperature specified in Table 1 below so that the vapor pressure of the precursor was constant. Argon was used as a transfer gas to transfer the vaporized precursor into the chamber and form a film on a silicon substrate.
具體而言，使矽基板維持於200°C，並將實施例3之前驅物填充至維持於83°C之不鏽鋼起泡器容器中。作為反應氣體，與氧氣一起使用氬氣，且使用作為惰性氣體之氬氣進行吹掃。詳細的氧化矽薄膜沈積方法係示於下表1中：Specifically, the silicon substrate was maintained at 200°C, and the former of Example 3 was filled into a stainless steel bubbler container maintained at 83°C. Argon was used as a reaction gas together with oxygen, and argon was used as an inert gas for purging. The detailed silicon oxide film deposition method is shown in Table 1 below:
[表1]藉由電漿增強型原子層沈積之氧化矽薄膜沈積條件
使用橢圓偏光儀（UV光譜橢圓偏光儀，Elli-SEU-am12，Ellipso technology（橢圓偏光技術公司））量測所沈積薄膜之厚度，使用紅外線光譜儀（傅立葉轉換紅外線（Fourier transform infrared），VERTEX 70v，Bruker（布魯克公司））分析氧化矽薄膜之形成，且使用X射線光電子光譜儀（K-Alpha+，ThermoFisher Scientific（賽默飛世爾科技公司））分析氧化矽薄膜之組成。此外，使用穿透式電子顯微鏡（Tecnai F-30 S-Twin，FEI公司）確認氧化矽薄膜之步階覆蓋。The thickness of the deposited film was measured using an elliptoscope (UV spectrometer elliptoscope, Elli-SEU-am12, Ellipso technology), the formation of the silicon oxide film was analyzed using an infrared spectrometer (Fourier transform infrared, VERTEX 70v, Bruker), and the composition of the silicon oxide film was analyzed using an X-ray photoelectron spectrometer (K-Alpha+, ThermoFisher Scientific). In addition, a transmission electron microscope (Tecnai F-30 S-Twin, FEI) was used to confirm the step coverage of the silicon oxide film.
[ 比較例 1]藉由電漿增強型原子層沈積（PEALD）來製造氧化矽薄膜 [ Comparative Example 1] Fabrication of silicon oxide thin film by plasma enhanced atomic layer deposition (PEALD)
除了使用冷卻至11°C之二異丙基胺基矽烷前驅物代替在實施例3中所製備之胺基烷氧基矽基胺化合物作為前驅物且在矽基板之溫度範圍為50°C至200°C之情況下實行實驗以外，使用與實施例4相同之方式來形成氧化矽薄膜。使用橢圓偏光儀（UV光譜橢圓偏光儀，Elli-SEU-am12，Ellipso technology）量測所沈積薄膜之厚度，且使用X射線光電子光譜儀（K-Alpha+，ThermoFisher Scientific）分析氧化矽薄膜之組成。The silicon oxide film was formed in the same manner as in Example 4, except that a diisopropylaminosilane precursor cooled to 11° C. was used instead of the aminoalkoxysilylamine compound prepared in Example 3 as the precursor and the experiment was conducted at a temperature range of 50° C. to 200° C. on the silicon substrate. The thickness of the deposited film was measured using an elliptical polarizer (UV spectrometer elliptical polarizer, Elli-SEU-am12, Ellipso technology), and the composition of the silicon oxide film was analyzed using an X-ray photoelectron spectrometer (K-Alpha+, ThermoFisher Scientific).
[ 比較例 2]藉由電漿增強型原子層沈積（PEALD）來製造氧化矽薄膜 [ Comparative Example 2] Fabrication of silicon oxide thin film by plasma enhanced atomic layer deposition (PEALD)
除了使用加熱至41°C之雙三級丁基胺基矽烷前驅物代替在實施例3中所製備之胺基烷氧基矽基胺化合物作為前驅物且在矽基板之溫度範圍為50°C至200°C之情況下實行實驗以外，使用與實施例4相同之方式來形成氧化矽薄膜。使用橢圓偏光儀（UV光譜橢圓偏光儀，Elli-SEU-am12，Ellipso technology）量測所沈積薄膜之厚度，且使用X射線光電子光譜儀（K-Alpha+，ThermoFisher Scientific）分析氧化矽薄膜之組成。The silicon oxide film was formed in the same manner as in Example 4, except that a bis(tri-butylamino)silane precursor heated to 41° C. was used instead of the aminoalkoxysilylamine compound prepared in Example 3 as the precursor and the experiment was conducted at a temperature range of 50° C. to 200° C. on the silicon substrate. The thickness of the deposited film was measured using an elliptical polarizer (UV spectrometer elliptical polarizer, Elli-SEU-am12, Ellipso technology), and the composition of the silicon oxide film was analyzed using an X-ray photoelectron spectrometer (K-Alpha+, ThermoFisher Scientific).
在第3圖中，示出藉由紅外線光譜儀對實施例4中所沈積之薄膜進行分析的結果光譜，且發現在為1060 cm -1之波數處確切地顯示出Si-O鍵。 FIG. 3 shows the spectrum of the thin film deposited in Example 4 analyzed by an infrared spectrometer, and it was found that Si—O bonds were clearly shown at a wave number of 1060 cm -1 .
第4圖為藉由對實施例4、比較例1及比較例2之薄膜進行橢圓偏光儀分析而示出之隨基板溫度所沈積之薄膜的厚度的曲線圖。實施例4之胺基烷氧基矽基胺化合物前驅物係顯示出在100°C至200°C之矽基板溫度下具有一原子層沈積製程段（atomic layer deposition process section）且在400°C或更高溫度下具有一原子層沈積製程段（ALD窗口（ALD window）），但在使用二異丙基胺基矽烷及雙三級丁基胺基矽烷前驅物之比較例1及比較例2中，觀察到在原子層沈積製程溫度範圍為50°C至200°C之情況下，每一個循環所沈積之薄膜厚度係隨基板溫度升高而減小。此外，在相同條件下，由於相較於比較例1及比較例2，實施例4顯示出每一個循環所沈積之薄膜的厚度較大，因此該前驅物可為有利於需要高產量製程之前驅物。FIG. 4 is a graph showing the thickness of the deposited thin film as a function of substrate temperature, obtained by performing elliptical polarizer analysis on the thin films of Example 4, Comparative Example 1, and Comparative Example 2. The aminoalkoxysilylamine compound precursor of Example 4 shows an atomic layer deposition process section at a silicon substrate temperature of 100°C to 200°C and an atomic layer deposition process section (ALD window) at 400°C or higher, but in Comparative Examples 1 and 2 using diisopropylaminosilane and bis(tributylaminosilane) precursors, it was observed that when the atomic layer deposition process temperature ranged from 50°C to 200°C, the thickness of the film deposited in each cycle decreased as the substrate temperature increased. In addition, under the same conditions, compared with Comparative Examples 1 and 2, Example 4 shows that the thickness of the film deposited in each cycle is larger, so the precursor can be a precursor that is beneficial to a process requiring high throughput.
此外，下表2示出使用X射線光電子光譜儀對所沈積之薄膜的組成及雜質進行分析的結果。在實施例4以及比較例1及比較例2中所沈積之薄膜皆顯示為不含碳雜質及氮雜質的薄膜，並且在實施例4中在100°C之相同矽基板溫度下的O/Si比率為1.99，此意味著形成理想的SiO 2薄膜，但在比較例1及比較例2中O/Si比率為2.04及2.08，此意味著薄膜含有大量O。 In addition, the following Table 2 shows the results of analyzing the composition and impurities of the deposited thin films using an X-ray photoelectron spectrometer. The thin films deposited in Example 4 and Comparative Examples 1 and 2 all showed films free of carbon impurities and nitrogen impurities, and the O/Si ratio at the same silicon substrate temperature of 100°C in Example 4 was 1.99, which means that an ideal SiO2 thin film was formed, but the O/Si ratios in Comparative Examples 1 and 2 were 2.04 and 2.08, which means that the films contained a large amount of O.
[表2]藉由X射線光電子光譜儀對氧化矽薄膜進行分析的結果
在第5圖及第6圖中，係顯示實行用於觀察實施例4之在200°C及400°C基板溫度下所製造之薄膜的步階覆蓋的穿透式電子顯微鏡分析結果。在長寬比（aspect ratio）為14之圖案基板中，基於下壁表面，顯示出101%及97%之步階覆蓋為優異的。FIG5 and FIG6 show the results of TEM analysis for observing the step coverage of the thin film fabricated at substrate temperatures of 200°C and 400°C in Example 4. In a patterned substrate with an aspect ratio of 14, the step coverage of 101% and 97% based on the lower wall surface is excellent.
根據第1圖及第2圖，證實了在實施例1至實施例3中所製備之胺基烷氧基矽基胺化合物前驅物具有高的揮發性、穩定性及熱分解性質。According to FIG. 1 and FIG. 2, it is confirmed that the aminoalkoxysilylamine compound precursor prepared in Examples 1 to 3 has high volatility, stability and thermal decomposition properties.
此外，由表2及第3圖、第4圖、第5圖及第6圖可知，根據本發明之示例性實施態樣的胺基烷氧基矽基胺化合物可作為用於薄膜沈積的前驅物，藉此以高產量產生具有優異特性之含矽薄膜，且所製造之含矽薄膜具有優異的步階覆蓋性質。In addition, it can be seen from Table 2 and Figures 3, 4, 5 and 6 that the aminoalkoxysilylamine compound according to the exemplary implementation of the present invention can be used as a precursor for thin film deposition, thereby producing a silicon-containing film with excellent properties at a high yield, and the produced silicon-containing film has excellent step coverage properties.
根據本發明之胺基烷氧基矽基胺化合物為一新穎化合物，且可被提供作為具有熱穩定性及高揮發性之含矽薄膜的前驅物，以形成具有優異特性之含矽薄膜。The aminoalkoxysilylamine compound according to the present invention is a novel compound and can be provided as a precursor of a silicon-containing film having thermal stability and high volatility to form a silicon-containing film having excellent properties.
此外，當使用根據本發明之胺基烷氧基矽基胺化合物製造含矽薄膜時，該化合物可在寬的溫度範圍內具有優異的反應性。Furthermore, when a silicon-containing thin film is produced using the aminoalkoxysilylamine compound according to the present invention, the compound can have excellent reactivity within a wide temperature range.
此外，根據本發明之示例性實施態樣的用於製備胺基烷氧基矽基胺化合物之方法可以高產率而高效地產生胺基烷氧基矽基胺化合物。In addition, the method for preparing an aminoalkoxysilylamine compound according to an exemplary embodiment of the present invention can produce the aminoalkoxysilylamine compound efficiently with high yield.
此外，根據本發明之示例性實施態樣的用於沈積含矽薄膜之組成物係包括根據本發明之示例性實施態樣的胺基烷氧基矽基胺化合物，藉此製造高品質含矽薄膜。In addition, a composition for depositing a silicon-containing film according to an exemplary embodiment of the present invention includes an aminoalkoxysilylamine compound according to an exemplary embodiment of the present invention, thereby producing a high-quality silicon-containing film.
以上，已詳細描述了本發明的特定部分，對本領域技藝人士而言顯而易見的是該等特定技術僅為較佳的實施態樣，本發明的範疇則不限定於此。因此，本發明的實質範疇將由後附申請專利範圍及其等效物所定義。 [相關申請案之交叉參考] Above, specific parts of the present invention have been described in detail. It is obvious to those skilled in the art that these specific technologies are only preferred embodiments, and the scope of the present invention is not limited thereto. Therefore, the substantial scope of the present invention will be defined by the scope of the attached patent application and its equivalents. [Cross-reference to related applications]
本案係主張2023年5月25日在韓國智慧財產局提出申請之韓國第10-2023-0067834號專利申請案及2024年5月23日在韓國智慧財產局提出申請之韓國第10-2024-0067176號專利申請案的優先權，該等申請案之揭露內容全文併入本案供參考。This case claims the priority of Korean Patent Application No. 10-2023-0067834 filed on May 25, 2023 with the Korean Intellectual Property Office and Korean Patent Application No. 10-2024-0067176 filed on May 23, 2024 with the Korean Intellectual Property Office. The disclosures of these applications are incorporated in full into this case for reference.
無without
第1圖為實施例3中所製備之胺基烷氧基矽基胺化合物的熱重分析（thermogravimetric analysis，TGA）曲線圖。 第2圖為實施例3中所製備之胺基烷氧基矽基胺化合物之微差掃描熱量（differential scanning calorimetry，DSC）曲線圖。 第3圖為使用紅外線光譜儀對實施例4中所製造之氧化矽薄膜進行分析而得到之光譜。 第4圖為藉由橢圓偏光分析所示出之實施例4、比較例1及比較例2的隨基板溫度之每沈積循環所沈積之薄膜的厚度的曲線圖。 第5圖為示出確認實施例4在基板溫度為200°C下所沈積之氧化矽薄膜之步階覆蓋（step coverage）的結果圖。 第6圖為示出確認實施例4在基板溫度為400°C下所沈積之氧化矽薄膜之步階覆蓋的結果圖。 FIG. 1 is a thermogravimetric analysis (TGA) curve of the aminoalkoxysilylamine compound prepared in Example 3. FIG. 2 is a differential scanning calorimetry (DSC) curve of the aminoalkoxysilylamine compound prepared in Example 3. FIG. 3 is a spectrum obtained by analyzing the silicon oxide film prepared in Example 4 using an infrared spectrometer. FIG. 4 is a curve of the thickness of the film deposited per deposition cycle of Example 4, Comparative Example 1 and Comparative Example 2 as the substrate temperature is analyzed by elliptical polarization analysis. FIG. 5 is a result diagram showing the step coverage of the silicon oxide film deposited at a substrate temperature of 200°C in Example 4. FIG. 6 is a result diagram showing the step coverage of the silicon oxide film deposited at a substrate temperature of 400°C in Example 4.
Claims (9)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2023-0067834 | 2023-05-25 | ||
| KR10-2024-0067176 | 2024-05-23 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| TW202506695A true TW202506695A (en) | 2025-02-16 |
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