CN101111501B - 环状硅氧烷化合物、含硅膜形成材料及其用途 - Google Patents
环状硅氧烷化合物、含硅膜形成材料及其用途 Download PDFInfo
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- CN101111501B CN101111501B CN200680003726.4A CN200680003726A CN101111501B CN 101111501 B CN101111501 B CN 101111501B CN 200680003726 A CN200680003726 A CN 200680003726A CN 101111501 B CN101111501 B CN 101111501B
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- Prior art keywords
- tetra
- tri
- cyclotrisiloxane
- cyclotetrasiloxane
- general formula
- Prior art date
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- -1 Cyclic siloxane compound Chemical class 0.000 title claims abstract description 88
- 239000000463 material Substances 0.000 title claims abstract description 57
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 claims abstract description 60
- 229910052796 boron Inorganic materials 0.000 claims abstract description 9
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 6
- JJRDHFIVAPVZJN-UHFFFAOYSA-N cyclotrisiloxane Chemical compound O1[SiH2]O[SiH2]O[SiH2]1 JJRDHFIVAPVZJN-UHFFFAOYSA-N 0.000 claims description 94
- 238000000034 method Methods 0.000 claims description 74
- RSNQKPMXXVDJFG-UHFFFAOYSA-N tetrasiloxane Chemical compound [SiH3]O[SiH2]O[SiH2]O[SiH3] RSNQKPMXXVDJFG-UHFFFAOYSA-N 0.000 claims description 40
- 238000004519 manufacturing process Methods 0.000 claims description 36
- 229910052710 silicon Inorganic materials 0.000 claims description 32
- 239000010703 silicon Substances 0.000 claims description 31
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 30
- 230000015572 biosynthetic process Effects 0.000 claims description 27
- 150000001875 compounds Chemical class 0.000 claims description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 13
- 239000001301 oxygen Substances 0.000 claims description 13
- 229910052760 oxygen Inorganic materials 0.000 claims description 13
- 230000008569 process Effects 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 239000012535 impurity Substances 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 238000005229 chemical vapour deposition Methods 0.000 claims description 3
- 125000004417 unsaturated alkyl group Chemical group 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims 1
- 125000004433 nitrogen atom Chemical group N* 0.000 abstract description 3
- 239000004065 semiconductor Substances 0.000 abstract description 2
- 125000004430 oxygen atom Chemical group O* 0.000 abstract 1
- 239000010408 film Substances 0.000 description 114
- DDJSWKLBKSLAAZ-UHFFFAOYSA-N cyclotetrasiloxane Chemical compound O1[SiH2]O[SiH2]O[SiH2]O[SiH2]1 DDJSWKLBKSLAAZ-UHFFFAOYSA-N 0.000 description 44
- 239000007789 gas Substances 0.000 description 21
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- QTXPTCOLKMGOPW-UHFFFAOYSA-N 2-propoxy-1,3,5,2,4,6-trioxatrisilinane Chemical compound C(CC)O[SiH]1O[SiH2]O[SiH2]O1 QTXPTCOLKMGOPW-UHFFFAOYSA-N 0.000 description 13
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 13
- 239000000758 substrate Substances 0.000 description 13
- BKMZIIHKCVIRPD-UHFFFAOYSA-N 2-propoxy-1,3,5,7,2,4,6,8-tetraoxatetrasilocane Chemical compound C(CC)O[SiH]1O[SiH2]O[SiH2]O[SiH2]O1 BKMZIIHKCVIRPD-UHFFFAOYSA-N 0.000 description 12
- 239000002585 base Substances 0.000 description 12
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- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 11
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 7
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- 238000004821 distillation Methods 0.000 description 6
- 125000001183 hydrocarbyl group Chemical group 0.000 description 6
- IMYAVYOZYTZVCV-UHFFFAOYSA-N 2,4,6,8-tetramethoxy-2,4,6,8-tetramethyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane Chemical compound CO[Si]1(C)O[Si](C)(OC)O[Si](C)(OC)O[Si](C)(OC)O1 IMYAVYOZYTZVCV-UHFFFAOYSA-N 0.000 description 5
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- 229940126639 Compound 33 Drugs 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 4
- PNUZDKCDAWUEGK-CYZMBNFOSA-N Sitafloxacin Chemical compound C([C@H]1N)N(C=2C(=C3C(C(C(C(O)=O)=CN3[C@H]3[C@H](C3)F)=O)=CC=2F)Cl)CC11CC1 PNUZDKCDAWUEGK-CYZMBNFOSA-N 0.000 description 4
- 125000003342 alkenyl group Chemical group 0.000 description 4
- 125000000304 alkynyl group Chemical group 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- YQGOWXYZDLJBFL-UHFFFAOYSA-N dimethoxysilane Chemical compound CO[SiH2]OC YQGOWXYZDLJBFL-UHFFFAOYSA-N 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 239000010948 rhodium Substances 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- YHQGMYUVUMAZJR-UHFFFAOYSA-N α-terpinene Chemical compound CC(C)C1=CC=C(C)CC1 YHQGMYUVUMAZJR-UHFFFAOYSA-N 0.000 description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- OOUFCOHCMJBYGV-UHFFFAOYSA-N 2-propan-2-yl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane Chemical compound C(C)(C)[SiH]1O[SiH2]O[SiH2]O[SiH2]O1 OOUFCOHCMJBYGV-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
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- AOBOMOUUYYHMOX-UHFFFAOYSA-N diethylboron Chemical compound CC[B]CC AOBOMOUUYYHMOX-UHFFFAOYSA-N 0.000 description 3
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 3
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- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
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- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 2
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- SZZPLCQSPMKTHA-UHFFFAOYSA-N 2,4,6,8-tetrabutyl-2,4,6,8-tetramethoxy-1,3,5,7,2,4,6,8-tetraoxatetrasilocane Chemical compound CCCC[Si]1(OC)O[Si](CCCC)(OC)O[Si](CCCC)(OC)O[Si](CCCC)(OC)O1 SZZPLCQSPMKTHA-UHFFFAOYSA-N 0.000 description 1
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- VZKXUCINOMAXSP-UHFFFAOYSA-N 2,4,6-tributyl-2,4,6-trimethoxy-1,3,5,2,4,6-trioxatrisilinane Chemical compound CCCC[Si]1(OC)O[Si](CCCC)(OC)O[Si](CCCC)(OC)O1 VZKXUCINOMAXSP-UHFFFAOYSA-N 0.000 description 1
- APLNMGCHVWDLPT-UHFFFAOYSA-N 2,4,6-tricyclopentyl-2,4,6-tris(2-methylpropoxymethyl)-1,3,5,2,4,6-trioxatrisilinane Chemical compound O1[Si](COCC(C)C)(C2CCCC2)O[Si](COCC(C)C)(C2CCCC2)O[Si]1(COCC(C)C)C1CCCC1 APLNMGCHVWDLPT-UHFFFAOYSA-N 0.000 description 1
- ZQBFYJLDJXOSIR-UHFFFAOYSA-N 2,4,6-tricyclopentyl-2,4,6-tris(ethoxymethyl)-1,3,5,2,4,6-trioxatrisilinane Chemical compound O1[Si](COCC)(C2CCCC2)O[Si](COCC)(C2CCCC2)O[Si]1(COCC)C1CCCC1 ZQBFYJLDJXOSIR-UHFFFAOYSA-N 0.000 description 1
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- 239000007858 starting material Substances 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 238000001149 thermolysis Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- FEQPHYCEZKWPNE-UHFFFAOYSA-K trichlororhodium;triphenylphosphane Chemical compound Cl[Rh](Cl)Cl.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 FEQPHYCEZKWPNE-UHFFFAOYSA-K 0.000 description 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 1
- 239000011882 ultra-fine particle Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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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
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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
- C23C16/448—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials
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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
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- 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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Abstract
本发明目的在于提供新型的含硅膜形成材料尤其是含有适用于PECVD装置的环状硅氧烷化合物的低介电常数绝缘膜用材料,并提供使用该材料的含硅膜及含这些膜的半导体器件。本发明涉及含有下述通式(1)(式中,A表示含有选自氧原子、硼原子及氮原子中至少一种的基团,n表示1或2、x表示2~10的整数)所示环状硅氧烷化合物的含硅膜形成材料及其用途等。
Description
技术领域
本发明涉及含硅膜形成材料,特别是涉及在逻辑(logic)ULSI的多层布线技术中使用的低介电常数层间绝缘膜材料。特别涉及含有用于等离子体聚合的环状硅氧烷化合物的含硅膜形成材料及其用途。
背景技术
在电子产业的集成电路领域的制造技术中,高集成化并且高速化的要求日益增高。在硅ULSI、尤其是逻辑ULSI中,连接它们的布线的性能比由MOSFET微细化产生的性能更成为问题。即,为了解决随多层布线化产生的布线延迟的问题,要求降低布线电阻和布线间以及层间容量。
因此,必须导入电阻更低、具有耐迁移性的铜布线代替目前大部分集成电路使用的铝布线,采用溅射法或化学气相沉积法(以下,简称CVD)形成种(seed)后进行镀铜的工艺正在实用化。
作为低介电常数层间绝缘膜材料有各种各样的提案。作为以往技术,无机类使用了二氧化硅(SiO2)、氮化硅、磷硅酸玻璃,有机类使用了聚酰亚胺,最近,为了得到更均匀的层间绝缘膜,提出预先使四乙氧基硅烷单体水解,即使之缩聚,得到SiO2,并作为称作无机Spin on Glass(无机SOG)的涂布材料使用,或者提出使烷氧基硅烷单体缩聚得到的聚硅氧烷作为有机SOG使用。
另外,作为绝缘膜形成方法,有以下两种方法:采用旋转涂布法等涂布绝缘膜聚合物溶液,进行成膜的涂布型方法和主要在等离子体增强化学气相沉积法(PECVD:Plasma Enhanced Chemical Vapor Deposition)装置中进行等离子体聚合而成膜的CVD法。
作为PECVD法的方案,例如,专利文献1中提出了通过PECVD法由三甲基硅烷和氧形成氧化三甲基硅烷薄膜的方法,而专利文献2中提出了采用PECVD法由具有甲基、乙基、正丙基等直链状烷基、乙烯基苯基等炔基(alkynyl)以及芳基的烷氧基硅烷形成氧化烷基硅烷薄膜的方法。这些使用 以往的PECVD法材料形成的绝缘膜,虽然与阻挡金属,作为布线材料的铜布线材料的粘合性良好,但另一方面,有时膜的均匀性成为问题,或成膜速度、电容率(dielectric constant)不充分。
作为使用环状硅氧烷的PECVD的方案,例如,专利文献3提出了使用四甲基环四硅氧烷的方法,而专利文献4提出了使用四烷基环四硅氧烷、四氨基环四硅氧烷、八烷基环四硅氧烷、八氨基环四硅氧烷的方法。在这些方法中,使用环状硅氧烷作为原料化合物,不仅在生成薄膜中维持其环状结构,而且在生成薄膜中形成孔穴,谋求降低电容率。然而,根据本发明者的见解,使用这些的取代环状硅氧烷进行PECVD成膜时,不能得到有小于2.7的电容率的薄膜。认为这是因为该环状硅氧烷化合物在等离子体中环状结构容易遭到破坏而成为链状结构,不能有助于薄膜多孔化的缘故。
另外,在专利文献5中提出了六甲基环三硅氧烷、1,3,5-三甲基-1,3,5-三乙烯基环三硅氧烷这些六员环状硅氧烷,专利文献6中提出在等离子体环境气氛下使双苯并环丁烯取代二硅氧烷化合物和作为八员环状硅氧烷的1,3,5,7-四甲基-1,3,5,7-四乙烯基环四硅氧烷共聚。然而,根据本发明者的知识,在使用这些方案中的乙烯基和/或甲基取代的环状硅氧烷的方法中,不能得到具有小于2.5的电容率的薄膜。
专利文献7和专利文献8提出了使用多孔化剂的PECVD法低介电常数薄膜的成膜方法。前者提出了向PECVD装置腔(chamber)内供给三乙氧基硅烷和二乙氧基甲基硅烷以及多孔化剂α-萜品烯,进行PECVD成膜后,在400℃以上的温度下进行退火处理,通过使薄膜中的来自α-萜品烯的成分挥发而多孔化,并进行低介电常数化的方法。后者提出了向PECVD装置腔内供给环-1,3,5,7-四亚硅烷基-2,6,二氧-4,8-二亚甲基和多孔化剂乙烯基呋喃醚及氧化剂一氧化二氮,进行PECVD成膜后,在400℃以上的温度下进行退火处理,通过使薄膜中的来自乙烯基呋喃醚的成分挥发而多孔化,并进行低介电常数化的方法。这些方法虽然可期待多孔化产生的低介电常数化,但由于通过后处理将多孔剂成分从一次形成的薄膜中除去至薄膜外,故存在以下问题:薄膜的基体遭到破坏,膜内部的组成变得不均匀,刚性或杨氏模量等机械强度降低,形成的孔成为连续开放体系的孔,不能防止金属成分向膜中扩散等。
另外,作为涂布型的方案,虽然膜的均匀性良好,但需要涂布、除去 溶剂,热处理三个工序,经济性比CVD材料差,并且与阻挡金属、作为布线材料的铜布线材料的粘合性,或涂布液对微细化的基板结构的均匀涂布本身往往成为问题。
另外,在涂布型材料中,为了实现电容率为2.5以下,甚至是2.0以下的UltraLow-k材料提出了制成多孔材料的方法。包括以下方法:使容易热分解的有机成分微粒分散在有机类或无机类材料的基体中热处理进行使之多孔化的方法,蒸镀使硅和氧在气体中蒸发形成的SiO2超微粒子,形成SiO2超微粒薄膜的方法等。然而,这些多孔化的方法虽然对低介电常数化有效,但往往机械强度降低,化学机械研磨(CMP)困难,或由于吸收水分导致介电常数上升及引起布线腐蚀。
因此,市场要求满足低介电常数,充分的机械强度,与阻挡金属的粘合性,防止铜扩散、耐等离子体灰化(ashing)性、耐吸湿性等全部要求性能的平衡性良好的材料,作为某种程度上平衡性良好地满足这些要求性能的方法,提出了,在有机硅烷类材料中,通过使有机取代基团的碳相对于硅烷的比例上升而具有有机聚合物和无机聚合物的中间特征的材料。例如,专利文献9提出了使用在酸性水溶液共存下,采用溶胶-凝胶法将具有金刚烷基的硅化合物水解缩聚得到的涂布溶液,不进行多孔化得到电容率为2.4以下的层间绝缘膜的方法。然而,这种材料是涂布型的材料,仍然有如上述的涂布型的成膜方法的问题。
专利文献1:特开2002-110670号公报
专利文献2:特开平11-288931号公报
专利文献3:日本专利第2067801号公报
专利文献4:特开平5-279856号公报
专利文献5:国际公开03/019645号小册子
专利文献6:特开2004-47873号公报
专利文献7:特开2005-19980号公报
专利文献8:特开2001-298023号公报
专利文献9:特开2000-302791号公报
发明内容
发明要解决的问题
本发明是鉴于上述的课题而进行的,其目的在于提供新型的含硅膜形成材料,尤其是含有适合PECVD装置的环状硅氧烷化合物的低介电常数绝缘膜用材料以及使用该材料的含硅膜及包含这些膜的半导体器件。
解决问题的方法
本发明者发现具有含杂原子的取代基的环状硅氧烷化合物适合作为绝缘膜,尤其是用于半导体器件的低介电常数层间绝缘膜材料,从而完成了本发明。
即,本发明涉及含硅膜形成材料,其含有下述通式(1)表示的环状硅氧烷化合物,
[化1]
式中,A表示含有选自氧原子、硼原子及氮原子中至少一种的基团,R1表示氢原子或烃基,n表示1或2,x表示2~10的整数。
另外,本发明涉及含硅膜的制造方法,该方法包括,使用上述的含硅膜形成材料作为原料。此外,本发明涉及含硅膜,其采用上述的制造方法制得。另外,本发明涉及含硅膜的制造方法,该方法包括,对上述的含硅膜进行热处理,紫外线照射处理,或电子射线处理。此外,本发明涉及含硅膜,其采用上述的制造方法制得。另外,本发明涉及半导体器件,其使用上述的含硅膜作为绝缘膜。
此外,本发明涉及环状硅氧烷化合物,其用下述通式(20)表示,
[化2]
(式中,R18表示烃基,R19表示氢原子或烃基,g表示2~10的整数,h表示1~3的整数)。
发明效果
按照本发明可以达到以下的显著效果。即,作为本发明的第一效果。通过使用通式(1)表示的环状硅氧烷化合物作为含硅的膜形成材料,可提供作为半导体器件层间绝缘膜中的低介电常数材料的低介电常数且高机械强度的材料。另外,本发明可高效率地制造作为PECVD法层间绝缘膜材料使用的高纯度的通式(1)表示的环状硅氧烷化合物。
附图说明
图1是表示平行平板电容耦合型PECVD装置的图。
图2是表示电感耦合型远程PECVD装置的图。
符号说明
1-PECVD装置
2-PECVD腔
3-上部电极
4-下部电极
5-薄膜形成用基板
6-匹配电路(matching circuit)
7-RF电源
8-温度控制装置
9-气化器
10-液体流量控制装置
11-气体流量控制装置
12-容器
13-通式(1)表示的化合物
14-配管
15-配管
16-排气装置
17-接地
18-接地
19-PECVD装置
20-PECVD腔
21-线圈
22-石英管
23-加热部
24-薄膜形成用基板
25-匹配电路
26-RF电源
27-温度控制装置
28-气化器
29-液体流量控制装置
30-气体流量控制装置
31-喷淋头(Shower head)
32-容器
33-通式(1)表示的化合物
34-配管
35-配管
36-排气装置
37-接地
具体实施方式
以下,对本发明的详细内容进行说明。
本发明中,作为R1及以下所述的R2、R4、R6、R8、R9、R10、R11、R12、R13、R14、R15、R16、R17、R18、R19表示的烃基,优选是C1~20的饱和或不饱和烃基,可以具有直链状、支链状、环状的任何结构。另外,下述通式(3)、(5)、(7)中,p、q或r为2以上时,这些烃基可以相互结合形成环状结构。碳原子数超过20时,相应的有机卤化物等原料的供给困难,或者即使能供给而有时纯度低。另外,考虑在CVD装置中的稳定使用时,从有机硅烷化合物的蒸气压不能太低的观点考虑,特别优选C1-6的烃基。
作为R1及以下所述的R2、R4、R6、R8、R9、R10、R11、R12、R13、R14、R15、R16、R17、R18、R19表示的烃基没有特殊限定,优选举出,C1~6的烷基、芳基、芳基烷基、烷基芳基、链烯基、芳基链烯基、链烯基芳基、炔基、芳基炔基、炔基芳基,更优选C1-6的烷基和芳基。
作为具体的例子,可举出甲基、乙基、正丙基、异丙基、环丙基、正丁基、异丁基、仲丁基、叔丁基、环丁基、正戊基、叔戊基、环戊基、正己基、环己基、2-乙基己基等烷基,苯基、联苯基、萘基等芳基,苄基、甲基苄基等芳基烷基,邻甲苯基、间甲苯基、对甲苯基、2,3-二甲基苯基、2,4-二甲基苯基、2,5-二甲基苯基、2,6-二甲基苯基、3,4-二甲基苯基、3,5-二甲基苯基、2,4,6-三甲基苯基、邻乙基苯基、间乙基苯基、对乙基苯基等烷基芳基等。
还可举出,乙烯基、烯丙基、1-丙烯基、1-丁烯基、1,3-丁二烯基、1-戊烯基、1-环戊烯基、2-环戊烯基、环戊二烯基、甲基环戊二烯基、乙基环戊二烯基、1-己烯基、1-环己烯基、2,4-环己二烯基、2,5-环己二烯基、2,4,6-环庚三烯基、5-降冰片烯-2-基等链烯基,2-苯基-1-乙烯基(エテニル)等芳基链烯基、邻苯乙烯基、间苯乙烯基、对苯乙烯基等链烯基芳基,乙炔基、1-丙炔基、2-丙炔基、1-丁炔基、2-丁炔基、3-丁炔基、1-戊炔基、2-戊炔基、3-戊炔基、4-戊炔基、1-己炔基、3-己炔基、5-己炔基等炔基,2-苯基-1-乙炔基等芳基炔基、2-乙炔基-2-苯基等炔基芳基等。
其中,特优选C1~4的烷基和苯基。
上述通式(1)中,A表示含有选自氧原子、硼原子和氮原子中至少一种的基团,可以具有直链状、支链状、环状中任何一种结构。
其中优选含氧的A,例如可举出下述通式(2)或下述通式(3)表示的含氧基团,
[化3]
-O-R2 (2)
(式中,R2与上述相同)
[化4]
-R3-(O-R2)p (3)
(式中,R2与上述相同,R3表示烃残基,p是R3上取代的OR2的数目,为1以上的整数)。
作为用上述通式(3)的R3及以下表示的R5、R7的例子,可以举出,从作为R1、R2、R4、R6、R8、R9、R10、R11、R12、R13、R14、R15、R16、R17、R18、R19的例子所示的烃基的结构中,分别除去p个、q个或r个氢原子得到的结构的烃残基,优选C1~20的饱和或不饱和烃残基,可以具有直链状、支链状、环状中的任何一种结构。
碳原子数超过20时,生成的有机硅烷的蒸气压变低,有时难以在PECVD装置中使用,故不优选。作为含氧的A,优选烷氧基、硅烷氧基、烷氧基芳基、或烷氧基烷基,更优选C1~4的烷氧基、被C1~4的烷氧基取代的苯基、或被C1~4的烷氧基取代的C1~4的烷基。作为此时的R1,优选C1~6的烷基,更优选C1~4的烷基。
作为含氮的A,例如,可举出,下述通式(4)或下述通式(5)表示的含氮基团,
[化5]
(式中,R4与上述相同)
[化6]
(式中,R4与上述相同,R5表示烃残基,q是R5上取代的NR4 2的数目,为1以上的整数)。上式中,R4彼此可以相同也可以不同。作为含氮的A,优选烷基氨基、二烷基氨基、芳基氨基或二芳基氨基。
作为含硼的A,例如可举出下述通式(6)、或下述通式(7)表示的含硼基团,
[化7]
(式中,R6与上述相同)
[化8]
(式中,R6与上述相同,R7表示烃残基,r是R7上取代的BR6 2的数目,为1以上的整数)。上式中R6彼此可以相同也可以不同。作为含硼的A,优选烷基硼残基,烷氧基硼残基。
另外,具有以下特征的含硅膜形成材料也落入本发明的范围,所述特征是,含有具有混合存在上述通式(2)~(7)的取代基的结构的上述通式(1)所示环状硅氧烷化合物。
上述通式(1)中,R1是与Si原子直接键合的仲烃基或叔烃基时,上述通式(1)表示的环状硅氧烷化合物在等离子体中稳定化,可得到具有低电容率值、高机械物性的薄膜,故而优选。并且,优选n是1、x是3~4,另外通式(1)表示的环状硅氧烷化合物的分子量优选低于1000。
作为上述通式(1)表示的环状硅氧烷化合物的具体例,可举出2,4,6-三叔丁基-2,4,6-三甲氧基环三硅氧烷、2,4,6-三仲丁基-2,4,6-三甲氧基环三硅氧烷、2,4,6-三异丁基-2,4,6-三甲氧基环三硅氧烷、2,4,6-三正丁基-2,4,6-三甲氧基环三硅氧烷、2,4,6-三环丁基-2,4,6-三甲氧基环三硅氧烷、2,4,6-三异丙基-2,4,6-三甲氧基环三硅氧烷、2,4,6-三正丙基-2,4,6-三甲氧基环三硅氧烷、2,4,6-三环丙基-2,4,6-三甲氧基环三硅氧烷、2,4,6-三乙基-2,4,6-三甲氧基环三硅氧烷、2,4,6-三甲基-2,4,6-三甲氧基环三硅氧烷等。
还可举出2,4,6-三叔丁基-2,4,6-三乙氧基环三硅氧烷、2,4,6-三仲丁基-2,4,6-三乙氧基环三硅氧烷、2,4,6-三异丁基-2,4,6-三乙氧基环三硅氧烷、2,4,6-三正丁基-2,4,6-三乙氧基环三硅氧烷、2,4,6-三环丁基-2,4,6-三乙氧基环三硅氧烷、2,4,6-三异丙基-2,4,6-三乙氧基环三硅氧烷、2,4,6-三正丙基-2,4,6-三乙氧基环三硅氧烷、2,4,6-三环丙基-2,4,6-三乙氧基环三硅氧烷、2,4,6-三乙基-2,4,6-三乙氧基环三硅氧烷、2,4,6-三甲基-2,4,6-三乙氧基环三硅氧烷等。
还可举出2,4,6-三叔丁基-2,4,6-三正丙氧基环三硅氧烷、2,4,6-三仲丁基-2,4,6-三正丙氧基环三硅氧烷、2,4,6-三异丁基-2,4,6-三正丙氧基环三硅氧烷、2,4,6-三正丁基-2,4,6-三正丙氧基环三硅氧烷、2,4,6-三环丁基-2,4,6-三正丙氧基环三硅氧烷、2,4,6-三异丙基-2,4,6-三正丙氧基环三硅氧烷、2,4,6-三正丙基-2,4,6-三正丙氧基环三硅氧烷、2,4,6-三环丙基-2,4,6-三正丙氧基环三硅氧烷、1,3,5-三乙基-1,3,5-三正丙氧基环三硅氧烷、2,4,6-三甲基-2,4,6-三正丙氧基环三硅氧烷等。
还可举出2,4,6-三叔丁基-2,4,6-三异丙氧基环三硅氧烷、2,4,6-三仲丁基-2,4,6-三异丙氧基环三硅氧烷、2,4,6-三异丁基-2,4,6-三异丙氧基环三硅氧烷、2,4,6-三正丁基-2,4,6-三异丙氧基环三硅氧烷、2,4,6-三环丁基-2,4,6-三异丙氧基环三硅氧烷、2,4,6-三异丙基-2,4,6-三异丙氧基环三硅氧烷、2,4,6-三正丙基-2,4,6-三异丙氧基环三硅氧烷、2,4,6-三环丙基-2,4,6-三异丙氧基环三硅氧烷、2,4,6-三乙基-2,4,6-三异丙氧基环三硅氧烷、2,4,6-三甲基-2,4,6-三异丙氧基环三硅氧烷等。
还可举出2,4,6,8-四叔丁基-2,4,6,8-四甲氧基环四硅氧烷、2,4,6,8-四仲丁基-2,4,6,8-四甲氧基环四硅氧烷、2,4,6,8-四异丁基-2,4,6,8-四甲氧基环四硅氧烷、2,4,6,8-四正丁基-2,4,6,8-四甲氧基环四硅氧烷、2,4,6,8-四环丁基-2,4,6,8- 四甲氧基环四硅氧烷、2,4,6,8-四异丙基-2,4,6,8-四甲氧基环四硅氧烷、2,4,6,8-四正丙基-2,4,6,8-四甲氧基环四硅氧烷、2,4,6,8-四环丙基-2,4,6,8-四甲氧基环四硅氧烷、2,4,6,8-四乙基-2,4,6,8-四甲氧基环四硅氧烷、2,4,6,8-四甲基-2,4,6,8-四甲氧基环四硅氧烷等。
还可举出2,4,6,8-四叔丁基-2,4,6,8-四乙氧基环四硅氧烷、2,4,6,8-四仲丁基-2,4,6,8-四乙氧基环四硅氧烷、2,4,6,8-四异丁基-2,4,6,8-四乙氧基环四硅氧烷、2,4,6,8-四正丁基-2,4,6,8-四乙氧基环四硅氧烷、2,4,6,8-四环丁基-2,4,6,8-四乙氧基环四硅氧烷、2,4,6,8-四异丙基-2,4,6,8-四乙氧基环四硅氧烷、2,4,6,8-四正丙基-2,4,6,8-四乙氧基环四硅氧烷、2,4,6,8-四环丙基-2,4,6,8-四乙氧基环四硅氧烷、2,4,6,8-四乙基-2,4,6,8-四乙氧基环四硅氧烷、2,4,6,8-四甲基-2,4,6,8-四乙氧基环四硅氧烷等。
还可举出2,4,6,8-四叔丁基-2,4,6,8-四正丙氧基环四硅氧烷、2,4,6,8-四仲丁基-2,4,6,8-四正丙氧基环四硅氧烷、2,4,6,8-四异丁基-2,4,6,8-四正丙氧基环四硅氧烷、2,4,6,8-四正丁基-2,4,6,8-四正丙氧基环四硅氧烷、2,4,6,8-四环丁基-2,4,6,8-四正丙氧基环四硅氧烷、2,4,6,8-四异丙基-2,4,6,8-四正丙氧基环四硅氧烷、2,4,6,8-四正丙基-2,4,6,8-四正丙氧基环四硅氧烷、2,4,6,8-四环丙基-2,4,6,8-四正丙氧基环四硅氧烷、2,4,6,8-四乙基-2,4,6,8-四正丙氧基环四硅氧烷、2,4,6,8-四甲基-2,4,6,8-四正丙氧基环四硅氧烷等。
还可举出2,4,6,8-四叔丁基-2,4,6,8-四异丙氧基环四硅氧烷、2,4,6,8-四仲丁基-2,4,6,8-四异丙氧基环四硅氧烷、2,4,6,8-四异丁基-2,4,6,8-四异丙氧基环四硅氧烷、2,4,6,8-四正丁基-2,4,6,8-四异丙氧基环四硅氧烷、2,4,6,8-四环丁基-2,4,6,8-四异丙氧基环四硅氧烷、2,4,6,8-四异丙基-2,4,6,8-四异丙氧基环四硅氧烷、2,4,6,8-四正丙基-2,4,6,8-四异丙氧基环四硅氧烷、2,4,6,8-四环丙基-2,4,6,8-四异丙氧基环四硅氧烷、2,4,6,8-四乙基-2,4,6,8-四异丙氧基环四硅氧烷、2,4,6,8-四甲基-2,4,6,8-四异丙氧基环四硅氧烷等。
还可举出2,4,6,8,10-五叔丁基-2,4,6,8,10-五甲氧基环五硅氧烷、2,4,6,8,10-五仲丁基-2,4,6,8,10-五甲氧基环五硅氧烷、2,4,6,8,10-五异丁基-2,4,6,8,10-五甲氧基环五硅氧烷、2,4,6,8,10-五正丁基-2,4,6,8,10-五甲氧基环五硅氧烷、2,4,6,8,10-五环丁基-2,4,6,8,10-五甲氧基环五硅氧烷、2,4,6,8,10-五异丙基-2,4,6,8,10-五甲氧基环五硅氧烷、2,4,6,8,10-五正丙基-2,4,6,8,10-五甲氧基环五硅氧烷、2,4,6,8,10-五环丙基-2,4,6,8,10-五甲氧基环五硅氧烷、 2,4,6,8,10-五乙基-2,4,6,8,10-五甲氧基环五硅氧烷、2,4,6,8,10-五甲基-2,4,6,8,10-五甲氧基环五硅氧烷等。
还可举出2,4,6,8,10-五叔丁基-2,4,6,8,10-五乙氧基环五硅氧烷、2,4,6,8,10-五仲丁基-2,4,6,8,10-五乙氧基环五硅氧烷、2,4,6,8,10-五异丁基-2,4,6,8,10-五乙氧基环五硅氧烷、2,4,6,8,10-五正丁基-2,4,6,8,10-五乙氧基环五硅氧烷、2,4,6,8,10-五环丁基-2,4,6,8,10-五乙氧基环五硅氧烷、2,4,6,8,10-五异丙基-2,4,6,8,10-五乙氧基环五硅氧烷、2,4,6,8,10-五正丙基-2,4,6,8,10-五乙氧基环五硅氧烷、2,4,6,8,10-五环丙基-2,4,6,8,10-五乙氧基环五硅氧烷、2,4,6,8,10-五乙基-2,4,6,8,10-五乙氧基环五硅氧烷、2,4,6,8,10-五甲基-2,4,6,8,10-五乙氧基环五硅氧烷等。
还可举出2,4,6,8,10-五叔丁基-2,4,6,8,10-五正丙氧基环五硅氧烷、2,4,6,8,10-五仲丁基-2,4,6,8,10-五正丙氧基环五硅氧烷、2,4,6,8,10-五异丁基-2,4,6,8,10-五正丙氧基环五硅氧烷、2,4,6,8,10-五正丁基-2,4,6,8,10-五正丙氧基环五硅氧烷、2,4,6,8,10-五环丁基-2,4,6,8,10-五正丙氧基环五硅氧烷、2,4,6,8,10-五异丙基-2,4,6,8,10-五正丙氧基环五硅氧烷、2,4,6,8,10-五正丙基-2,4,6,8,10-五正丙氧基环五硅氧烷、2,4,6,8,10-五环丙基-2,4,6,8,10-五正丙氧基环五硅氧烷、2,4,6,8,10-五乙基-2,4,6,8,10-五正丙氧基环五硅氧烷、2,4,6,8,10-五甲基-2,4,6,8,10-五正丙氧基环五硅氧烷等。
还可举出2,4,6,8,10-五叔丁基-2,4,6,8,10-五异丙氧基环五硅氧烷、2,4,6,8,10-五仲丁基-2,4,6,8,10-五异丙氧基环五硅氧烷、2,4,6,8,10-五异丁基-2,4,6,8,10-五异丙氧基环五硅氧烷、2,4,6,8,10-五正丁基-2,4,6,8,10-五异丙氧基环五硅氧烷、2,4,6,8,10-五环丁基-2,4,6,8,10-五异丙氧基环五硅氧烷、2,4,6,8,10-五异丙基-2,4,6,8,10-五异丙氧基环五硅氧烷、2,4,6,8,10-五正丙基-2,4,6,8,10-五异丙氧基环五硅氧烷、2,4,6,8,10-五环丙基-2,4,6,8,10-五异丙氧基环五硅氧烷、2,4,6,8,10-五乙基-2,4,6,8,10-五异丙氧基环五硅氧烷、2,4,6,8,10-五甲基-2,4,6,8,10-五异丙氧基环五硅氧烷等。
还可举出2,2,4,4,6,6-六甲氧基环三硅氧烷、2,2,4,4,6,6-六乙氧基环三硅氧烷、2,2,4,4,6,6-六正丙氧基环三硅氧烷、2,2,4,4,6,6-六异丙氧基环三硅氧烷、2,2,4,4,6,6-六环丙氧基环三硅氧烷、2,2,4,4,6,6-六叔丁氧基环三硅氧烷、2,2,4,4,6,6-六仲丁氧基环三硅氧烷、2,2,4,4,6,6-六异丁氧基环三硅氧烷、2,2,4,4,6,6-六正丁氧基环三硅氧烷、2,2,4,4,6,6-六环丁氧基环三硅氧烷等。
还可举出2,2,4,4,6,6,8,8-八甲氧基环四硅氧烷、2,2,4,4,6,6,8,8-八乙氧基环四硅氧烷、2,2,4,4,6,6,8,8-八正丙氧基环四硅氧烷、2,2,4,4,6,6,8,8-八异丙氧基环四硅氧烷、2,2,4,4,6,6,8,8-八环丙氧基环四硅氧烷、2,2,4,4,6,6,8,8-八叔丁氧基环四硅氧烷、2,2,4,4,6,6,8,8-八仲丁氧基环四硅氧烷、2,2,4,4,6,6,8,8-八异丁氧基环四硅氧烷、2,2,4,4,6,6,8,8-八正丁氧基环四硅氧烷、2,2,4,4,6,6,8,8-八环丁氧基环四硅氧烷等。
还可举出2,2,4,4,6,6,8,8,10,10-十甲氧基环五硅氧烷、2,2,4,4,6,6,8,8,10,10-十乙氧基环五硅氧烷、2,2,4,4,6,6,8,8,10,10-十正丙氧基环五硅氧烷、2,2,4,4,6,6,8,8,10,10-十异丙氧基环五硅氧烷、2,2,4,4,6,6,8,8,10,10-十环丙氧基环五硅氧烷、2,2,4,4,6,6,8,8,10,10-十叔丁氧基环五硅氧烷、2,2,4,4,6,6,8,8,10,10-十仲丁氧基环五硅氧烷、2,2,4,4,6,6,8,8,10,10-十异丁氧基环五硅氧烷、2,2,4,4,6,6,8,8,10,10-十正丁氧基环五硅氧烷、2,2,4,4,6,6,8,8,10,10-十环丁氧基环五硅氧烷等。
还可举出2,4,6-三(2-甲氧基乙基)-2,4,6-三甲基环三硅氧烷、2,4,6-三(2-叔丁氧基乙基)-2,4,6-三甲基环三硅氧烷、2,4,6,8-四(2-甲氧基乙基)-2,4,6,8-四甲基环四硅氧烷、2,4,6,8-四(2-叔丁氧基乙基)-2,4,6,8-四甲基环四硅氧烷、2,4,6,8,10-五(2-甲氧基乙基)-2,4,6,8,10-五甲基环五硅氧烷、2,4,6,8,10-五(2-叔丁氧基乙基)-2,4,6,8,10-五甲基环五硅氧烷等。
还可举出2,4,6-三(4-甲氧基苯基)-2,4,6-三甲基环三硅氧烷、2,4,6-三(4-叔丁氧基苯基)-2,4,6-三甲基环三硅氧烷、2,4,6,8-四(4-甲氧基苯基)-2,4,6,8-四甲基环四硅氧烷、2,4,6,8-四(4-叔丁氧基苯基)-2,4,6,8-四甲基环四硅氧烷、2,4,6,8,10-五(4-甲氧基苯基)-2,4,6,8,10-五甲基环五硅氧烷、2,4,6,8,10-五(4-叔丁氧基苯基)-2,4,6,8,10-五甲基环五硅氧烷等。
还可举出2,4,6-三(甲氧基甲基)-2,4,6-三甲基环三硅氧烷、2,4,6-三(乙氧基甲基)-2,4,6-三甲基环三硅氧烷、2,4,6-三(正丙氧基甲基)-2,4,6-三甲基环三硅氧烷、2,4,6-三(异丙氧基甲基)-2,4,6-三甲基环三硅氧烷、2,4,6-三(正丁氧基甲基)-2,4,6-三甲基环三硅氧烷、2,4,6-三(异丁氧基甲基)-2,4,6-三甲基环三硅氧烷、2,4,6-三(叔丁氧基甲基)-2,4,6-三甲基环三硅氧烷等。
还可举出2,4,6-三(甲氧基甲基)-2,4,6-三乙基环三硅氧烷、2,4,6-三(乙氧基甲基)-2,4,6-三乙基环三硅氧烷、2,4,6-三(正丙氧基甲基)-2,4,6-三乙基环三硅氧烷、2,4,6-三(异丙氧基甲基)-2,4,6-三乙基环三硅氧烷、2,4,6-三(正丁氧 基甲基)-2,4,6-三乙基环三硅氧烷、2,4,6-三(异丁氧基甲基)-2,4,6-三乙基环三硅氧烷、2,4,6-三(叔丁氧基甲基)-2,4,6-三乙基环三硅氧烷等。
还可举出2,4,6-三(甲氧基甲基)-2,4,6-三异丙基环三硅氧烷、2,4,6-三(乙氧基甲基)-2,4,6-三异丙基环三硅氧烷、2,4,6-三(正丙氧基甲基)-2,4,6-三异丙基环三硅氧烷、2,4,6-三(异丙氧基甲基)-2,4,6-三异丙基环三硅氧烷、2,4,6-三(正丁氧基甲基)-2,4,6-三异丙基环三硅氧烷、2,4,6-三(异丁氧基甲基)-2,4,6-三异丙基环三硅氧烷、2,4,6-三(叔丁氧基甲基)-2,4,6-三异丙基环三硅氧烷等。
还可举出2,4,6-三(甲氧基甲基)-2,4,6-三正丙基环三硅氧烷、2,4,6-三(乙氧基甲基)-2,4,6-三正丙基环三硅氧烷、2,4,6-三(正丙氧基甲基)-2,4,6-三正丙基环三硅氧烷、2,4,6-三(异丙氧基甲基)-2,4,6-三正丙基环三硅氧烷、2,4,6-三(正丁氧基甲基)-2,4,6-三正丙基环三硅氧烷、2,4,6-三(异丁氧基甲基)-2,4,6-三正丙基环三硅氧烷、2,4,6-三(叔丁氧基甲基)-2,4,6-三正丙基环三硅氧烷等。
还可举出2,4,6-三(甲氧基甲基)-2,4,6-三叔丁基环三硅氧烷、2,4,6-三(乙氧基甲基)-2,4,6-三叔丁基环三硅氧烷、2,4,6-三(正丙氧基甲基)-2,4,6-三叔丁基环三硅氧烷、2,4,6-三(异丙氧基甲基)-2,4,6-三叔丁基环三硅氧烷、2,4,6-三(正丁氧基甲基)-2,4,6-三叔丁基环三硅氧烷、2,4,6-三(异丁氧基甲基)-2,4,6-三叔丁基环三硅氧烷、2,4,6-三(叔丁氧基甲基)-2,4,6-三叔丁基环三硅氧烷等。
还可举出2,4,6-三(甲氧基甲基)-2,4,6-三环戊基环三硅氧烷、2,4,6-三(乙氧基甲基)-2,4,6-三环戊基环三硅氧烷、2,4,6-三(正丙氧基甲基)-2,4,6-三环戊基环三硅氧烷、2,4,6-三(异丙氧基甲基)-2,4,6-三环戊基环三硅氧烷、2,4,6-三(正丁氧基甲基)-2,4,6-三环戊基环三硅氧烷、2,4,6-三(异丁氧基甲基)-2,4,6-三环戊基环三硅氧烷、2,4,6-三(叔丁氧基甲基)-2,4,6-三环戊基环三硅氧烷等。
还可举出2,4,6-三(甲氧基甲基)-2,4,6-三环己基环三硅氧烷、2,4,6-三(乙氧基甲基)-2,4,6-三环己基环三硅氧烷、2,4,6-三(正丙氧基甲基)-2,4,6-三环己基环三硅氧烷、2,4,6-三(异丙氧基甲基)-2,4,6-三环己基环三硅氧烷、2,4,6-三(正丁氧基甲基)-2,4,6-三环己基环三硅氧烷、2,4,6-三(异丁氧基甲基)-2,4,6-三环己基环三硅氧烷、2,4,6-三(叔丁氧基甲基)-2,4,6-三环己基环三 硅氧烷等。
还可举出2,4,6-三(甲氧基乙基)-2,4,6-三甲基环三硅氧烷、2,4,6-三(乙氧基乙基)-2,4,6-三甲基环三硅氧烷、2,4,6-三(正丙氧基乙基)-2,4,6-三甲基环三硅氧烷、2,4,6-三(异丙氧基乙基)-2,4,6-三甲基环三硅氧烷、2,4,6-三(正丁氧基乙基)-2,4,6-三甲基环三硅氧烷、2,4,6-三(异丁氧基乙基)-2,4,6-三甲基环三硅氧烷、2,4,6-三(叔丁氧基乙基)-2,4,6-三甲基环三硅氧烷等。
还可举出2,4,6-三(甲氧基乙基)-2,4,6-三乙基环三硅氧烷、2,4,6-三(乙氧基乙基)-2,4,6-三乙基环三硅氧烷、2,4,6-三(正丙氧基乙基)-2,4,6-三乙基环三硅氧烷、2,4,6-三(异丙氧基乙基)-2,4,6-三乙基环三硅氧烷、2,4,6-三(正丁氧基乙基)-2,4,6-三乙基环三硅氧烷、2,4,6-三(异丁氧基乙基)-2,4,6-三乙基环三硅氧烷、2,4,6-三(叔丁氧基乙基)-2,4,6-三乙基环三硅氧烷等。
还可举出2,4,6-三(甲氧基乙基)-2,4,6-三异丙基环三硅氧烷、2,4,6-三(乙氧基乙基)-2,4,6-三异丙基环三硅氧烷、2,4,6-三(正丙氧基乙基)-2,4,6-三异丙基环三硅氧烷、2,4,6-三(异丙氧基乙基)-2,4,6-三异丙基环三硅氧烷、2,4,6-三(正丁氧基乙基)-2,4,6-三异丙基环三硅氧烷、2,4,6-三(异丁氧基乙基)-2,4,6-三异丙基环三硅氧烷、2,4,6-三(叔丁氧基乙基)-2,4,6-三异丙基环三硅氧烷等。
还可举出2,4,6-三(甲氧基乙基)-2,4,6-三正丙基环三硅氧烷、2,4,6-三(乙氧基乙基)-2,4,6-三正丙基环三硅氧烷、2,4,6-三(正丙氧基乙基)-2,4,6-三正丙基环三硅氧烷、2,4,6-三(异丙氧基乙基)-2,4,6-三正丙基环三硅氧烷、2,4,6-三(正丁氧基乙基)-2,4,6-三正丙基环三硅氧烷、2,4,6-三(异丁氧基乙基)-2,4,6-三正丙基环三硅氧烷、2,4,6-三(叔丁氧基乙基)-2,4,6-三正丙基环三硅氧烷等。
还可举出2,4,6-三(甲氧基乙基)-2,4,6-三叔丁基环三硅氧烷、2,4,6-三(乙氧基乙基)-2,4,6-三叔丁基环三硅氧烷、2,4,6-三(正丙氧基乙基)-2,4,6-三叔丁基环三硅氧烷、2,4,6-三(异丙氧基乙基)-2,4,6-三叔丁基环三硅氧烷、2,4,6-三(正丁氧基乙基)-2,4,6-三叔丁基环三硅氧烷、2,4,6-三(异丁氧基乙基)-2,4,6-三叔丁基环三硅氧烷、2,4,6-三(叔丁氧基乙基)-2,4,6-三叔丁基环三硅氧烷等。
还可举出2,4,6-三(甲氧基乙基)-2,4,6-三环戊基环三硅氧烷、2,4,6-三(乙氧基乙基)-2,4,6-三环戊基环三硅氧烷、2,4,6-三(正丙氧基乙基)-2,4,6-三环戊 基环三硅氧烷、2,4,6-三(异丙氧基乙基)-2,4,6-三环戊基环三硅氧烷、2,4,6-三(正丁氧基乙基)-2,4,6-三环戊基环三硅氧烷、2,4,6-三(异丁氧基乙基)-2,4,6-三环戊基环三硅氧烷、2,4,6-三(叔丁氧基乙基)-2,4,6-三环戊基环三硅氧烷等。
还可举出2,4,6-三(甲氧基乙基)-2,4,6-三环己基环三硅氧烷、2,4,6-三(乙氧基乙基)-2,4,6-三环己基环三硅氧烷、2,4,6-三(正丙氧基乙基)-2,4,6-三环己基环三硅氧烷、2,4,6-三(异丙氧基乙基)-2,4,6-三环己基环三硅氧烷、2,4,6-三(正丁氧基乙基)-2,4,6-三环己基环三硅氧烷、2,4,6-三(异丁氧基乙基)-2,4,6-三环己基环三硅氧烷、2,4,6-三(叔丁氧基乙基)-2,4,6-三环己基环三硅氧烷等。
还可举出2,4,6-三(甲氧基丙基)-2,4,6-三甲基环三硅氧烷、2,4,6-三(甲氧基丙基)-2,4,6-三乙基环三硅氧烷、2,4,6-三(甲氧基丙基)-2,4,6-三异丙基环三硅氧烷、2,4,6-三(甲氧基丁基)-2,4,6-三甲基环三硅氧烷、2,4,6-三(甲氧基戊基)-2,4,6-三甲基环三硅氧烷、2,4,6-三(甲氧基己基)-2,4,6-三甲基环三硅氧烷等。
还可举出2,4,6,8-四(甲氧基甲基)-2,4,6,8-四甲基环四硅氧烷、2,4,6,8-四(乙氧基甲基)-2,4,6,8-四甲基环四硅氧烷、2,4,6,8-四(正丙氧基甲基)-2,4,6,8-四甲基环四硅氧烷、2,4,6,8-四(异丙氧基甲基)-2,4,6,8-四甲基环四硅氧烷、2,4,6,8-四(正丁氧基甲基)-2,4,6,8-四甲基环四硅氧烷、2,4,6,8-四(异丁氧基甲基)-2,4,6,8-四甲基环四硅氧烷、2,4,6,8-四(叔丁氧基甲基)-2,4,6,8-四甲基环四硅氧烷等。
还可举出2,4,6,8-四(甲氧基甲基)-2,4,6,8-四乙基环四硅氧烷、2,4,6,8-四(乙氧基甲基)-2,4,6,8-四乙基环四硅氧烷、2,4,6,8-四(正丙氧基甲基)-2,4,6,8-四乙基环四硅氧烷、2,4,6,8-四(异丙氧基甲基)-2,4,6,8-四乙基环四硅氧烷、2,4,6,8-四(正丁氧基甲基)-2,4,6,8-四乙基环四硅氧烷、2,4,6,8-四(异丁氧基甲基)-2,4,6,8-四乙基环四硅氧烷、2,4,6,8-四(叔丁氧基甲基)-2,4,6,8-四乙基环四硅氧烷等。
还可举出2,4,6,8-四(甲氧基甲基)-2,4,6,8-四正丙基环四硅氧烷、2,4,6,8-四(乙氧基甲基)-2,4,6,8-四正丙基环四硅氧烷、2,4,6,8-四(正丙氧基甲基)-2,4,6,8-四正丙基环四硅氧烷、2,4,6,8-四(异丙氧基甲基)-2,4,6,8-四正丙基环四硅氧烷、2,4,6,8-四(正丁氧基甲基)-2,4,6,8-四正丙基环四硅氧烷、2,4,6,8- 四(异丁氧基甲基)-2,4,6,8-四正丙基环四硅氧烷、2,4,6,8-四(叔丁氧基甲基)-2,4,6,8-四正丙基环四硅氧烷等。
还可举出2,4,6,8-四(甲氧基甲基)-2,4,6,8-四异丙基环四硅氧烷、2,4,6,8-四(乙氧基甲基)-2,4,6,8-四异丙基环四硅氧烷、2,4,6,8-四(正丙氧基甲基)-2,4,6,8-四异丙基环四硅氧烷、2,4,6,8-四(异丙氧基甲基)-2,4,6,8-四异丙基环四硅氧烷、2,4,6,8-四(正丁氧基甲基)-2,4,6,8-四异丙基环四硅氧烷、2,4,6,8-四(异丁氧基甲基)-2,4,6,8-四异丙基环四硅氧烷、2,4,6,8-四(叔丁氧基甲基)-2,4,6,8-四异丙基环四硅氧烷等。
还可举出2,4,6,8-四(甲氧基甲基)-2,4,6,8-四叔丁基环四硅氧烷、2,4,6,8-四(乙氧基甲基)-2,4,6,8-四叔丁基环四硅氧烷、2,4,6,8-四(正丙氧基甲基)-2,4,6,8-四叔丁基环四硅氧烷、2,4,6,8-四(异丙氧基甲基)-2,4,6,8-四叔丁基环四硅氧烷、2,4,6,8-四(正丁氧基甲基)-2,4,6,8-四叔丁基环四硅氧烷、2,4,6,8-四(异丁氧基甲基)-2,4,6,8-四叔丁基环四硅氧烷、2,4,6,8-四(叔丁氧基甲基)-2,4,6,8-四叔丁基环四硅氧烷等。
还可举出2,4,6,8-四(甲氧基甲基)-2,4,6,8-四环戊基环四硅氧烷、2,4,6,8-四(乙氧基甲基)-2,4,6,8-四环戊基环四硅氧烷、2,4,6,8-四(正丙氧基甲基)-2,4,6,8-四环戊基环四硅氧烷、2,4,6,8-四(异丙氧基甲基)-2,4,6,8-四环戊基环四硅氧烷、2,4,6,8-四(正丁氧基甲基)-2,4,6,8-四环戊基环四硅氧烷、2,4,6,8-四(异丁氧基甲基)-2,4,6,8-四环戊基环四硅氧烷、2,4,6,8-四(叔丁氧基甲基)-2,4,6,8-四环戊基环四硅氧烷等。
还可举出2,4,6,8-四(甲氧基甲基)-2,4,6,8-四环己基环四硅氧烷、2,4,6,8-四(乙氧基甲基)-2,4,6,8-四环己基环四硅氧烷、2,4,6,8-四(正丙氧基甲基)-2,4,6,8-四环己基环四硅氧烷、2,4,6,8-四(异丙氧基甲基)-2,4,6,8-四环己基环四硅氧烷、2,4,6,8-四(正丁氧基甲基)-2,4,6,8-四环己基环四硅氧烷、2,4,6,8-四(异丁氧基甲基)-2,4,6,8-四环己基环四硅氧烷、2,4,6,8-四(叔丁氧基甲基)-2,4,6,8-四环己基环四硅氧烷等。
还可举出2,4,6,8-四(甲氧基乙基)-2,4,6,8-四甲基环四硅氧烷、2,4,6,8-四(乙氧基乙基)-2,4,6,8-四甲基环四硅氧烷、2,4,6,8-四(正丙氧基乙基)-2,4,6,8-四甲基环四硅氧烷、2,4,6,8-四(异丙氧基乙基)-2,4,6,8-四甲基环四硅氧烷、2,4,6,8-四(正丁氧基乙基)-2,4,6,8-四甲基环四硅氧烷、2,4,6,8-四(异丁氧基乙基)-2,4,6,8-四甲基环四硅氧烷、2,4,6,8-四(叔丁氧基乙基)-2,4,6,8-四甲基环四 硅氧烷等。
还可举出2,4,6,8-四(甲氧基乙基)-2,4,6,8-四乙基环四硅氧烷、2,4,6,8-四(乙氧基乙基)-2,4,6,8-四乙基环四硅氧烷、2,4,6,8-四(正丙氧基乙基)-2,4,6,8-四乙基环四硅氧烷、2,4,6,8-四(异丙氧基乙基)-2,4,6,8-四乙基环四硅氧烷、2,4,6,8-四(正丁氧基乙基)-2,4,6,8-四乙基环四硅氧烷、2,4,6,8-四(异丁氧基乙基)-2,4,6,8-四乙基环四硅氧烷、2,4,6,8-四(叔丁氧基乙基)-2,4,6,8-四乙基环四硅氧烷等。
还可举出2,4,6,8-四(甲氧基乙基)-2,4,6,8-四正丙基环四硅氧烷、2,4,6,8-四(乙氧基乙基)-2,4,6,8-四正丙基环四硅氧烷、2,4,6,8-四(正丙氧基乙基)-2,4,6,8-四正丙基环四硅氧烷、2,4,6,8-四(异丙氧基乙基)-2,4,6,8-四正丙基环四硅氧烷、2,4,6,8-四(正丁氧基乙基)-2,4,6,8-四正丙基环四硅氧烷、2,4,6,8-四(异丁氧基乙基)-2,4,6,8-四正丙基环四硅氧烷、2,4,6,8-四(叔丁氧基乙基)-2,4,6,8-四正丙基环四硅氧烷等。
还可举出2,4,6,8-四(甲氧基乙基)-2,4,6,8-四异丙基环四硅氧烷、2,4,6,8-四(乙氧基乙基)-2,4,6,8-四异丙基环四硅氧烷、2,4,6,8-四(正丙氧基乙基)-2,4,6,8-四异丙基环四硅氧烷、2,4,6,8-四(异丙氧基乙基)-2,4,6,8-四异丙基环四硅氧烷、2,4,6,8-四(正丁氧基乙基)-2,4,6,8-四异丙基环四硅氧烷、2,4,6,8-四(异丁氧基乙基)-2,4,6,8-四异丙基环四硅氧烷、2,4,6,8-四(叔丁氧基乙基)-2,4,6,8-四异丙基环四硅氧烷等。
还可举出2,4,6,8-四(甲氧基乙基)-2,4,6,8-四叔丁基环四硅氧烷、2,4,6,8-四(乙氧基乙基)-2,4,6,8-四叔丁基环四硅氧烷、2,4,6,8-四(正丙氧基乙基)-2,4,6,8-四叔丁基环四硅氧烷、2,4,6,8-四(异丙氧基乙基)-2,4,6,8-四叔丁基环四硅氧烷、2,4,6,8-四(正丁氧基乙基)-2,4,6,8-四叔丁基环四硅氧烷、2,4,6,8-四(异丁氧基乙基)-2,4,6,8-四叔丁基环四硅氧烷、2,4,6,8-四(叔丁氧基乙基)-2,4,6,8-四叔丁基环四硅氧烷等。
还可举出2,4,6,8-四(甲氧基乙基)-2,4,6,8-四环戊基环四硅氧烷、2,4,6,8-四(乙氧基乙基)-2,4,6,8-四环戊基环四硅氧烷、2,4,6,8-四(正丙氧基乙基)-2,4,6,8-四环戊基环四硅氧烷、2,4,6,8-四(异丙氧基乙基)-2,4,6,8-四环戊基环四硅氧烷、2,4,6,8-四(正丁氧基乙基)-2,4,6,8-四环戊基环四硅氧烷、2,4,6,8-四(异丁氧基乙基)-2,4,6,8-四环戊基环四硅氧烷、2,4,6,8-四(叔丁氧基乙基)-2,4,6,8-四环戊基环四硅氧烷等。
还可举出2,4,6,8-四(甲氧基乙基)-2,4,6,8-四环己基环四硅氧烷、2,4,6,8-四(乙氧基乙基)-2,4,6,8-四环己基环四硅氧烷、2,4,6,8-四(正丙氧基乙基)-2,4,6,8-四环己基环四硅氧烷、2,4,6,8-四(异丙氧基乙基)-2,4,6,8-四环己基环四硅氧烷、2,4,6,8-四(正丁氧基乙基)-2,4,6,8-四环己基环四硅氧烷、2,4,6,8-四(异丁氧基乙基)-2,4,6,8-四环己基环四硅氧烷、2,4,6,8-四(叔丁氧基乙基)-2,4,6,8-四环己基环四硅氧烷等。
还可举出2,4,6,8-四(甲氧基丙基)-2,4,6,8-四甲基环三硅氧烷、2,4,6,8-四(甲氧基丙基)-2,4,6,8-四乙基环三硅氧烷、2,4,6,8-四(甲氧基丙基)-2,4,6,8-四异丙基环三硅氧烷、2,4,6,8-四(甲氧基丁基)-2,4,6,8-四甲基环三硅氧烷、2,4,6,8-四(甲氧基戊基)-2,4,6,8-四甲基环三硅氧烷、2,4,6,8-四(甲氧基己基)-2,4,6,8-四甲基环三硅氧烷等。
还可举出2,4,6,8,10-五(甲氧基甲基)-2,4,6,8,10-五甲基环五硅氧烷、2,4,6,8,10-五(甲氧基甲基)-2,4,6,8,10-五乙基环五硅氧烷、2,4,6,8,10-五(甲氧基甲基)-2,4,6,8,10-五异丙基环五硅氧烷等。
还可举出2,4,6,8,10-五(甲氧基乙基)-2,4,6,8,10-五甲基环五硅氧烷、2,4,6,8,10-五(甲氧基乙基)-2,4,6,8,10-五乙基环五硅氧烷、2,4,6,8,10-五(甲氧基乙基)-2,4,6,8,10-五异丙基环五硅氧烷等。
还可举出2,4,6-三叔丁基-2,4,6-三(二甲基氨基)环三硅氧烷、2,4,6-三叔丁基-2,4,6-三(二乙基氨基)环三硅氧烷、2,4,6,8-四叔丁基-2,4,6,8-四(二甲基氨基)环四硅氧烷、2,4,6,8-四叔丁基-2,4,6,8-四(二乙基氨基)环四硅氧烷、2,4,6,8,10-五叔丁基-2,4,6,8,10-五(二甲基氨基)环五硅氧烷、2,4,6,8,10-五叔丁基-2,4,6,8,10-五(二乙氨基)环五硅氧烷等。
还可举出2,4,6-三异丙基-2,4,6-三(二甲基氨基)环三硅氧烷、2,4,6-三异丙基-2,4,6-三(二乙基氨基)环三硅氧烷、2,4,6,8-四异丙基-2,4,6,8-四(二甲基氨基)环四硅氧烷、2,4,6,8-四异丙基-2,4,6,8-四(二乙基氨基)环四硅氧烷、2,4,6,8,10-五异丙基-2,4,6,8,10-五(二甲基氨基)环五硅氧烷、2,4,6,8,10-五异丙基-2,4,6,8,10-五(二乙基氨基)环五硅氧烷等。
还可举出2,4,6-三甲基-2,4,6-三(二甲基氨基)环三硅氧烷、2,4,6-三甲基-2,4,6-三(二乙基氨基)环三硅氧烷、2,4,6,8-四甲基-2,4,6,8-四(二甲基氨基)环四硅氧烷、2,4,6,8-四甲基-2,4,6,8-四(二乙基氨基)环四硅氧烷、2,4,6,8,10-五甲基-2,4,6,8,10-五(二甲基氨基)环五硅氧烷、2,4,6,8,10-五甲基-2,4,6,8,10-五 (二乙基氨基)环五硅氧烷等。
还可举出2,4,6-三(4-二甲氨基苯基)-2,4,6-三甲基环三硅氧烷、2,4,6-三(4-二乙氨基苯基)-2,4,6-三甲基环三硅氧烷、2,4,6,8-四(4-二甲氨基苯基)-2,4,6,8-四甲基环四硅氧烷、2,4,6,8-四(4-二乙氨基苯基)-2,4,6,8-四甲基环四硅氧烷、2,4,6,8,10-五(4-二甲氨基苯基)-2,4,6,8,10-五甲基环五硅氧烷、2,4,6,8,10-五(4-二乙氨基苯基)-2,4,6,8,10-五甲基环五硅氧烷等。
还可举出2,4,6-三叔丁基-2,4,6-三(二甲基硼)环三硅氧烷、2,4,6-三叔丁基-2,4,6-三(二乙基硼)环三硅氧烷、2,4,6,8-四叔丁基-2,4,6,8-四(二甲基硼)环四硅氧烷、2,4,6,8-四叔丁基-2,4,6,8-四(二乙基硼)环四硅氧烷、2,4,6,8,10-五叔丁基-2,4,6,8,10-五(二甲基硼)环五硅氧烷、2,4,6,8,10-五叔丁基-2,4,6,8,10-五(二乙基硼)环五硅氧烷等。
还可举出2,4,6-三异丙基-2,4,6-三(二甲基硼)环三硅氧烷、2,4,6-三异丙基-2,4,6-三(二乙基硼)环三硅氧烷、2,4,6,8-四异丙基-2,4,6,8-四(二甲基硼)环四硅氧烷、2,4,6,8-四异丙基-2,4,6,8-四(二乙基硼)环四硅氧烷、2,4,6,8,10-五异丙基-2,4,6,8,10-五(二甲基硼)环五硅氧烷、2,4,6,8,10-五异丙基-2,4,6,8,10-五(二乙基硼)环五硅氧烷等。
还可举出2,4,6-三甲基-2,4,6-三(二甲基硼)环三硅氧烷、2,4,6-三甲基-2,4,6-三(二乙基硼)环三硅氧烷、2,4,6,8-四甲基-2,4,6,8-四(二甲基硼)环四硅氧烷、2,4,6,8-四甲基-2,4,6,8-四(二乙基硼)环四硅氧烷、2,4,6,8,10-五甲基-2,4,6,8,10-五(二甲基硼)环五硅氧烷、2,4,6,8,10-五甲基-2,4,6,8,10-五(二乙基硼)环五硅氧烷等。
还可举出2,4,6-三(4-二甲基硼苯基)-2,4,6-三甲基环三硅氧烷、2,4,6-三(4-二乙基硼苯基)-2,4,6-三甲基环三硅氧烷、2,4,6,8-四(4-二甲基硼苯基)-2,4,6,8-四甲基环四硅氧烷、2,4,6,8-四(4-二乙基硼苯基)-2,4,6,8-四甲基环四硅氧烷、2,4,6,8,10-五(4-二甲基硼苯基)-2,4,6,8,10-五甲基环五硅氧烷、2,4,6,8,10-五(4-二乙基硼苯基)-2,4,6,8,10-五甲基环五硅氧烷等。
本发明的含硅膜形成材料含有通式(1)表示的环状硅氧烷化合物,为了作为绝缘膜材料使用,优选除了硅、碳、氧、氢、氮、硼以外,杂质量少于10ppb,并且含水量少于50ppm。
上述通式(1)表示的环状硅氧烷化合物的制造方法没有特殊限制,例如,作为制造具有上述通式(2)的结构的环状硅氧烷化合物的方法,可以采用在 酸或碱的共存或不共存下将下述通式(8)表示的含氧硅烷化合物进行水解的方法,
[化9]
(式中,R1、R8与上述相同)
或在Pd、Ni或Rh催化剂下使下述通式(9)表示的环状硅氧烷与醇类反应,进行制造的方法。
[化10]
(式中,R1、n、x与上式相同)
作为制造具有上述通式(3)的结构的环状硅氧烷化合物的方法,例如可以采用以下方法,在酸或碱的共存下或不共存下,将使相应的格利雅试剂或有机锂化合物与有机硅烷化合物反应得到的下述通式(10)表示的含氧硅烷化合物进行水解的方法,
[化11]
(式中,R1、R2、R3、R9、p与上述相同。s表示1或2,t表示0或1,s+t为1~2),
或在Pt催化剂下使上述通式(9)表示的环状硅氧烷与具有R2O基的炔烃化合物反应进行制造的方法。
作为制造有上述通式(4)的结构的环状硅氧烷的方法,例如可以采用在酸或碱的共存或不共存下将下述通式(11)表示的含氮及氧的硅烷化合物进行水解的方法。
[化12]
(式中,R1、R4、R10与上述相同。u表示1或2,v表示0或1,u+v为1~2。)
作为制造具有上述通式(5)的结构的环状硅氧烷化合物的方法,例如可以采用在酸或碱的共存或不共存下将例如下述通式(12)表示的含氮和氧的硅烷化合物进行水解的方法,
[化13]
(式中,R1、R4、R5、R11,q与上述相同。y表示1或2,z表示0或1,y+z是1~2)。
作为制造具有上述通式(6)的结构的环状硅氧烷的方法,例如可以采用在酸或碱的共存或不共存下将例如下述通式(13)表示的含有硼和氧的硅烷化合物进行水解的方法,
[化14]
(式中,R1、R6、R12与上述相同。a表示1或2,b表示0或1,a+b是1~2)。
作为制造具有上述通式(7)的结构的环状硅氧烷的方法,例如可以采用在酸或碱的共存或不共存下将下述通式(14)表示的含有硼和氧的硅烷化合物进行水解的方法,
[化15]
(式中,R1、R6、R7、R13,r与上述相同。c表示1或2,d表示0或1,c+d是1~2)。
反应时,作为共存的酸,例如可以使用盐酸、硝酸、硫酸等无机酸,及甲苯磺酸等有机酸。另外,反应时,作为共存的碱,例如可以使用氢氧化钠、氢氧化钾、甲醇钠、甲醇钾、乙醇钠、乙醇钾、叔丁醇钠、叔丁醇钾等。
作为使上述通式(9)的环状硅氧烷化合物和醇类反应时可以使用的Pd、Ni或Rh催化剂,可以使用载负在高表面积活性炭上的Pd(0)、Ni(0)或Rh(0)催化剂,或者下述通式(15)表示的非均相或均相类催化剂。
[化16]
MXeLf (15)
(式中,M表示Pd、Ni或Rh,X表示氟、氯、溴或碘,L表示给电子性化合物。e及f表示0以上的数,e+f是满足M的价数及配位数的数)。
作为上述通式(15)中L表示的给电子性化合物,例如,可以使用膦类化合物、胺类化合物等。具体地,可以使用下述通式(16)或下述通式(17)表示的膦化合物。
[化17]
PR14 3 (16)
(式中,R14与上述相同。R14彼此可以相同也可以不同)。
[化18]
(式中,R15与上述相同,R15彼此可以相同也可以不同)。
或者通式(18)或(19)表示的胺化合物。
[化19]
NR16 3 (18)
(式中,R16表示与前述同样,R16彼此可以相同也可以不同)。
[化20]
(式中,R17表示与前述同样。R17彼此可以相同也可以不同)。
制造通式(1)表示的环状硅氧烷化合物时可使用的反应溶剂,只要是该技术领域中使用的溶剂则没有特殊限定,例如,可以使用正戊烷、异戊烷、正己烷、环己烷、正庚烷、正癸烷等饱和烃类,甲苯、二甲苯、癸烯-1等不饱和烃类,乙醚、丙醚、叔丁基甲基醚、丁醚、环戊基甲基醚、四氢呋喃等醚类,甲醇、乙醇、异丙醇、正丁醇、叔丁醇、2-乙基己醇等醇。还可以使用这些溶剂的混合溶剂。尤其是使用醚类或醇类的场合,有时可高收率地制造具有特定分子量的通式(1)表示的环状硅氧烷化合物。
制造通式(1)表示的环状硅氧烷化合物时的反应温度,通常在作为工业上使用的温度的-100~200℃的范围,优选在-85~150℃的范围进行。反应的压力条件可以是加压下、常压下、减压下任何一种。
对于制造的通式(1)表示的环状硅氧烷化合物的精制方法,为了使作为绝缘膜材料使用中有用的水分含量为低于50ppm,使硅、碳、氧、氢以外的杂质,例如,金属杂质量为低于10ppb,可以采用常压或减压蒸馏或者使用二氧化硅、氧化铝、高分子凝胶的柱分离等的精制方法。此时,可以根据需要将这些的方法组合使用。
最终制得的通式(1)表示的环状硅氧烷化合物中的水分或硅、碳、氧、氢以外的元素杂质,尤其是金属杂质残渣高时,成为不适合作为绝缘膜材料使用的化合物。
制造时,其他的条件优选参照该有机合成及有机金属化合物合成领域中的方法。即,优选在脱水及脱氧的氮或氩环境气氛下进行,使用的溶剂及精制用的柱填充剂等优选预先实施脱水操作。并优选预先除去金属残渣及粒子等杂质。
本发明的通式(1)表示的环状硅氧烷化合物可以作为含硅膜形成材料使用,可以以这种环状硅氧烷化合物作为原料制造含硅膜。此时的成膜方法没有特殊限定,优选采用CVD进行,特优选采用PECVD。
此时的PECVD的种类及使用的装置没有特殊限定,例如该PECVD可以使用半导体制造领域、液晶显示器制造领域等该技术领域中一般使用的PECVD。
在PECVD装置中,可利用气化器使本发明的含硅膜形成材料气化,导入成膜腔内,利用高频电源施加到成膜腔内的电极上产生等离子体,在成膜腔内的硅衬底等上形成等离子体CVD薄膜。此时,为了使之产生等离子体,可以导入氩、氖等的气体、氧、一氧化二氮等氧化剂。另外,为了薄膜的多孔化,同时导入有机过氧化物或环氧化合物也落入本发明的范围。使用PECVD装置,使用本发明的含硅膜形成材料进行成膜时,可以形成作为用于半导体器件的低介电常数材料(Low-k材料)使用的适合的薄膜。
PECVD装置的等离子体产生方法没有特殊限定,可以使用该技术中使用的电感耦合型等离子体、电容耦合型等离子体、ECR等离子体、微波等离子体等。优选是电感耦合型等离子体、电容耦合型等离子体。另外,作 为等离子体发生源,可以使用平行平板型、天线型等各种等离子体发生源,作为对PECVD装置的腔内供给的非活性气体,可以使用该技术领域中使用的氦、氩、氪、氖、氙等。
作为PECVD装置的一例,图1中示出了平行平板电容耦合型PECVD装置。图1所示的平行平板电容耦合型PECVD装置1,包括PECVD装置腔内喷淋头上部电极和可控制基板温度的下部电极、将上述通式(1)气化后向腔内供给的气化器装置、高频电源以及匹配电路构成的等离子体发生装置、由真空泵构成的排气系统。
具体地,该PECVD装置1包括PECVD腔2、具有用于向腔内均匀供给上述通式(1)的化合物的喷淋头的上部电极3、具有用于设置硅基板等的薄膜形成用基板5的温度控制装置8的下部电极4、用于使通式(1)的化合物气化的气化装置9~15,作为等离子体发生源的匹配电路6和RF电源7,用于将室内的未反应物和副产物进行排气的排气装置16。17、18是接地。
作为等离子体发生源的匹配电路6和RF电源7与上部电极3相连,通过放电使之产生等离子体。RF电源7的规格没有特殊限定,可以使用该技术领域中使用的电力为1W~2000W,优选10W~1000W,频率50kHz~2.5GHz,优选100kHz~100MHz,特优选200kHz~50MHz的RF电源。
基板温度的控制没有特殊限定,通常为-90~1,000℃,优选是0~500℃的范围。
气化装置包括:充填常温常压下是液体的通式(1)的化合物13,并具有滴液配管和利用上述非活性气体进行加压的配管15的容器12、控制液体的通式(1)的化合物13流量的液体流量控制装置10,使液体的通式(1)的化合物气化的气化器9、经由气化器将上述非活性气体向PECVD装置腔内供给的配管14及控制气体流量的气体流量控制装置11。本气化装置从气化器9通过配管连接到具有喷淋头的上部电极3。
另外,作为PECVD装置的一例,图2示出了电感耦合型远程PECVD装置。图2所示的电感耦合型远程PECVD装置19包括等离子体发生装置和排气系统,所述等离子体发生装置包括,在PECVD装置腔上部的石英的周围缠绕成线圈状的等离子体发生部、可控制温度的基板设置部、将上述通式(1)表示的化合物气化并向腔内供给的气化器装置、高频电源和匹配电路的等离子体发生装置,所述排气系统包括真空泵。
具体地,该PECVD装置19包括PECVD腔20,作为等离子体发生部的线圈21和石英管22、用于设置硅基板等的薄膜形成用基板24的加热器部23、温度控制装置27、用于使通式(1)的化合物气化的气化装置28~35、作为等离子体发生源的匹配电路25、RF电源、电源26、用于排放腔内的未反应物及副产物的排气装置36。37是接地。
作为等离子体发生部的石英周围的线圈与匹配电路25相连,石英管中在RF电流形成的天线电流磁场下放电,产生等离子体。有关RF电源26的规格没有特殊限定,可以使用该技术领域中使用的电力为1W~2000W,优选10W~1000W,频率50kHz~2.5GHz,优选100kHz~100MHz,特优选200kHz~50MHz的RF电源。
基板温度的控制没有特殊限定,通常为-90~1,000℃,优选是0~500℃的范围。
气化装置包括:充填常温常压下是液体的通式(1)的化合物33,具有滴液配管和利用上述非活性气体加压的配管35的容器32、控制液体的通式(1)的化合物33流量的液体流量控制装置29、使液体的通式(1)的化合物33气化的气化器28,经由气化器向PECVD装置腔内供给上述非活性气体的配管34、控制气体流量的气体流量控制装置30、用于将非活性气体和气化的通式(1)的化合物33均匀地向腔内供给的喷淋头31。
通式(1)表示的化合物使用上述举出的PECVD装置等进行气化,根据需要与非活性气体一起向腔内供给,采用PECVD进行成膜。此时腔内的压力没有特殊限定,通常是0.1Pa~10000Pa,优选是1Pa~5000Pa。
这样地可制得含硅膜,该膜的电容率低,由于根据条件可得到具有2.0以下的电容率的膜,故可作为低介电常数膜使用。另外,优选该膜具有环状硅氧烷结构,该环状硅氧烷结构可以是残留有通式(1)表示的环状硅氧烷化合物中的环状硅氧烷结构的结构,还可以是利用等离子体新生成的结构。结果,具有环状硅氧烷结构的膜成为主要的细孔径为1nm以下的多孔性膜,又由于该孔不连续,金属不会向膜中扩散,并且具有高的机械物性和高的传热性,成为特别适合作为用于半导体器件的低介电常数材料(Low-k材料)使用的薄膜。即,更优选在不破坏通式(1)所示环状硅氧烷化合物中的环状硅氧烷结构的这种PECVD条件下进行成膜。
另外,通过对上述的含硅膜进行热处理,紫外线照射处理或电子射线 处理,可以得到多孔化或机械强度提高的薄膜。实施这些组合处理的含硅膜也落入本发明的范围。通过本处理制得的薄膜是适合作为低介电常数绝缘材料的薄膜。
本发明的含硅膜均适合作为低介电常数材料。可以将这些膜作为绝缘膜用于半导体器件。特别适用于使用多层布线的ULSI的制造。
本发明的通式(1)表示的化合物之中,尤其是通式(20)表示的化合物是新型化合物。其中R18、R19、g、h如前述,优选R18是C1~6的烷基、R19是C1~6的烷基、g是3或4,h是1或2,更优选R18是C1~4的烷基,R19是C1~4的烷基。
作为通式(20)表示的化合物的具体例,可举出2,4,6-三异丙基-2,4,6-三甲氧基环三硅氧烷、2,4,6-三异丙基-2,4,6-三乙氧基环三硅氧烷、2,4,6-三异丙基-2,4,6-三正丙氧基环三硅氧烷、2,4,6-三异丙基-2,4,6-三异丙氧基环三硅氧烷、2,4,6-三(甲氧基甲基)-2,4,6-三甲基环三硅氧烷、2,4,6,8-四(甲氧基甲基)-2,4,6,8-四甲基环四硅氧烷、2,4,6-三(乙氧基甲基)-2,4,6-三甲基环三硅氧烷、2,4,6,8-四(乙氧基甲基)-2,4,6,8-四甲基环四硅氧烷、2,4,6-三(异丙氧基甲基)-2,4,6-三甲基环三硅氧烷、2,4,6,8-四(异丙氧基甲基)-2,4,6,8-四甲基环四硅氧烷等。
还可举出2,4,6-三(甲氧基乙基)-2,4,6-三甲基环三硅氧烷、2,4,6,8-四(甲氧基乙基)-2,4,6,8-四甲基环四硅氧烷、2,4,6-三(乙氧基乙基)-2,4,6-三甲基环三硅氧烷、2,4,6,8-四(乙氧基乙基)-2,4,6,8-四甲基环四硅氧烷、2,4,6-三(异丙氧基乙基)-2,4,6-三甲基环三硅氧烷、或2,4,6,8-四(异丙氧基乙基)-2,4,6,8-四甲基环四硅氧烷等。
以下举出实施例,但本发明不受这些的实施例任何限定。再者膜厚测定使用堀场制作所公司制造的干涉式膜厚测定装置。另外,电容率(k值)的测定使用Four Dimension Inc.公司制汞探针(mercury prober)进行测定,刚性及杨氏模量使用Hysitron Inc.公司制造的纳米压头(nanoindentater)进行测定。
实施例1
[通式(10)表示的有机硅烷化合物的制造]
在氮气流下向具有滴液漏斗、搅拌装置的1L的四口烧瓶中加入 26.7g(2.20mol)金属镁和0.53L干燥四氢呋喃,冷却到0℃。然后边搅拌边用5小时滴加187g(1.00mol)的4-溴苯甲醚,在室温下反应3小时,制得4-甲氧基苯基溴化镁的四氢呋喃溶液。在氮气流下向具有滴液漏斗,搅拌装置的2L的四口烧瓶中加入130g(0.952mol)甲基三甲氧基硅烷和52.0mol干燥四氢呋喃,冷却到0℃。然后边搅拌边用1小时滴加1.00mol上述制备的4-甲氧基苯基溴化镁的四氢呋喃溶液,在室温下反应4小时。反应结束后,过滤除去副产的甲醇镁残渣,通过对得到的滤液进行减压蒸馏得到106g(0.501mol)作为目的物的甲基(4-甲氧基苯基)二甲氧基硅烷。收率是52.6%。
使用1H-NMR、13C-NMR、GC-MS对分离的甲基(4-甲氧基苯基)二甲氧基硅烷进行分析的结果如以下所述。
1H-NMR;δ0.33ppm(s,3H,CH 3-Si)、δ3.55ppm(s,6H,2CH 3-O-Si)、δ3.81ppm(s,3H,CH 3-O-Ph)、δ6.93~6.94ppm(m,2H,Ph-H)、δ7.55~7.56ppm(m,2H,Ph-H)、
13C-NMR;δ4.8ppm(CH3-Si)、50.7ppm(CH3-O-Si)、55.2ppm(CH3-O-Ph)、δ113.9ppm(Ph)、δ125.0ppm(Ph)、δ135.8ppm(Ph)、δ161.5ppm(Ph)
GC-MS;Mw=212、C10H16O3Si。
[通式(1)表示的环状硅氧烷化合物的制造]
向100ml的Schlenk管中加入21.2g(100mmol)甲基(4-甲氧基苯基)二甲氧基硅烷、1.80g(100mmol)纯水、9.81g(100mmol)硫酸、20ml四氢呋喃,在室温、搅拌条件下反应1小时。反应结束后,馏去THF和水。使用分子筛干燥得到的有机层,减压蒸馏后,得到作为目的物的2,4,6-三(4-甲氧基苯基)-2,4,6-三甲基环三硅氧烷。收率是11.3%,甲基(4-甲氧基苯基)二甲氧基硅烷的转化率是33.8%。
使用GC-MS对分离出的2,4,6-三(4-甲氧基苯基)-2,4,6-三甲基环三硅氧烷进行分析的结果如下述。
GC-MS;Mw=498、C24H30O6Si3。
实施例2
[通式(1)表示的环状硅氧烷化合物的制造]
向具有搅拌装置和滴液漏斗的50ml的Schlenk管中加入0.0141g(0.0800mmol)氯化钯、20.5g(640mmol)甲醇,进行搅拌。在室温下用 30分钟由滴液漏斗滴加4.81g(20.0mmol)的2,4,6,8-四甲基环四硅氧烷。滴加结束后,再在室温下搅拌15小时。反应结束后馏去甲醇,使用玻璃过滤器过滤出Pd残渣,得到作为目的物的2,4,6,8-四甲基-2,4,6,8-四甲氧基环四硅氧烷。采用气相色谱测得的收率是1.5%。
使用GC-MS对分离出的2,4,6,8-四甲基-2,4,6,8-四甲氧基环四硅氧烷进行分析的结果如下述。
GC-MS;Mw=360、C8H24O8Si4。
实施例3
[通式(1)表示的环状硅氧烷化合物的制造]
向具有搅拌装置和滴液漏斗的200ml的Schlenk管中加入13.62g(0.100mol)甲基三甲氧基硅烷和100ml甲苯,搅拌,调整为80℃。在80℃下用10分钟由滴液漏斗滴加1.35g纯水。滴加结束后,再在回流条件下搅拌2小时。反应结束后馏去甲苯、减压蒸馏得到作为目的物的2,4,6,8-四甲基-2,4,6,8-四甲氧基环四硅氧烷。收率是4.6%。甲基三甲氧基硅烷的转化率是13.8%。
使用GC-MS对分离出的2,4,6,8-四甲基-2,4,6,8-四甲氧基环四硅氧烷进行分析的结果如下述。
GC-MS;Mw=360、C8H24O8Si4。
实施例4
[通式(1)表示的环状硅氧烷化合物的制造]
向具有搅拌装置和滴液漏斗的200ml的Schlenk管中加入96.2g(1.60mol)异丙醇和0.740g(0.80mmol)的三(三苯基膦)氯化铑(I),搅拌,在室温下用20分钟由滴液漏斗滴加48.1g(0.20mol)的2,4,6,8-四甲基环四硅氧烷。滴加结束后,在异丙醇回流条件下搅拌4小时。反应结束后,馏去异丙醇、减压蒸馏,得到作为目的物的2,4,6,8-四甲基-2,4,6,8-四异丙氧基环四硅氧烷。收率是54.9%。
使用GC-MS对分离出的2,4,6,8-四甲基-2,4,6,8-四异丙氧基环四硅氧烷进行分析的结果如下述。
GC-MS;Mw=472、C16H40O8Si4。
实施例5
[通式(1)表示的环状硅氧烷化合物的制造]
向具有搅拌装置和滴液漏斗的200ml的Schlenk管中加入20.0g(0.217mol)的甲苯、0.01N的硫酸水溶液2.4g,进行搅拌。在室温下用5分钟由滴液漏斗滴加20.0g(0.133mol)甲基(甲氧基甲基)二甲氧基硅烷。滴加结束后在室温下搅拌7小时。反应结束后馏去甲苯、减压蒸馏,得到作为目的物的2,4,6,8-四(甲氧基甲基)-2,4,6,8-四甲基环四硅氧烷。收率是15.3%。甲基(甲氧基甲基)二甲氧基硅烷的转化率是61.2%。
使用1H-NMR、13C-NMR、GC-MS对分离出的2,4,6,8-四(甲氧基甲基)-2,4,6,8-四甲基环四硅氧烷进行分析的结果如下述。
1H-NMR;δ0.17~0.19ppm(m,12H,4CH 3-Si)、
δ3.04~3.07ppm(m,8H,4CH3-O-CH 2Si)、
δ3.34~3.36ppm(m,12H,4CH 3-O-CH2Si)
13C-NMR;δ-2.2ppm(CH3-Si)、
δ62.9ppm(CH3-O-CH2Si)、
δ65.8ppm(CH3-O-CH2Si)。
GC-MS;Mw=416、C12H32O8Si4。
实施例6
[使用式(1)所示的环状硅氧烷化合物的PECVD成膜]
使用图1表示的电容耦合型PECVD装置将实施例1合成的2,4,6-三(4-甲氧基苯基)-2,4,6-三甲基环三硅氧烷在硅基板上进行成膜。成膜条件,按10sccm供给作为非活性气体的氩气,连续供给气化的2,4,6-三(4-甲氧基苯基)-2,4,6-三甲基环三硅氧烷使腔内压力为10Pa,在基板温度150℃、RF电源电力为30W、RF电源频率为13.56MHz的条件下进行成膜。结果成膜速度是4.3nm/分、电容率(k值)是2.7。有关机械特性,刚性是1.3GPa,杨氏模量是13.9GPa。
实施例7
[使用式(1)所示环状硅氧烷化合物的PECVD成膜]
除了将2,4,6-三(4-甲氧基苯基)-2,4,6-三甲基环三硅氧烷改成实施例3合成的2,4,6,8-四甲基-2,4,6,8-四甲氧基环四硅氧烷以外,与实施例6同样地制得PECVD薄膜。结果,成膜速度是12.8nm/分,电容率(k值)是2.6。有关机械特性,刚性是1.36GPa,杨氏模量是15.2GPa。
实施例8
[使用通式(1)所示的环状硅氧烷化合物的PECVD成膜]
除了使2,4,6-三(4-甲氧基苯基)-2,4,6-三甲基环三硅氧烷改成实施例4合成的2,4,6,8-四甲基-2,4,6,8-四异丙氧基环四硅氧烷以外,与实施例6同样地制得PECVD薄膜。结果,成膜速度是11.2nm/分,电容率(k值)是2.4。有关机械特性,刚性是1.1GPa,杨氏模量是17.1GPa。
实施例9
[使用通式(1)所示环状硅氧烷化合物的PECVD成膜]
除了使2,4,6-三(4-甲氧基苯基)-2,4,6-三甲基环三硅氧烷改成实施例5合成的2,4,6,8-四(甲氧基甲基)-2,4,6,8-四甲基环四硅氧烷以外,与实施例6同样地制得PECVD薄膜。结果,成膜速度是6.8nm/分,电容率(k值)是1.8。有关机械特性,刚性是1.6GPa,杨氏模量是22.1GPa。
比较例1
除了使2,4,6-三(4-甲氧基苯基)-2,4,6-三甲基环三硅氧烷改成2,4,6,8-四甲基环四硅氧烷以外,与实施例6同样地制得PECVD薄膜。结果,成膜速度是10.4nm/分,电容率(k值)是2.9。有关机械特性,刚性是1.1GPa,杨氏模量是10.7GPa。
参照特定的实施方式详细地说明了本发明,但是对于本领域技术人员来说,不脱离本发明的精神和范围而加以各种变更和修改是显而易见的。
本申请是基于2005年1月31日申请的日本专利申请(特愿2005-023256)及2005年12月2日申请的日本专利申请(特愿2005-349432)的申请,这里引入其内容作为参考。
工业实用性
根据本发明可提供新型的含硅膜形成材料,尤其是适用于PECVD装置的含环状硅氧烷化合物的低介电常数绝缘膜用材料,还可提供使用该材料的含硅膜及含这些膜的半导体器件。
Claims (13)
1.一种含硅膜形成材料,其含有下述通式(20)表示的环状硅氧烷化合物,
[化1]
式中,R18表示碳原子数1~4的烷基,R19表示氢原子或碳原子数1~20的饱和或不饱和烃基,g表示2~10的整数,h表示1或2。
2.权利要求1所述的含硅膜形成材料,其中,通式(20)表示的环状硅氧烷化合物中的g是3~4。
3.权利要求1或2所述的含硅膜形成材料,其中,通式(20)表示的环状硅氧烷化合物的分子量小于1000。
4.权利要求1或2所述的含硅膜形成材料,其中,硅、碳、氧、氢、氮、硼以外的杂质量小于10ppb,并且含水量小于50ppm。
5.一种含硅膜的制造方法,其中,使用权利要求1~4中任何一项所述的含硅膜形成材料作为原料。
6.权利要求5所述的制造方法,其中,通过化学气相沉积法进行成膜。
7.权利要求6所述的制造方法,其中,化学气相沉积法是等离子体增强化学气相沉积法。
8.一种含硅膜,其通过权利要求5~7中任何一项所述的制造方法制得。
9.权利要求8所述的含硅膜,其含有通式(20)表示的环状硅氧烷化合物中的环状硅氧烷结构。
10.一种含硅膜的制造方法,该方法包括,对权利要求8或9所述的含硅膜进行热处理、紫外线照射处理或电子射线处理。
11.一种含硅膜,其通过权利要求10所述的制造方法制得。
12.一种半导体器件,其使用权利要求8、9或11所述的膜作为绝缘膜。
13.权利要求1所述的含硅膜形成材料,其中,通式(20)表示的化合物是2,4,6-三(甲氧基甲基)-2,4,6-三甲基环三硅氧烷、2,4,6,8-四(甲氧基甲基)-2,4,6,8-四甲基环四硅氧烷、2,4,6-三(乙氧基甲基)-2,4,6-三甲基环三硅氧烷、2,4,6,8-四(乙氧基甲基)-2,4,6,8-四甲基环四硅氧烷、2,4,6-三(异丙氧基甲基)-2,4,6-三甲基环三硅氧烷、2,4,6,8-四(异丙氧基甲基)-2,4,6,8-四甲基环四硅氧烷、2,4,6-三(甲氧基乙基)-2,4,6-三甲基环三硅氧烷、2,4,6,8-四(甲氧基乙基)-2,4,6,8-四甲基环四硅氧烷、2,4,6-三(乙氧基乙基)-2,4,6-三甲基环三硅氧烷、2,4,6,8-四(乙氧基乙基)-2,4,6,8-四甲基环四硅氧烷、2,4,6-三(异丙氧基乙基)-2,4,6-三甲基环三硅氧烷、或2,4,6,8-四(异丙氧基乙基)-2,4,6,8-四甲基环四硅氧烷。
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JP5410758B2 (ja) * | 2006-11-01 | 2014-02-05 | 昭和電工株式会社 | 環状シロキサン化合物、有機エレクトロルミネッセンス素子およびその用途 |
JP2010519773A (ja) * | 2007-02-27 | 2010-06-03 | シクストロン アドヴァンスド マテリアルズ、インコーポレイテッド | 基板上に膜を形成するための方法 |
CN104392957A (zh) * | 2014-10-30 | 2015-03-04 | 苏州大学 | 低介电常数薄膜层的制备方法 |
US10669294B2 (en) | 2018-04-17 | 2020-06-02 | Gelest Technologies, Inc. | Alkyl ether substituted cyclotrisiloxanes and preparation method thereof |
KR102409869B1 (ko) * | 2018-08-10 | 2022-06-16 | 버슘머트리얼즈 유에스, 엘엘씨 | 규소 화합물 및 이를 사용하여 막을 증착시키는 방법 |
JP2023535068A (ja) * | 2020-07-24 | 2023-08-15 | バーサム マテリアルズ ユーエス,リミティド ライアビリティ カンパニー | 環状シロキサン、及びこれを用いて製造された膜 |
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