CN102762763A - SiCOH低K膜的气相沉积法 - Google Patents
SiCOH低K膜的气相沉积法 Download PDFInfo
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- CN102762763A CN102762763A CN2011800100663A CN201180010066A CN102762763A CN 102762763 A CN102762763 A CN 102762763A CN 2011800100663 A CN2011800100663 A CN 2011800100663A CN 201180010066 A CN201180010066 A CN 201180010066A CN 102762763 A CN102762763 A CN 102762763A
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- 238000000034 method Methods 0.000 title claims description 29
- 238000007740 vapor deposition Methods 0.000 title 1
- 239000003795 chemical substances by application Substances 0.000 claims description 35
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 33
- 229920002554 vinyl polymer Polymers 0.000 claims description 33
- 238000000151 deposition Methods 0.000 claims description 25
- 239000011159 matrix material Substances 0.000 claims description 23
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 17
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 13
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 125000003545 alkoxy group Chemical group 0.000 claims description 11
- -1 vinyl-dimethyl TMOS Chemical compound 0.000 claims description 11
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 claims description 8
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 6
- MBGQQKKTDDNCSG-UHFFFAOYSA-N ethenyl-diethoxy-methylsilane Chemical compound CCO[Si](C)(C=C)OCC MBGQQKKTDDNCSG-UHFFFAOYSA-N 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 238000005229 chemical vapour deposition Methods 0.000 claims description 5
- XMKVMJPCDLDMTQ-UHFFFAOYSA-N ethenyl(diethoxy)silane Chemical compound CCO[SiH](C=C)OCC XMKVMJPCDLDMTQ-UHFFFAOYSA-N 0.000 claims description 3
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 3
- ZLNAFSPCNATQPQ-UHFFFAOYSA-N ethenyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C=C ZLNAFSPCNATQPQ-UHFFFAOYSA-N 0.000 claims description 3
- JAGYXYUAYDLKNO-UHFFFAOYSA-N hepta-2,5-diene Chemical compound CC=CCC=CC JAGYXYUAYDLKNO-UHFFFAOYSA-N 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 claims description 3
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- 229910001882 dioxygen Inorganic materials 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
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- 239000007818 Grignard reagent Chemical group 0.000 description 3
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- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- NBBQQQJUOYRZCA-UHFFFAOYSA-N diethoxymethylsilane Chemical compound CCOC([SiH3])OCC NBBQQQJUOYRZCA-UHFFFAOYSA-N 0.000 description 3
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- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical group CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
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- NQCATFRVLGDUOK-INWUZDNDSA-N CC1N2[C@]1(C)C2 Chemical compound CC1N2[C@]1(C)C2 NQCATFRVLGDUOK-INWUZDNDSA-N 0.000 description 1
- UCDDBGNUBRVKGO-ZHACJKMWSA-N CCC/N=C(\C1C)/C1C1CC1 Chemical compound CCC/N=C(\C1C)/C1C1CC1 UCDDBGNUBRVKGO-ZHACJKMWSA-N 0.000 description 1
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- 229910019001 CoSi Inorganic materials 0.000 description 1
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- 238000003747 Grignard reaction Methods 0.000 description 1
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- 229910000577 Silicon-germanium Inorganic materials 0.000 description 1
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- 229910004200 TaSiN Inorganic materials 0.000 description 1
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- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
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- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
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- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 1
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- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- XZWYZXLIPXDOLR-UHFFFAOYSA-N metformin Chemical compound CN(C)C(=N)NC(N)=N XZWYZXLIPXDOLR-UHFFFAOYSA-N 0.000 description 1
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- 150000004767 nitrides Chemical class 0.000 description 1
- SJYNFBVQFBRSIB-UHFFFAOYSA-N norbornadiene Chemical compound C1=CC2C=CC1C2 SJYNFBVQFBRSIB-UHFFFAOYSA-N 0.000 description 1
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- 238000002360 preparation method Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
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- 238000010992 reflux Methods 0.000 description 1
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- 238000007789 sealing Methods 0.000 description 1
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- 239000012686 silicon precursor Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
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- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
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- 238000001039 wet etching Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
- H01L21/02123—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon
- H01L21/02126—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material containing Si, O, and at least one of H, N, C, F, or other non-metal elements, e.g. SiOC, SiOC:H or SiONC
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/06—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 metallic material
- C23C16/18—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 metallic material from metallo-organic compounds
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/40—Oxides
- C23C16/401—Oxides containing silicon
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/50—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
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/56—After-treatment
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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Abstract
公开了适于沉积具有适于后代介电膜的介电常数和杨氏模量的SiCOH膜的前驱体。
Description
相关申请案的交叉引用
本申请主张2010年2月17日提交的美国临时申请第61/305,491号的权益，其全部内容以引用的方式并入本文中。
技术领域
本发明公开了适于沉积具有适于后代介电膜的介电常数和杨氏模量的SiCOH膜的前驱体，其用于制造半导体、光伏、LCD-TFT或平板型器件基质。
背景技术
JSR公司的EP2264219公开了一种具有下式的有机硅烷化学气相沉积化合物：
其中R1及R2独立地表示氢原子、具有1至4个碳原子的烷基、乙烯基或苯基，R3和R4独立地表示具有1至4个碳原子的烷基、乙酰基或苯基，m为0至2的整数，且n为1至3的整数。
JSR公司公开了170种以上满足该式的特定化合物，且那些化合物可能并非穷尽该式的可用迭代。JSR公司在0033段、0045段及0052段公开了：根据易于合成、纯化及处理的观点，具有所公开式的化合物在R1及R2中包含0至1个H原子；根据降低化合物沸点且增加机械强度的观点，该化合物在R1及R2中包含1至2个H原子。
JSR公司进一步公开了170种以上特定化合物与致孔剂（porogen）和具有式R6 aSi(OR7)4-a、R8 b(R9O)3-bSi-Oe-Si(OR10)3-cR11 c及-[R13 f(R14O)2-fSi-(R15)g]-的另一硅烷化合物的组合，其中R6、R8至R11、R13及R14独立地表示H原子、F原子或单价有机基团，R7独立地表示单价有机基团，R15表示O原子、亚苯基或由-(CH2)n-所示的基团，a为0至4的整数，b及c独立地为0至3的整数，e为0或1，f为0至2，g为0或1，h为2至3的整数，且n为1至6的整数（0062段）。成孔剂可为具有环结构的任何化合物（0094段）。声称数值上有希望的组合产生展现“更优良”的机械强度及低相对介电常数的绝缘膜（0067段）。
使用前驱体的组合进行沉积可提供介电常数及杨氏模量为单独由前驱体产生的膜的介电常数及杨氏模量的近似平均值的膜。该现象部分说明于本申请的对比例1中，其总结了EP2264219的实施例2及14-18。该现象进一步说明于对比例2、4和5中。
另外，对于特定前驱体或前驱体的组合而言，杨氏模量结果的任何改进通常伴随着介电常数的提高。该现象说明于本申请的对比例1中，其总结了EP2264219的实施例14至17。该现象进一步说明于对比例6中。
仍需要具有低介电常数和高机械强度的绝缘膜。
发明内容
本发明公开了在一个或多个安置于反应室内的基质上形成SiCOH膜层的方法。将含Si-(CH2)n-Si的前驱体（其中n=1或2）引入反应室中。该含Si-(CH2)n-Si的前驱体选自由以下组成的组：
和
其中R1至R4各自独立地选自由H、甲基、乙基、丙基、乙烯基和C1-C3烷氧基组成的组；R5选自由甲基、乙基和丙基组成的组；优选R1至R4中至少一个为甲基、乙基或丙基；且R1至R3中至少一个为烷氧基，其可与-OR5相同或不同。将含乙烯基的前驱体引入反应室中。该含乙烯基的前驱体具有式Si(R1)x(O(R2))4-x，其中至少一个R1为乙烯基，任选的第二R1为氢或烷基，优选为甲基或乙基；各R2独立地选自烷基，优选甲基或乙基；且x为1或2。将致孔剂引入反应室中。使Si-(CH2)n-Si前驱体、含乙烯基的前驱体、致孔剂及基质接触以使用沉积方法、优选化学气相沉积在基质的至少一个表面上形成SiCOH膜。该方法可进一步包括一个或多个以下方面：
.含乙烯基的前驱体选自由乙烯基二乙氧基硅烷、乙烯基二甲氧基硅烷、乙烯基三甲氧基硅烷、乙烯基三乙氧基硅烷、乙烯基甲基二甲氧基硅烷及乙烯基甲基二乙氧基硅烷组成的组；
.含乙烯基的前驱体选自由乙烯基三乙氧基硅烷或乙烯基甲基二乙氧基硅烷组成的组；
.致孔剂为经取代或未经取代的双环[2.2.1]庚-2,5-二烯；
.沉积方法为单频PECVD；
.使SiCOH膜变得多孔；
.R1至R4不为H；
.含Si-(CH2)n-Si的前驱体选自由(EtO)3Si-CH2-Si(OEt)2H、Me(OEt)2Si-CH2-Si(OEt)2H、Me(OEt)2Si-CH2-Si(OEt)HMe、Me2(OEt)Si-CH2-Si(OEt)2H、(EtO)Me2SiCH2Si(OMe)2H、Me2(OEt)Si-CH2-Si(OEt)HMe、(OEt)3Si-CH2-Si(OEt)HMe、(EtO)3Si-CH2-Si(OMe)HMe、Me(OMe)2Si-CH2-Si(OMe)2H、Me(OMe)2Si-CH2-Si(OMe)HMe、Me2(OMe)SiCH2Si(OMe)2H和Me2(OEt)Si-CH2-Si(OMe)HMe组成的组；
.含Si-(CH2)n-Si的前驱体选自由Me(OEt)2Si-CH2-Si(OEt)2H、Me2(OEt)Si-CH2-Si(OEt)2H和Me(OEt)2Si-CH2-Si(OEt)HMe组成的组；
.含Si-(CH2)n-Si的前驱体选自由(EtO)3Si-CH2CH2-Si(OEt)2H、Me(OEt)2Si-CH2CH2-Si(OEt)2H、Me(OEt)2Si-CH2CH2-Si(OEt)HMe、Me2(OEt)Si-CH2CH2-Si(OEt)2H、(EtO)Me2SiCH2CH2Si(OMe)2H、Me2(OEt)Si-CH2CH2-Si(OEt)HMe、(OEt)3Si-CH2CH2-Si(OEt)HMe、(EtO)3Si-CH2CH2-Si(OMe)HMe、Me(OMe)2Si-CH2CH2-Si(OMe)2H、Me(OMe)2Si-CH2CH2-Si(OMe)HMe、Me2(OMe)SiCH2CH2Si(OMe)2H和Me2(OEt)Si-CH2CH2-Si(OMe)Hme组成的组；
.含Si-(CH2)n-Si的前驱体选自由Me(OEt)2Si-CH2CH2-Si(OEt)2H、Me2(OEt)Si-CH2CH2-Si(OEt)2H和Me(OEt)2Si-CH2CH2-Si(OEt)HMe组成的组；
.R1至R3中仅一个为H；
.含Si-(CH2)n-Si的前驱体选自由MeH(OMe)Si-CH2-Si(OMe)HMe、(EtO)2HSi-CH2-Si(OEt)2H、(EtO)HMeSi-CH2-Si(OEt)HMe和(iPrO)HMeSi-CH2-Si(OiPr)HMe组成的组；及
.SiCOH膜具有低于以下两者的介电常数：（1）由含Si-(CH2)n-Si的前驱体和致孔剂形成的SiCOH膜的介电常数；及（2）由含乙烯基的前驱体和致孔剂形成的SiCOH膜的介电常数。
还公开了通过所公开方法形成的膜。优选通过所公开方法形成的膜具有在约2.0至约2.7、优选约2.0至约2.5的介电常数，及在约4GPa至约10GPa、优选约5GPa至约10GPa的杨氏模量。
符号及命名
某些缩写、符号及术语在整个以下说明书和权利要求书中使用且包括：缩写“SiCOH”指含有Si、C、O和H原子的介电膜；缩写“pSiCOH”指已使SiCOH膜变得多孔后的SiCOH膜；缩写“BCHD”指双环[2.2.1]庚-2,5-二烯，也称作2,5-降冰片二烯；缩写“PECVD”指等离子体增强化学气相沉积；缩写“CVD”指化学气相沉积；缩写“MIM”指金属绝缘体金属（电容器中所用的结构）；缩写“DRAM”指动态随机存取内存；缩写“FeRAM”指铁电随机存取内存；缩写“CMOS”指互补金属氧化物半导体；缩写“UV”指紫外线；且缩写“RF”指射频。
此外，本发明预期使用三种前驱体（Si-(CH2)n-Si前驱体、含乙烯基的前驱体和致孔剂）各自中的一种或多种且互换地以单数或复数形式指代各者，而不意欲借此限制范围。
术语“烷基”指仅含有碳和氢原子的饱和官能基团。此外，术语“烷基”指直链、支化或环烷基。直链烷基的实例包括（不限于）甲基、乙基、丙基、丁基等。支化烷基的实例包括（不限于）叔丁基。环烷基的实例包括（不限于）环丙基、环丁基、环戊基、环己基等。
如本文中所用的缩写“Me”指甲基；缩写“Et”指乙基；缩写“Pr”指丙基；缩写“nPr”指链丙基(chain propyl group)；缩写“iPr”指异丙基；缩写“Bu”指丁基（正丁基）；缩写“tBu”指叔丁基；缩写“sBu”指仲丁基；缩写“iBu”指异丁基；且缩写“TMS”指三甲代甲硅烷基。
本文中使用来自元素周期表的元素的标准缩写。应了解，元素可由这些缩写表示（例如Si指硅，C指碳等）。
实施方式
本申请人已惊讶地发现使用特定含Si-(CH2)n-Si的前驱体（其中n为1或2）、特定乙烯基烷氧基硅烷或乙烯基烷基烷氧基硅烷前驱体和特定致孔剂的组合进行CVD沉积导致SiCOH膜与由单独任一前驱体/致孔剂组合沉积的SiCOH膜的介电常数和杨氏模量相比具有相同或改进的介电常数和改进的杨氏模量。本申请人认为含Si-(CH2)n-Si的前驱体中的Si-H键与乙烯基烷氧基硅烷或乙烯基烷基烷氧基硅烷上的乙烯基反应产生具有较低介电常数和改进机械强度的膜。
使用一种或多种下文更详细描述的含Si-(CH2)n-Si的前驱体、一种或多种第二含硅前驱体和一种或多种致孔剂，通过气相沉积、优选CVD、更优选PECVD沉积SiCOH膜。该膜优选使用紫外光或另一能量源移除致孔剂而固化，以产生具有较低介电常数的pSiCOH膜。
本申请人认为所公开的含Si-(CH2)n-Si的前驱体适于沉积含有Si-(CH2)n-Si结构的膜。一般而言，含Si-(CH2)n-Si的前驱体可由下式描述：
或
（式2）
其中R1至R4各自独立地选自由H、甲基、乙基、丙基、乙烯基及C1-C3烷氧基组成的组；R5选自由甲基、乙基及丙基组成的组；优选R1至R4中至少一个为甲基、乙基或丙基；且R1至R3中至少一个为烷氧基，其可与-OR5相同或不同。优选地，R1和R2为Me，R3和R4为OEt，且R5为Et。
烷氧基配体（即甲氧基、乙氧基或丙氧基）导致SiCOH膜中产生交联Si-O-Si结构。因此，至少一个烷氧基配体应存在于各Si原子处以使得充分交联。Si-OEt基团为优选的，因为其比Si-OMe基团稍不具反应性，且因此更不易导致前驱体在储存期间本体聚合或在环境暴露于前驱体时的不良健康影响。
Si-Me基团将开放体积或超微孔引入结构中且降低介电常数。它们还增加最终膜的碳含量，这有助于增加对等离子体损坏及湿法蚀刻的抗性。还认为高碳含量会增加对“图像上下跳动”的抗性。“图像上下跳动”为高纵横比的紧密间隔特征叠并于彼此之上。因此理想的是分子内有至少一个甲基。然而，甲基也导致交联降低且因此对机械性能有害。可根据低介电常数与所需机械性能之间的平衡来选择甲基数目。
Si-(CH2)n-Si子结构允许并入碳以提供对等离子体损害及翻转的良好抗性，同时维持交联以保持机械性能。
前驱体中的Si-H已显示有利于并入一些致孔剂。然而，膜中的残余Si-H趋向于与大气氧和/或水分反应以形成Si-OH，其转而导致水分吸收入膜中且k增加。因此，具有适当数目Si-H键是重要的。本发明人认为每个前驱体分子一个Si-H键可能是最佳的。
在第一实施方案中，R1至R4不为H，前驱体仅具有一个Si-H键。实施例1及对比例4和6证明，仅具有一个Si-H键的含Si-(CH2)n-Si的前驱体与含乙烯基的前驱体和BCHD的组合（实施例1）产生的膜与由各单独前驱体/BCHD组合（对比例4和6）产生的膜相比具有改进的介电常数结果及变化最小的杨氏模量结果。相反，对比例2、3和5证明，不含Si-H键的Si-(CH2)n-Si前驱体由于添加含乙烯基的前驱体而不产生具有改进的介电常数或杨氏模量的膜。本申请人认为来自含乙烯基的前驱体的乙烯基与含Si-(CH2)n-Si的前驱体的Si-H基团反应，导致碳并入膜中。
第一实施方案的例示性分子包括(EtO)3Si-CH2-Si(OEt)2H、Me(OEt)2Si-CH2-Si(OEt)2H、Me(OEt)2Si-CH2-Si(OEt)HMe、Me2(OEt)Si-CH2-Si(OEt)2H、(EtO)Me2SiCH2Si(OMe)2H、Me2(OEt)Si-CH2-Si(OEt)HMe、(OEt)3Si-CH2-Si(OEt)HMe、(EtO)3Si-CH2-Si(OMe)HMe、Me(OMe)2Si-CH2-Si(OMe)2H、Me(OMe)2Si-CH2-Si(OMe)HMe、Me2(OMe)SiCH2Si(OMe)2H和/或Me2(OEt)Si-CH2-Si(OMe)HMe，优选Me(OEt)2Si-CH2-Si(OEt)2H、Me2(OEt)Si-CH2-Si(OEt)2H和/或Me(OEt)2Si-CH2-Si(OEt)HMe。
或者，第一实施方案的含Si-(CH2)n-Si的前驱体包括(EtO)3Si-CH2CH2-Si(OEt)2H、Me(OEt)2Si-CH2CH2-Si(OEt)2H、Me(OEt)2Si-CH2CH2-Si(OEt)HMe、Me2(OEt)Si-CH2CH2-Si(OEt)2H、(EtO)Me2SiCH2CH2Si(OMe)2H、Me2(OEt)Si-CH2CH2-Si(OEt)HMe、(OEt)3Si-CH2CH2-Si(OEt)HMe、(EtO)3Si-CH2CH2-Si(OMe)HMe、Me(OMe)2Si-CH2CH2-Si(OMe)2H、Me(OMe)2Si-CH2CH2-Si(OMe)HMe、Me2(OMe)SiCH2CH2Si(OMe)2H和/或Me2(OEt)Si-CH2CH2-Si(OMe)HMe，优选Me(OEt)2Si-CH2CH2-Si(OEt)2H、Me2(OEt)Si-CH2CH2-Si(OEt)2H和/或Me(OEt)2Si-CH2CH2-Si(OEt)HMe。
在第二实施方案中，R1、R2或R3为H，前驱体在各个Si上键合有一个H。理论上，本申请人认为在第二实施方案中将发生与第一实施方案中所述相同的乙烯基/Si-H反应机制。然而，一个特定分子的极小数目的初步测试结果不提供预期协同作用。
第二实施方案的例示性分子包括MeH(OMe)Si-CH2-Si(OMe)HMe、(EtO)2HSi-CH2-Si(OEt)2H、(EtO)HMeSi-CH2-Si(OEt)HMe和(iPrO)HMeSi-CH2-Si(OiPr)HMe。
可使用常规方法根据以下流程实现这些Si-CH2-Si前驱体的合成：
(式3) (式4) (式1)
其中R'为乙基或甲基且格氏试剂R1R2R3SiCH2MgCl以中间物形式形成。可通过在干的回流溶剂如四氢呋喃（THF）中逐滴添加起始氯化合物（式3）至镁屑(magnesium turning)中来形成格氏试剂。随后逐滴添加甲氧基或乙氧基化合物（式4）至格氏反应溶液中以形成所需产物（式1）。可通过过滤移除反应的镁盐副产物，接着蒸发溶剂以从溶液中分离所需产物（式1）。关于经由格氏试剂形成Si-CH2-Si键的程序的其他详情可见于美国专利第5,296,624号（Larson等人）及美国专利申请公开案第2009/0299086号（Nobe等人）中。应在惰性氛围下（例如在流动的干燥氮气下）进行本文所述的所有反应。
根据上述程序，优选化合物的起始材料如下：
(EtO)MeHSiCH2SiHMe(OEt)MeH(OEt)2SiCH2Cl+Si(OEt)2MeH
(EtO)3Si-CH2-Si(OEt)2H(EtO)3SiCH2Cl+Si(OEt)3H
Me(OEt)2Si-CH2-Si(OEt)2H Me(OEt)2SiCH2Cl+Si(OEt)3H
Me(OEt)2Si-CH2-Si(OEt)HMe Me(OEt)2SiCH2Cl+Si(OEt)2MeH
Me2(OEt)Si-CH2-Si(OEt)2H Me2(OEt)SiCH2Cl+Si(OEt)3H
Me2(OEt)Si-CH2-Si(OEt)HMe Me(OEt)2SiCH2Cl+Si(OEt)2MeH
(OEt)3Si-CH2-Si(OEt)HMe(OEt)3SiCH2Cl+Si(OEt)2MeH
这些起始材料可市购。
另一合成方法（最适用于对称分子）根据以下流程：
其中RO为烷氧基。举例而言，对于R1=R6=H，且R=Et，流程A可用于制备(EtO)2HSiCH2SiH(OEt)2。这些起始材料可市购。应在溶剂如THF中进行反应，其中试剂在搅拌下缓慢添加。替代RONa，醇ROH可与碱如三烷基胺或吡啶一起使用。
可根据流程B制备化合物(EtO)MeHSiCH2SiHMe(OEt)，其中R=Et，R1=R6=H，R2=R5=Me，且其中起始材料根据Hemida等人,J.Mat.Sci323485(1997)所述的程序制备。
可使用以下例示性方法实现Si-CH2-CH2-Si前驱体的合成：
(式5) (式6) (式2)
其中R可以为烷基或烷氧基。产物可通过在室温下在干溶剂如甲苯中连续逐滴搅拌添加起始材料(式5和6)而形成。将氯铂酸加入该混合物中。使反应混合物回流。将混合物冷却至室温以后，将吡啶引入该混合物中。然后逐滴加入理想的醇。在加入以后，使混合物在室温下反应。反应的盐副产物可通过过滤、之后分馏而除去以分离所需产物(式2)。形成Si-CH2-CH2-Si键的程序的其他细节可在EP2264219的Gelest目录的第484页找到。
如上所述的Si-(CH2)n-Si前驱体可彼此组合及与一种或多种适于沉积低k SiCOH膜的含乙烯基的前驱体组合。文献中已知许多含乙烯基的前驱体。这种前驱体的一重要种类由式Si(R1)x(O(R2))4-x描述，其中第一R1为乙烯基且任选的第二R1为氢或烷基，优选甲基或乙基；各R2独立地为烷基；且x为1或2。优选地，含乙烯基的前驱体为乙烯基二乙氧基硅烷、乙烯基二甲氧基硅烷、乙烯基三甲氧基硅烷、乙烯基三乙氧基硅烷、乙烯基甲基二甲氧基硅烷及乙烯基甲基二乙氧基硅烷，更优选乙烯基三乙氧基硅烷或乙烯基甲基二乙氧基硅烷。
合适的致孔剂包括不饱和多环烃如2,5-降冰片二烯（双环[2.2.1]庚-2,5-二烯或BCHD）及经取代的BCHD。
可使用Si-(CH2)n-Si前驱体、含乙烯基的前驱体及致孔剂通过本领域已知的气相沉积方法在基质上形成多孔SiCOH膜，该基质上可能已包括或可能不包括其他层。美国专利第6,312,793号、第6,479,110号、第6,756,323号、第6,953,984号、第7,030,468号、第7,049,427号、第7,282,458号、第7,288,292号、第7,312,524号、第7,479,306号及美国专利申请公开案第2007/0057235号中所公开的关于气相沉积方法的例示性、但非限制性参考以引用的方式并入本文中。
举例而言，预期本文所公开的Si-(CH2)n-Si前驱体、含乙烯基的前驱体及致孔剂可用于美国专利第7,479,306号中公开的沉积SiCOH介电材料的方法中，且更特别的如实施例6中所公开的。如实施例6中所述，将基质置于PECVD沉积反应室中的经加热的接受器（也称作晶片夹盘(waferchuck)）上。将接受器在300℃下加热至425℃，优选在350℃下加热至400℃，但该温度也可介于150℃与300℃之间。前驱体流速可在100mg/min至2000mg/min之间变化。He气可以10sccm至500sccm之间的速率流动。致孔剂流速可在50mg/min至2000mg/min之间变化。前驱体流动经稳定以达到压力在1-10Torr（133-1333Pa）范围内。将RF辐射施加至簇射头（shower head），持续5秒至500秒的时间。本领域技术人员将认识到不同沉积器件可需要不同参数。
当利用BCHD作为致孔剂时，应注意向其中并入聚合抑制剂如由同在申请中的美国专利申请案第12/613,260号所公开的聚合抑制剂，该专利申请案以全文引用的方式并入本文中。本文进一步描述这些方法的常见重点部分。
将基质置于气相沉积装置的反应室中。用于形成绝缘膜的Si-(CH2)n-Si前驱体及含乙烯基的前驱体以及致孔剂可以气态直接传递至反应室中，以蒸发的液体形式传递且引入反应室中，或通过惰性载气（包括但不限于氦气或氩气）传输。优选地，在引入反应室中之前，Si-(CH2)n-Si前驱体、含乙烯基的前驱体及致孔剂在载气如He或Ar的存在下在介于约70℃与约150℃之间的温度下蒸发。
上面将要沉积SiCOH层的基质的类型将根据预期最终用途而变化。基质可包括掺杂或未掺杂的含硅材料如SiCN，任选涂布有氧化硅层，及在这种应用中用作导电材料的金属如钨、钛、钽、钌或铜。或者，基质可包括铜互连及绝缘区如另一低k材料，任选涂布有密封层如SiO2或SiN。上面可涂布pSiCOH膜的基质的其他实例包括但不限于固体基质如金属基质（例如Ru、Al、Ni、Ti、Co、Pt和金属硅化物，例如TiSi2、CoSi2和NiSi2）；含金属氮化物的基质（例如TaN、TiN、WN、TaCN、TiCN、TaSiN及TiSiN）；半导体材料（例如Si、SiGe、GaAs、InP、钻石、GaN及SiC）；绝缘体（例如SiO2、Si3N4、HfO2、Ta2O5、ZrO2、TiO2、Al2O3及钛酸钡锶）；或包括这些材料的任何数目的组合的其他基质。所用实际基质也将取决于所用SiCOH层。
将含Si-(CH2)n-Si的前驱体、含乙烯基的前驱体和致孔剂同时或以脉冲顺序引入膜沉积室中且与基质接触以在基质的至少一个表面上形成绝缘层。普遍地，将前驱体和致孔剂同时引入PECVD室中。膜沉积室可以为进行沉积方法的器件的任何封闭空间或室，例如（不限于）平行板型反应器、冷壁型反应器、热壁型反应器、单晶片反应器、多晶片反应器或其他这种类型的沉积系统。
本领域技术人员应能够容易地选择在低k膜沉积期间控制工艺变量的适当值，包括RF功率、前驱体混合物及流速、反应室中的压力和基质温度。
随后可通过额外加工使SiCOH层变得多孔以降低绝缘层的介电常数。该加工包括但不限于退火、UV光或电子束。
所得膜优选具有低于以下两者的介电常数：（1）由含Si-(CH2)n-Si的前驱体和致孔剂形成的SiCOH膜的介电常数；及（2）由含乙烯基的前驱体和致孔剂形成的SiCOH膜的介电常数。所得膜优选具有在约2.0至约2.7的范围内的介电常数和在约4至约10的范围内的杨氏模量。
实施例
提供以下非限制性实施例以进一步说明本发明的实施方案。然而，这些实施例不意欲全部包括在内且不意欲限制本文所述本发明的范围。
在以下实施例中，使用配备有DxZ沉积室和TEOS组的AppliedMaterials P5000等离子体增强化学气相沉积装置来沉积SiCOH膜。通过经TEOS或DMDMOS校准的质量流量控制器来控制前驱体的流速。通过关于BCHD校准的质量流量控制器来控制致孔剂的流速。
沉积后，使膜在另一定制室（也基于DxZ室）中固化，该室经改进而包括在室盖中的熔融二氧化硅窗和透过该窗照射晶片的UV灯。膜在1Torr压力、1slm氮气流速和400℃接受器温度下固化3-30分钟。
为了评估除对比例1以外的以下实施例中沉积膜的介电常数，用汞探针测定介电常数。
为了评估除对比例1以外的以下实施例中沉积膜的机械效能，通过纳米压痕（nanoindentation）测定其杨氏模量。为了实现代表性测量，各膜厚度为纳米压痕尖端的特征尺寸的约10倍或大于10倍。选择该厚度以消除基质的影响。对各样品在该深度测定的杨氏模量一般为其最小值。
对比例1
表1总结了JSR公司在EP2264219的实施例中获得的结果。
EP2264219的实施例2和14-18的结果似乎说明所提出的含Si-(CH2)n-Si的前驱体与第二前驱体和致孔剂的组合对介电常数和杨氏模量结果不产生任何显著改变。不幸的是，由于未提供(CH3CH2O)2CH3SiH+成孔剂的结果，因此未明确说明由于将两种前驱体（即Si-(CH2)n-Si前驱体和二乙氧基甲基硅烷前驱体）混合而出现的平均效应。然而，由于由含Si-(CH2)n-Si的前驱体与BCHD形成的膜的大部分介电常数结果和所有杨氏模量结果优于由含Si-(CH2)n-Si的前驱体、二乙氧基甲基硅烷前驱体和BCHD形成的膜的结果，因此本领域技术人员将推断出，由二乙氧基甲基硅烷前驱体与BCHD的组合形成的膜的杨氏模量将低于由含Si-(CH2)n-Si的前驱体和BCHD形成的膜的杨氏模量。
EP2264219的实施例16、14、17和15的结果证明了对于特定前驱体或前驱体的组合，杨氏模量的任何改进通常伴随介电常数的提高。
EP2264219的实施例1、3-6及对比例1和2总结了使用BCHD作为致孔剂形成的膜的结果。EP2264219的实施例10、12、13及对比例5和6总结了使用对二甲苯作为致孔剂所形成的膜的结果。EP2264219的实施例7-9和11及对比例3和4总结了使用环戊烯氧化物作为致孔剂所形成的膜的结果。除了EP2264219的实施例11以外，使用BCHD或对二甲苯作为致孔剂所形成的膜与使用环戊烯氧化物所形成的膜相比具有较低的介电常数。在特定致孔剂的结果内，杨氏模量结果变化极大（即杨氏模量对于BCHD在9.3至16.5的范围内，对于环戊烯氧化物在11.2至14.4的范围内，对于对二甲苯在9.1至14.2的范围内）。最终，EP2264219的实施例3、4和13的结果似乎表明向沉积方法中添加氧气导致膜具有较高的杨氏模量。
请注意，EP2264219中的例示性沉积方法利用双频等离子体CVD装置，而本申请人在以下实施例中利用单频等离子体。因此，在以下表1中由JSR公司提供的实施例所获得的结果无法与本申请人的以下实施例相比。
表1
对比例2：Me(EtO)2Si-CH2-SiMe(OEt)2
使用Me(EtO)2Si-CH2-SiMe(OEt)2和BCHD沉积SiCOH膜来进行多项测试。Me(EtO)2Si-CH2-SiMe(OEt)2流速从300mg/min变为800mg/min。BCHD流速从300mg/min变为750mg/min。氦气载气流速保持在350sccm。氧气流速介于5sccm与30sccm之间。接受器温度设定为260℃或300℃。等离子体功率介于200W与600W之间。间隔设定为0.275英寸（6.985mm）或0.500英寸（12.7mm）之间。“间隔”指上面停置有晶片的接受器与“簇射头”之间的间距，“簇射头”为引入气体所穿过的上部电极。所得最佳介电常数为约2.5。所得膜在约2.51的k值下具有约4.4GPa的杨氏模量。
对比例3：Me(EtO)2Si-CH2CH2-SiMe(OEt)2
使用Me(EtO)2Si-CH2CH2-SiMe(OEt)2和BCHD沉积SiCOH膜来进行多项测试。Me(EtO)2Si-CH2CH2-SiMe(OEt)2流速从300mg/min变为600mg/min。BCHD流速从300mg/min变为800mg/min。氦气载气流速保持在350sccm或1000sccm。氧气流速介于5sccm与30sccm之间。接受器温度设定为260℃或300℃。等离子体功率介于200W与500W之间。间隔设定为0.275英寸（6.985mm）或0.500英寸（12.7mm）之间。所得最佳介电常数为约2.4。所得膜具有约3.5GPa的杨氏模量。
对比例4：(HC=CH2)(EtO)3Si
使用(HC=CH2)(EtO)3Si和BCHD沉积SiCOH膜来进行多项测试。(HC=CH2)(EtO)3Si流速为750mg/min。BCHD流速为800mg/min。氦气载气流速保持在750sccm。氧气流速设定为0sccm。接受器温度设定为260℃。等离子体功率设定为150W。间隔设定为0.500英寸（12.7mm）。所得最佳介电常数为约2.31。所得膜具有5.5GPa的杨氏模量。
对比例5：Me(EtO)2Si-CH2-SiMe(OEt)2+(HC=CH2)(EtO)3Si
用Me(EtO)2Si-CH2-SiMe(OEt)2、(HC=CH2)(EtO)3Si和BCHD沉积SiCOH膜来进行测试。Me(EtO)2Si-CH2-SiMe(OEt)2流速为200mg/min。(HC=CH2)(EtO)3Si流速为500mg/min。BCHD流速为800mg/min。氦气载气流速保持在500sccm。氧气流速为5sccm。接受器温度设定为300℃。等离子体功率为500W。间隔设定为0.500英寸（12.7mm）。所得介电常数为约2.41。所得膜具有约3.6GPa的杨氏模量。
由Me(EtO)2Si-CH2-SiMe(OEt)2、(HC=CH2)(EtO)3Si和BCHD的组合（即2.41）形成的膜得到的介电常数几乎是由Me(EtO)2Si-CH2-SiMe(OEt)2与BCHD（即2.5）和由(HC=CH2)(EtO)3Si与BCHD（即2.31）形成的膜的介电常数的精确的平均值。此外，当与由单独前驱体/BCHD组合形成的膜相比时，由Me(EtO)2Si-CH2-SiMe(OEt)2、(HC=CH2)(EtO)3Si和BCHD的组合形成的膜具有较低的杨氏模量结果。
对比例6：Me2(EtO)Si-CH2-SiH(OEt)2
使用Me2(EtO)Si-CH2-SiH(OEt)2和BCHD沉积SiCOH膜来进行多项测试。Me2(EtO)Si-CH2-SiH(OEt)2流速从300mg/min变为750mg/min。BCHD流速从300mg/min变为750mg/min。氦气载气流速保持在500sccm。氧气流速设定为0sccm、5sccm、15sccm、30sccm或50sccm。接受器温度设定为260℃或300℃。等离子体功率设定为250W、300W、400W或500W。间隔设定为0.275英寸（6.985mm）或0.500英寸（12.7mm）之间。所得最佳介电常数为约2.3。所得膜在2.31的k值下在5sccmO2下具有4.2GPa的杨氏模量，且在2.39的k值下在30sccm O2下具有6.5GPa的杨氏模量。再一次，对于特定前驱体组合，杨氏模量的改进伴随介电常数的提高。
实施例1：Me2(EtO)Si-CH2-SiH(OEt)2+(HC=CH2)(EtO)3Si
使用Me2(EtO)Si-CH2-SiH(OEt)2、(HC=CH2)(EtO)3Si和BCHD沉积SiCOH膜来进行多项测试。Me2(EtO)Si-CH2-SiH(OEt)2流速从250mg/min变为500mg/min。(HC=CH2)(EtO)3Si流速从250mg/min变为500mg/min。BCHD流速为800mg/min。氦气载气流速保持在500sccm。氧气流速在5sccm与30sccm之间变化。接受器温度设定为260℃或300℃。等离子体功率设定为300W或500W。反应室压力设定为8Torr。间隔设定为0.500英寸（12.7mm）。所得最佳介电常数为约2.17，其出人意料地优于对比例4和6中所得的介电常数。另外，所得膜在2.28的k值下具有6.0GPa的杨氏模量且在2.23的k值下具有6.1GPa的杨氏模量。
如表2中所示，除了由Me2(EtO)Si-CH2-SiH(OEt)2、(HC=CH2)(EtO)3Si和BCHD的混合物所形成的膜之一以外所有的膜的介电常数（测量的k）均低于由Me2(EtO)Si-CH2-SiH(OEt)2和BCHD或(HC=CH2)(EtO)3Si和BCHD所获得的膜的最佳介电常数。
表2
应了解，本领域技术人员可在如所附权利要求所表示的本发明的原理和范围内对本文中已描述及说明以解释本发明本质的详情、材料、步骤及零件配置作出多种其他改变。因此，本发明并不意欲局限于上文和/或附图中给出的实施例中的特定实施方案。
Claims (13)
1.一种在基质上形成SiCOH膜层的方法，所述方法包括以下步骤：
-提供安置有至少一个基质的反应室；
-向反应室中引入含Si-(CH2)n-Si的前驱体，其中n=1或2，含Si-(CH2)n-Si的前驱体选自由以下组成的组：
和
其中R1至R4各自独立地选自由H、甲基、乙基、丙基、乙烯基和C1-C3烷氧基组成的组；R5选自由甲基、乙基和丙基组成的组；优选R1至R4中至少一个为甲基、乙基或丙基；且R1至R3中至少一个为烷氧基，其可与-OR5相同或不同；
-向反应室中引入具有式Si(R1)x(O(R2))4-x的含乙烯基的前驱体，其中至少一个R1为乙烯基，任选第二R1为氢或烷基，优选甲基或乙基；各R2独立地选自烷基，优选甲基或乙基；且x为1或2；和
-向反应室中引入致孔剂；及
-使Si-(CH2)n-Si前驱体、含乙烯基的前驱体、致孔剂和基质接触以使用沉积方法，优选化学气相沉积在基质的至少一个表面上形成SiCOH膜。
2.根据权利要求1的方法，其中该含乙烯基的前驱体选自由乙烯基二乙氧基硅烷、乙烯基二甲氧基硅烷、乙烯基三甲氧基硅烷、乙烯基三乙氧基硅烷、乙烯基甲基二甲氧基硅烷和乙烯基甲基二乙氧基硅烷组成的组，优选为乙烯基三乙氧基硅烷或乙烯基甲基二乙氧基硅烷。
3.根据权利要求1或2的方法，其中致孔剂为经取代或未经取代的双环[2.2.1]庚-2,5-二烯。
4.根据权利要求1-3中任一项的方法，其中沉积方法为单频PECVD。
5.根据权利要求1-4中任一项的方法，其进一步包含使SiCOH膜变得多孔的步骤。
6.根据权利要求1-5中任一项的方法，其中R1至R4不为H。
7.根据权利要求6的方法，其中含Si-(CH2)n-Si的前驱体选自由(EtO)3Si-CH2-Si(OEt)2H、Me(OEt)2Si-CH2-Si(OEt)2H、Me(OEt)2Si-CH2-Si(OEt)HMe、Me2(OEt)Si-CH2-Si(OEt)2H、(EtO)Me2SiCH2Si(OMe)2H、Me2(OEt)Si-CH2-Si(OEt)HMe、(OEt)3Si-CH2-Si(OEt)HMe、(EtO)3Si-CH2-Si(OMe)HMe、Me(OMe)2Si-CH2-Si(OMe)2H、Me(OMe)2Si-CH2-Si(OMe)HMe、Me2(OMe)SiCH2Si(OMe)2H和Me2(OEt)Si-CH2-Si(OMe)HMe组成的组，优选Me(OEt)2Si-CH2-Si(OEt)2H、Me2(OEt)Si-CH2-Si(OEt)2H和Me(OEt)2Si-CH2-Si(OEt)HMe。
8.根据权利要求6的方法，其中含Si-(CH2)n-Si的前驱体选自由(EtO)3Si-CH2CH2-Si(OEt)2H、Me(OEt)2Si-CH2CH2-Si(OEt)2H、Me(OEt)2Si-CH2CH2-Si(OEt)HMe、Me2(OEt)Si-CH2CH2-Si(OEt)2H、(EtO)Me2Si-CH2CH2Si(OMe)2H、Me2(OEt)Si-CH2CH2-Si(OEt)HMe、(OEt)3Si-CH2CH2-Si(OEt)HMe、(EtO)3Si-CH2CH2-Si(OMe)HMe、Me(OMe)2Si-CH2CH2-Si(OMe)2H、Me(OMe)2Si-CH2CH2-Si(OMe)HMe、Me2(OMe)Si-CH2CH2Si(OMe)2H和Me2(OEt)Si-CH2CH2-Si(OMe)HMe组成的组，优选Me(OEt)2Si-CH2CH2-Si(OEt)2H、Me2(OEt)Si-CH2CH2-Si(OEt)2H和Me(OEt)2Si-CH2CH2-Si(OEt)HMe。
9.根据权利要求1-5中任一项的方法，其中R1至R3中仅一个为H。
10.根据权利要求9的方法，其中含Si-(CH2)n-Si的前驱体选自由MeH(OMe)Si-CH2-Si(OMe)HMe、(EtO)2HSi-CH2-Si(OEt)2H、(EtO)HMeSi-CH2-Si(OEt)HMe和(iPrO)HMeSi-CH2-Si(OiPr)HMe组成的组。
11.根据权利要求6的方法，其中SiCOH膜具有低于以下两者的介电常数：（1）由含Si-(CH2)n-Si的前驱体和致孔剂形成的SiCOH膜的介电常数；和（2）由含乙烯基的前驱体和致孔剂形成的SiCOH膜的介电常数。
12.根据权利要求1-11中任一项的方法形成的膜。
13.根据权利要求12的膜，其中所述膜具有在约2.0至约2.7、优选约2.0至约2.5的范围内的介电常数，及在约4GPa至约10GPa、优选约5GPa至约10GPa的范围内的杨氏模量。
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| JP5365785B2 (ja) | 2008-05-30 | 2013-12-11 | Ｊｓｒ株式会社 | 有機ケイ素化合物の製造方法 |
| US8298965B2 (en) * | 2008-09-03 | 2012-10-30 | American Air Liquide, Inc. | Volatile precursors for deposition of C-linked SiCOH dielectrics |
| KR20110125651A (ko) * | 2009-03-10 | 2011-11-21 | 레르 리키드 쏘시에떼 아노님 뿌르 레드 에렉스뿔라따시옹 데 프로세데 조르즈 클로드 | 저 유전상수 실릴화를 위한 시클릭 아미노 화합물 |
| JP4379637B1 (ja) | 2009-03-30 | 2009-12-09 | Ｊｓｒ株式会社 | 有機ケイ素化合物の製造方法 |
| KR101263789B1 (ko) | 2009-07-13 | 2013-05-13 | 제이에스아이실리콘주식회사 | 유기 클로로하이드로실란과 이의 제조방법 |
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2011
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- 2011-02-17 TW TW100105218A patent/TWI550121B/zh not_active IP Right Cessation
- 2011-02-17 WO PCT/US2011/025234 patent/WO2011103282A2/en active Application Filing
- 2011-02-17 CN CN201180010066.3A patent/CN102762763B/zh not_active Expired - Fee Related
- 2011-02-17 SG SG2012059812A patent/SG183291A1/en unknown
- 2011-02-17 JP JP2012554022A patent/JP2013520030A/ja not_active Withdrawn
- 2011-02-17 KR KR1020127021433A patent/KR20130043084A/ko not_active Application Discontinuation
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| WO2005080629A2 (en) * | 2004-02-19 | 2005-09-01 | Degussa Ag | SILICON COMPOUNDS FOR PRODUCING SiO2-CONTAINING INSULATING LAYERS ON CHIPS |
| JP2009132855A (ja) * | 2007-11-01 | 2009-06-18 | Jsr Corp | ケイ素含有膜形成用組成物、ケイ素含有絶縁膜、およびケイ素含有絶縁膜の形成方法 |
| WO2009119583A1 (ja) * | 2008-03-26 | 2009-10-01 | Jsr株式会社 | 化学気相成長法用材料ならびにケイ素含有絶縁膜およびその製造方法 |
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| CN110073030A (zh) * | 2016-11-02 | 2019-07-30 | 弗萨姆材料美国有限责任公司 | 甲硅烷基桥联烷基化合物用于致密osg膜的用途 |
Also Published As
| Publication number | Publication date |
|---|---|
| TWI550121B (zh) | 2016-09-21 |
| KR20130043084A (ko) | 2013-04-29 |
| EP2536867A4 (en) | 2013-07-10 |
| US8932674B2 (en) | 2015-01-13 |
| EP2536867A2 (en) | 2012-12-26 |
| CN102762763B (zh) | 2014-12-31 |
| SG183291A1 (en) | 2012-09-27 |
| JP2013520030A (ja) | 2013-05-30 |
| TW201134976A (en) | 2011-10-16 |
| WO2011103282A3 (en) | 2012-02-02 |
| US20130042790A1 (en) | 2013-02-21 |
| WO2011103282A2 (en) | 2011-08-25 |
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