JP6202179B2 - Disiloxane compound - Google Patents
Disiloxane compound Download PDFInfo
- Publication number
- JP6202179B2 JP6202179B2 JP2016213486A JP2016213486A JP6202179B2 JP 6202179 B2 JP6202179 B2 JP 6202179B2 JP 2016213486 A JP2016213486 A JP 2016213486A JP 2016213486 A JP2016213486 A JP 2016213486A JP 6202179 B2 JP6202179 B2 JP 6202179B2
- Authority
- JP
- Japan
- Prior art keywords
- divinyldisiloxane
- diisopropyl
- general formula
- hydroxy
- compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- -1 Disiloxane compound Chemical class 0.000 title claims description 31
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 19
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 7
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 239000010408 film Substances 0.000 description 24
- 150000001875 compounds Chemical class 0.000 description 22
- 238000006243 chemical reaction Methods 0.000 description 20
- 238000000034 method Methods 0.000 description 15
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 14
- SSJSQLFCGFXNDZ-UHFFFAOYSA-N 2,4,6,8-tetrakis(ethenyl)-2,4,6,8-tetra(propan-2-yl)-1,3,5,7,2,4,6,8-tetraoxatetrasilocane Chemical compound CC(C)[Si]1(C=C)O[Si](C(C)C)(C=C)O[Si](C(C)C)(C=C)O[Si](C(C)C)(C=C)O1 SSJSQLFCGFXNDZ-UHFFFAOYSA-N 0.000 description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 12
- ZOAUCLPLIFDWHD-UHFFFAOYSA-N O[Si](O[Si](C=C)(C(C)C)OC)(C=C)C(C)C Chemical compound O[Si](O[Si](C=C)(C(C)C)OC)(C=C)C(C)C ZOAUCLPLIFDWHD-UHFFFAOYSA-N 0.000 description 9
- 239000002253 acid Substances 0.000 description 9
- 239000010410 layer Substances 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- MYIJOUFUSXNPJD-UHFFFAOYSA-N CO[Si](O[Si](C=C)(C(C)C)OC)(C=C)C(C)C Chemical compound CO[Si](O[Si](C=C)(C(C)C)OC)(C=C)C(C)C MYIJOUFUSXNPJD-UHFFFAOYSA-N 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- RUPRNLBNBISIOX-UHFFFAOYSA-N O[Si](O[Si](C=C)(C(C)C)O)(C=C)C(C)C Chemical compound O[Si](O[Si](C=C)(C(C)C)O)(C=C)C(C)C RUPRNLBNBISIOX-UHFFFAOYSA-N 0.000 description 7
- 239000002243 precursor Substances 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- DDJSWKLBKSLAAZ-UHFFFAOYSA-N cyclotetrasiloxane Chemical compound O1[SiH2]O[SiH2]O[SiH2]O[SiH2]1 DDJSWKLBKSLAAZ-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 5
- 230000008030 elimination Effects 0.000 description 5
- 238000003379 elimination reaction Methods 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- 239000007810 chemical reaction solvent Substances 0.000 description 4
- 238000005229 chemical vapour deposition Methods 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000012159 carrier gas Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- LTFFPRXIELHUGX-UHFFFAOYSA-N dimethoxy(3-methylbut-1-enyl)silane Chemical compound C(C)(C)C=C[SiH](OC)OC LTFFPRXIELHUGX-UHFFFAOYSA-N 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000011229 interlayer Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000001819 mass spectrum Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- BOHZRSRHHJHLHQ-UHFFFAOYSA-N 2,4,6-tris(ethenyl)-2,4,6-tri(propan-2-yl)-1,3,5,2,4,6-trioxatrisilinane Chemical compound CC(C)[Si]1(C=C)O[Si](C(C)C)(C=C)O[Si](C(C)C)(C=C)O1 BOHZRSRHHJHLHQ-UHFFFAOYSA-N 0.000 description 2
- HCFAJYNVAYBARA-UHFFFAOYSA-N 4-heptanone Chemical compound CCCC(=O)CCC HCFAJYNVAYBARA-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- MLFHJEHSLIIPHL-UHFFFAOYSA-N isoamyl acetate Chemical compound CC(C)CCOC(C)=O MLFHJEHSLIIPHL-UHFFFAOYSA-N 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000012264 purified product Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 229930195734 saturated hydrocarbon Natural products 0.000 description 2
- 230000036962 time dependent Effects 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- 239000006200 vaporizer Substances 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- JMROMRCGLWRYBP-UHFFFAOYSA-N 2,4,6,8-tetrakis(ethenyl)-2,4,6,8-tetraethyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane Chemical compound CC[Si]1(C=C)O[Si](CC)(C=C)O[Si](CC)(C=C)O[Si](CC)(C=C)O1 JMROMRCGLWRYBP-UHFFFAOYSA-N 0.000 description 1
- VMAWODUEPLAHOE-UHFFFAOYSA-N 2,4,6,8-tetrakis(ethenyl)-2,4,6,8-tetramethyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane Chemical compound C=C[Si]1(C)O[Si](C)(C=C)O[Si](C)(C=C)O[Si](C)(C=C)O1 VMAWODUEPLAHOE-UHFFFAOYSA-N 0.000 description 1
- IUXIKQGXIZRSBF-UHFFFAOYSA-N 2,4,6,8-tetrakis(ethenyl)-2,4,6,8-tetrapropyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane Chemical compound CCC[Si]1(C=C)O[Si](CCC)(C=C)O[Si](CCC)(C=C)O[Si](CCC)(C=C)O1 IUXIKQGXIZRSBF-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- WGYDXYBQNYQPIU-UHFFFAOYSA-N 3,3-di(propan-2-yloxy)prop-1-enylsilane Chemical compound C(C)(C)OC(OC(C)C)C=C[SiH3] WGYDXYBQNYQPIU-UHFFFAOYSA-N 0.000 description 1
- RZUCEHQWIXHNJQ-UHFFFAOYSA-N 3,3-dipropoxyprop-1-enylsilane Chemical compound C(CC)OC(OCCC)C=C[SiH3] RZUCEHQWIXHNJQ-UHFFFAOYSA-N 0.000 description 1
- YNWJPOVPFGCGLE-UHFFFAOYSA-N 4,4-diethoxybut-1-enylsilane Chemical compound C(C)OC(CC=C[SiH3])OCC YNWJPOVPFGCGLE-UHFFFAOYSA-N 0.000 description 1
- MZZPECHJKDVTOI-UHFFFAOYSA-N 4,4-dimethoxybut-1-enylsilane Chemical compound COC(CC=C[SiH3])OC MZZPECHJKDVTOI-UHFFFAOYSA-N 0.000 description 1
- SKVCJVZPSWVBPA-UHFFFAOYSA-N 5,5-dimethoxypent-1-enylsilane Chemical compound COC(CCC=C[SiH3])OC SKVCJVZPSWVBPA-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- LNMWLIIGGDQOLF-UHFFFAOYSA-N C(C)(C)OC(CC=C[SiH3])OC(C)C Chemical compound C(C)(C)OC(CC=C[SiH3])OC(C)C LNMWLIIGGDQOLF-UHFFFAOYSA-N 0.000 description 1
- BYOGLIHTFXFXFD-UHFFFAOYSA-N C(C)(C)OC(CCC=C[SiH3])OC(C)C Chemical compound C(C)(C)OC(CCC=C[SiH3])OC(C)C BYOGLIHTFXFXFD-UHFFFAOYSA-N 0.000 description 1
- ZEUXXDSMNYJDRD-UHFFFAOYSA-N C(C)(C)O[SiH](C=CC(C)C)OC(C)C Chemical compound C(C)(C)O[SiH](C=CC(C)C)OC(C)C ZEUXXDSMNYJDRD-UHFFFAOYSA-N 0.000 description 1
- ITVRTTQZRGCQMW-UHFFFAOYSA-N C(C)(C)O[Si](O[Si](C=C)(C(C)C)OC(C)C)(C=C)C(C)C Chemical compound C(C)(C)O[Si](O[Si](C=C)(C(C)C)OC(C)C)(C=C)C(C)C ITVRTTQZRGCQMW-UHFFFAOYSA-N 0.000 description 1
- OESCDJVFVOQKFG-UHFFFAOYSA-N C(C)(C)O[Si](O[Si](C=C)(CCC)OC(C)C)(C=C)CCC Chemical compound C(C)(C)O[Si](O[Si](C=C)(CCC)OC(C)C)(C=C)CCC OESCDJVFVOQKFG-UHFFFAOYSA-N 0.000 description 1
- LRBLQAZTWZPJQL-UHFFFAOYSA-N C(C)(C)[Si]1(O[SiH](O[SiH](O[SiH](O1)C=C)C=C)C=C)C=C Chemical compound C(C)(C)[Si]1(O[SiH](O[SiH](O[SiH](O1)C=C)C=C)C=C)C=C LRBLQAZTWZPJQL-UHFFFAOYSA-N 0.000 description 1
- QODXJGHBRUAVNW-UHFFFAOYSA-N C(C)O[Si](O[Si](C=C)(C(C)C)O)(C=C)C(C)C Chemical compound C(C)O[Si](O[Si](C=C)(C(C)C)O)(C=C)C(C)C QODXJGHBRUAVNW-UHFFFAOYSA-N 0.000 description 1
- BPGYADUCVJTXJT-UHFFFAOYSA-N C(C)O[Si](O[Si](C=C)(C(C)C)OCC)(C=C)C(C)C Chemical compound C(C)O[Si](O[Si](C=C)(C(C)C)OCC)(C=C)C(C)C BPGYADUCVJTXJT-UHFFFAOYSA-N 0.000 description 1
- LNCDEJXVHSSUTM-UHFFFAOYSA-N C(C)O[Si](O[Si](C=C)(C)O)(C=C)C Chemical compound C(C)O[Si](O[Si](C=C)(C)O)(C=C)C LNCDEJXVHSSUTM-UHFFFAOYSA-N 0.000 description 1
- SMVUSQJQPLAEIF-UHFFFAOYSA-N C(C)O[Si](O[Si](C=C)(CC)O)(C=C)CC Chemical compound C(C)O[Si](O[Si](C=C)(CC)O)(C=C)CC SMVUSQJQPLAEIF-UHFFFAOYSA-N 0.000 description 1
- IMBVBIDAUVHZES-UHFFFAOYSA-N C(C)O[Si](O[Si](C=C)(CC)OCC)(C=C)CC Chemical compound C(C)O[Si](O[Si](C=C)(CC)OCC)(C=C)CC IMBVBIDAUVHZES-UHFFFAOYSA-N 0.000 description 1
- UYHNHOAZZKEDII-UHFFFAOYSA-N C(C)O[Si](O[Si](C=C)(CCC)O)(C=C)CCC Chemical compound C(C)O[Si](O[Si](C=C)(CCC)O)(C=C)CCC UYHNHOAZZKEDII-UHFFFAOYSA-N 0.000 description 1
- DNPNQFKQOACMDT-UHFFFAOYSA-N C(CC)OC(CC=C[SiH3])OCCC Chemical compound C(CC)OC(CC=C[SiH3])OCCC DNPNQFKQOACMDT-UHFFFAOYSA-N 0.000 description 1
- RDDLHCSYKNEYEO-UHFFFAOYSA-N C(CC)OC(CCC=C[SiH3])OCCC Chemical compound C(CC)OC(CCC=C[SiH3])OCCC RDDLHCSYKNEYEO-UHFFFAOYSA-N 0.000 description 1
- UUKSIDWUJGUFBJ-UHFFFAOYSA-N C(CC)O[SiH](C=CC(C)C)OCCC Chemical compound C(CC)O[SiH](C=CC(C)C)OCCC UUKSIDWUJGUFBJ-UHFFFAOYSA-N 0.000 description 1
- GXCMCXQPMQAUDD-UHFFFAOYSA-N C(CC)O[Si](O[Si](C=C)(C)OCCC)(C=C)C Chemical compound C(CC)O[Si](O[Si](C=C)(C)OCCC)(C=C)C GXCMCXQPMQAUDD-UHFFFAOYSA-N 0.000 description 1
- LUVCJLPMZCCXTP-UHFFFAOYSA-N C(CC)O[Si](O[Si](C=C)(CC)OCCC)(C=C)CC Chemical compound C(CC)O[Si](O[Si](C=C)(CC)OCCC)(C=C)CC LUVCJLPMZCCXTP-UHFFFAOYSA-N 0.000 description 1
- FJCLGHXBHRLHGS-UHFFFAOYSA-N CO[Si](O[Si](C=C)(CC)OC)(C=C)CC Chemical compound CO[Si](O[Si](C=C)(CC)OC)(C=C)CC FJCLGHXBHRLHGS-UHFFFAOYSA-N 0.000 description 1
- KTBIQPOENQFEIK-UHFFFAOYSA-N CO[Si](O[Si](C=C)(CCC)OC)(C=C)CCC Chemical compound CO[Si](O[Si](C=C)(CCC)OC)(C=C)CCC KTBIQPOENQFEIK-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- YLPLLAJISQVFBF-UHFFFAOYSA-N O[Si](O[Si](C=C)(C(C)C)OC(C)C)(C=C)C(C)C Chemical compound O[Si](O[Si](C=C)(C(C)C)OC(C)C)(C=C)C(C)C YLPLLAJISQVFBF-UHFFFAOYSA-N 0.000 description 1
- LIVULFVVQRZYEL-UHFFFAOYSA-N O[Si](O[Si](C=C)(C(C)C)OCCC)(C=C)C(C)C Chemical compound O[Si](O[Si](C=C)(C(C)C)OCCC)(C=C)C(C)C LIVULFVVQRZYEL-UHFFFAOYSA-N 0.000 description 1
- NHGDEUJCBGJNDU-UHFFFAOYSA-N O[Si](O[Si](C=C)(C)OC(C)C)(C=C)C Chemical compound O[Si](O[Si](C=C)(C)OC(C)C)(C=C)C NHGDEUJCBGJNDU-UHFFFAOYSA-N 0.000 description 1
- IXJJVOWVNDJTSX-UHFFFAOYSA-N O[Si](O[Si](C=C)(C)OCCC)(C=C)C Chemical compound O[Si](O[Si](C=C)(C)OCCC)(C=C)C IXJJVOWVNDJTSX-UHFFFAOYSA-N 0.000 description 1
- FFQSPVKHSBTLFF-UHFFFAOYSA-N O[Si](O[Si](C=C)(CC)O)(C=C)CC Chemical compound O[Si](O[Si](C=C)(CC)O)(C=C)CC FFQSPVKHSBTLFF-UHFFFAOYSA-N 0.000 description 1
- WAUGXXVMPWJGDO-UHFFFAOYSA-N O[Si](O[Si](C=C)(CC)OC(C)C)(C=C)CC Chemical compound O[Si](O[Si](C=C)(CC)OC(C)C)(C=C)CC WAUGXXVMPWJGDO-UHFFFAOYSA-N 0.000 description 1
- ZINODFAMIWWOAT-UHFFFAOYSA-N O[Si](O[Si](C=C)(CC)OC)(C=C)CC Chemical compound O[Si](O[Si](C=C)(CC)OC)(C=C)CC ZINODFAMIWWOAT-UHFFFAOYSA-N 0.000 description 1
- VIZBZZHYIOGBTN-UHFFFAOYSA-N O[Si](O[Si](C=C)(CCC)O)(C=C)CCC Chemical compound O[Si](O[Si](C=C)(CCC)O)(C=C)CCC VIZBZZHYIOGBTN-UHFFFAOYSA-N 0.000 description 1
- CDWHIECTPDXZFT-UHFFFAOYSA-N O[Si](O[Si](C=C)(CCC)OC(C)C)(C=C)CCC Chemical compound O[Si](O[Si](C=C)(CCC)OC(C)C)(C=C)CCC CDWHIECTPDXZFT-UHFFFAOYSA-N 0.000 description 1
- GMKZSJQPTNIOJJ-UHFFFAOYSA-N O[Si](O[Si](C=C)(CCC)OC)(C=C)CCC Chemical compound O[Si](O[Si](C=C)(CCC)OC)(C=C)CCC GMKZSJQPTNIOJJ-UHFFFAOYSA-N 0.000 description 1
- GJNDDCJZGNOSDL-UHFFFAOYSA-N O[Si](O[Si](C=C)(CCC)OCCC)(C=C)CCC Chemical compound O[Si](O[Si](C=C)(CCC)OCCC)(C=C)CCC GJNDDCJZGNOSDL-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- CGMFKBXPQJJHBR-UHFFFAOYSA-N [SiH3]O[SiH](C=C)C=C Chemical compound [SiH3]O[SiH](C=C)C=C CGMFKBXPQJJHBR-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- UWKZJHALFALBFZ-UHFFFAOYSA-N diethoxy(3-methylbut-1-enyl)silane Chemical compound C(C)(C)C=C[SiH](OCC)OCC UWKZJHALFALBFZ-UHFFFAOYSA-N 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- HPEASWRSAOKIDT-UHFFFAOYSA-N ethenyl-(ethenyl-ethoxy-methylsilyl)oxy-ethoxy-methylsilane Chemical compound CCO[Si](C)(C=C)O[Si](C)(C=C)OCC HPEASWRSAOKIDT-UHFFFAOYSA-N 0.000 description 1
- HKGQTXCGPDIVTR-UHFFFAOYSA-N ethenyl-(ethenyl-hydroxy-methylsilyl)oxy-hydroxy-methylsilane Chemical compound C=C[Si](O)(C)O[Si](C)(O)C=C HKGQTXCGPDIVTR-UHFFFAOYSA-N 0.000 description 1
- SPCHDFGQKLHKIZ-UHFFFAOYSA-N ethenyl-(ethenyl-methoxy-methylsilyl)oxy-methoxy-methylsilane Chemical compound CO[Si](C)(C=C)O[Si](C)(OC)C=C SPCHDFGQKLHKIZ-UHFFFAOYSA-N 0.000 description 1
- PPWZUVSYOBJOHN-UHFFFAOYSA-N ethenyl-[ethenyl(propan-2-yl)silyl]oxy-propan-2-ylsilane Chemical compound CC(C)[SiH](C=C)O[SiH](C=C)C(C)C PPWZUVSYOBJOHN-UHFFFAOYSA-N 0.000 description 1
- MBGQQKKTDDNCSG-UHFFFAOYSA-N ethenyl-diethoxy-methylsilane Chemical compound CCO[Si](C)(C=C)OCC MBGQQKKTDDNCSG-UHFFFAOYSA-N 0.000 description 1
- ZLNAFSPCNATQPQ-UHFFFAOYSA-N ethenyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C=C ZLNAFSPCNATQPQ-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 description 1
- NGAZZOYFWWSOGK-UHFFFAOYSA-N heptan-3-one Chemical compound CCCCC(=O)CC NGAZZOYFWWSOGK-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- QWTDNUCVQCZILF-UHFFFAOYSA-N iso-pentane Natural products CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 1
- 229940117955 isoamyl acetate Drugs 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- SKTCDJAMAYNROS-UHFFFAOYSA-N methoxycyclopentane Chemical compound COC1CCCC1 SKTCDJAMAYNROS-UHFFFAOYSA-N 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- AFFLGGQVNFXPEV-UHFFFAOYSA-N n-decene Natural products CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000002230 thermal chemical vapour deposition Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 1
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- 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
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- 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
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- 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
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- 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
- H01L21/02205—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 the layer being characterised by the precursor material for deposition
- H01L21/02208—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 the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si
- H01L21/02214—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 the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si the compound comprising silicon and oxygen
- H01L21/02216—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 the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si the compound comprising silicon and oxygen the compound being a molecule comprising at least one silicon-oxygen bond and the compound having hydrogen or an organic group attached to the silicon or oxygen, e.g. a siloxane
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- H01L21/02107—Forming insulating materials on a substrate
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Description
本発明は、効率よく製造できる環状シロキサン化合物の製造方法および該製造方法における中間体であるジシロキサン化合物に関するものである。 The present invention relates to a method for producing a cyclic siloxane compound that can be produced efficiently, and a disiloxane compound that is an intermediate in the production method.
近年の半導体素子の高集積化に伴い、LSI配線として従来のAlから低抵抗でマイグレーション耐性に優れるCuが用いられるようになり、一方で層間絶縁膜としては従来の酸化シリコン膜(SiO2膜)から、より低誘電率の層関絶縁膜(Low−k膜)が検討されている。 With the recent high integration of semiconductor elements, Cu, which has low resistance and excellent migration resistance, has been used as an LSI wiring from conventional Al, while a conventional silicon oxide film (SiO 2 film) is used as an interlayer insulating film. Therefore, a layered dielectric film (Low-k film) having a lower dielectric constant has been studied.
現在、層間絶縁膜の形成方法としては、プラズマ化学気相成長法(PECVD法)が主に用いられている。これまでに環状シロキサンを、分子内ポアを有する前駆体(プレカーサー)として用いて、低k値の膜を成膜する検討がなされている。例えば蒸気圧が低い環状シロキサン化合物に、重合基であるビニル基を結合させることで、成膜速度を速くすることに成功している(例えば特許文献1参照)。 At present, plasma chemical vapor deposition (PECVD) is mainly used as a method for forming an interlayer insulating film. So far, studies have been made to form a film having a low k value using cyclic siloxane as a precursor (precursor) having an intramolecular pore. For example, it has succeeded in increasing the film-forming speed | rate by combining the vinyl group which is a polymeric group with the cyclic siloxane compound with a low vapor pressure (for example, refer patent document 1).
前述の環状シロキサン化合物において、PECVD法のプレカーサーとして最適な環サイズは、低k値を達成できること、および蒸気圧を考慮すると6員環または8員環である。蒸気圧の面では分子量の小さい6員環が好ましいが、低k値に寄与する分子内ポアの大きさを考慮すると8員環が好ましい。特許文献1においてジアルコキシアルキルビニルシラン化合物を原料とし、6員環の環状シロキサン化合物を得る方法は記載されているが、効率よく製造できる8員環の環状シロキサン化合物の製造方法については見出されていない。
In the cyclic siloxane compound described above, the optimum ring size as a precursor for the PECVD method is a 6-membered ring or an 8-membered ring in consideration of the ability to achieve a low k value and vapor pressure. In terms of vapor pressure, a 6-membered ring having a small molecular weight is preferable, but an 8-membered ring is preferable in consideration of the size of an intramolecular pore contributing to a low k value.
本発明はジアルコキシアルキルビニルシラン化合物から8員環環状シロキサン、特に2,4,6,8−テトラアルキル−2,4,6,8−テトラビニルシクロテトラシロキサンを効率的に製造する方法を提供することを目的とする。 The present invention provides a method for efficiently producing 8-membered cyclic siloxanes, especially 2,4,6,8-tetraalkyl-2,4,6,8-tetravinylcyclotetrasiloxane, from dialkoxyalkylvinylsilane compounds. For the purpose.
本発明者らは、ジアルコキシアルキルビニルシラン化合物を酸または塩基共存下、水と反応させることで一旦ジシロキサン化合物を製造し、次いで水層を除去して非水条件下としたのち、酸または塩基を添加し反応させることで、目的のシクロテトラシロキサン化合物が効率的に得られることを見出し、本発明を完成するにいたった。 The inventors of the present invention once produced a disiloxane compound by reacting a dialkoxyalkylvinylsilane compound with water in the presence of an acid or a base, and then removed the aqueous layer to obtain non-aqueous conditions. It was found that the target cyclotetrasiloxane compound can be efficiently obtained by adding and reacting, and the present invention was completed.
すなわち本発明は、以下のとおりである。
[1]下記一般式(2)で表されることを特徴とするジシロキサン化合物。
That is, the present invention is as follows.
[1] A disiloxane compound represented by the following general formula (2).
[2]R1がイソプロピル基であることを特徴とする上述の[1]に記載のジシロキサン化合物。
[2] The disiloxane compound as described in [1] above, wherein R 1 is an isopropyl group.
以下、本発明をさらに詳細に説明する。 Hereinafter, the present invention will be described in more detail.
本発明において、一般式(1)におけるR1、R2は炭素数1〜3の直鎖または分岐鎖のアルキル基を示し、具体的には例えばメチル基、エチル基、ノルマルプロピル基、イソプロピル基等が挙げられる。また、R3、R4は上記R2と同じかまたは水素原子を示す。これらの中でも、最終目的物である一般式(3)で表される環状シロキサン化合物の収率の観点から、好ましくはR1がイソプロピル基、R2がメチル基、R3、R4はメチル基または水素原子である。 In the present invention, R 1 and R 2 in the general formula (1) represent a linear or branched alkyl group having 1 to 3 carbon atoms, and specifically include, for example, a methyl group, an ethyl group, a normal propyl group, and an isopropyl group. Etc. R 3 and R 4 are the same as R 2 or a hydrogen atom. Among these, from the viewpoint of the yield of the cyclic siloxane compound represented by the general formula (3), which is the final target product, R 1 is preferably an isopropyl group, R 2 is a methyl group, R 3 and R 4 are methyl groups. Or it is a hydrogen atom.
具体的な一般式(1)で表されるジアルコキシアルキルビニルシラン化合物としては、例えばジメトキシメチルビニルシラン、ジメトキシエチルビニルシラン、ジメトキシプロピルビニルシラン、ジメトキシイソプロピルビニルシラン、ジエトキシメチルビニルシラン、ジエトキシエチルビニルシラン、ジエトキシプロピルビニルシラン、ジエトキシイソプロピルビニルシラン、ジプロポキシメチルビニルシラン、ジプロポキシエチルビニルシラン、ジプロポキシプロピルビニルシラン、ジプロポキシイソプロピルビニルシラン、ジイソプロポキシメチルビニルシラン、ジイソプロポキシエチルビニルシラン、ジイソプロポキシプロピルビニルシラン、ジイソプロポキシイソプロピルビニルシラン等が挙げられる。 Specific examples of the dialkoxyalkylvinylsilane compound represented by the general formula (1) include dimethoxymethylvinylsilane, dimethoxyethylvinylsilane, dimethoxypropylvinylsilane, dimethoxyisopropylvinylsilane, diethoxymethylvinylsilane, diethoxyethylvinylsilane, diethoxypropyl. Vinylsilane, diethoxyisopropylvinylsilane, dipropoxymethylvinylsilane, dipropoxyethylvinylsilane, dipropoxypropylvinylsilane, dipropoxyisopropylvinylsilane, diisopropoxymethylvinylsilane, diisopropoxyethylvinylsilane, diisopropoxypropylvinylsilane, diisopropoxyisopropylvinylsilane Etc.
上記一般式(1)で表されるジアルコキシアルキルビニルシラン化合物を酸または塩基の共存下、水と反応させて、下記一般式(2)で表されるジシロキサン化合物を製造する。 The dialkoxyalkylvinylsilane compound represented by the general formula (1) is reacted with water in the presence of an acid or a base to produce a disiloxane compound represented by the following general formula (2).
一般式(2)におけるR1はエチル基、ノルマルプロピル基、イソプロピル基であり、R3、R4は炭素数1〜3の直鎖または分岐鎖のアルキル基若しくは水素原子を示し、好ましくはR1がイソプロピル基、R3、R4はメチル基または水素原子である。
R 1 in the general formula (2) is an ethyl group, a normal propyl group, or an isopropyl group, and R 3 and R 4 each represent a linear or branched alkyl group having 1 to 3 carbon atoms or a hydrogen atom, preferably
具体的な一般式(2)で表される化合物としては、例えば1,3−ジヒドロキシ−1,3−ジメチル−1,3−ジビニルジシロキサン、1−ヒドロキシ−3−メトキシ−1,3−ジメチル−1,3−ジビニルジシロキサン、1−エトキシ−3−ヒドロキシ−1,3−ジメチル−1,3−ジビニルジシロキサン、1−ヒドロキシ−3−プロポキシ−1,3−ジメチル−1,3−ジビニルジシロキサン、1−ヒドロキシ−3−イソプロポキシ−1,3−ジメチル−1,3−ジビニルジシロキサン、1,3−ジメトキシ−1,3−ジメチル−1,3−ジビニルジシロキサン、1,3−ジエトキシ−1,3−ジメチル−1,3−ジビニルジシロキサン、1,3−ジプロポキシ−1,3−ジメチル−1,3−ジビニルジシロキサン、1,3−ジイソプロポキシ−1,3−ジメチル−1,3−ジビニルジシロキサン、1,3−ジヒドロキシ−1,3−ジエチル−1,3−ジビニルジシロキサン、1−ヒドロキシ−3−メトキシ−1,3−ジエチル−1,3−ジビニルジシロキサン、1−エトキシ−3−ヒドロキシ−1,3−ジエチル−1,3−ジビニルジシロキサン、1−ヒドロキシ−3−プロポキシ−1,3−ジエチル−1,3−ジビニルジシロキサン、1−ヒドロキシ−3−イソプロポキシ−1,3−ジエチル−1,3−ジビニルジシロキサン、1,3−ジメトキシ−1,3−ジエチル−1,3−ジビニルジシロキサン、1,3−ジエトキシ−1,3−ジエチル−1,3−ジビニルジシロキサン、1,3−ジプロポキシ−1,3−ジエチル−1,3−ジビニルジシロキサン、1,3−ジイソプロポキシ−1,3−ジエチル−1,3−ジビニルジシロキサン、1,3−ジヒドロキシ−1,3−ジプロピル−1,3−ジビニルジシロキサン、1−ヒドロキシ−3−メトキシ−1,3−ジプロピル−1,3−ジビニルジシロキサン、1−エトキシ−3−ヒドロキシ−1,3−ジプロピル−1,3−ジビニルジシロキサン、1−ヒドロキシ−3−プロポキシ−1,3−ジ−n−プロピル−1,3−ジビニルジシロキサン、1−ヒドロキシ−3−イソプロポキシ−1,3−ジプロピル−1,3−ジビニルジシロキサン、1,3−ジメトキシ−1,3−ジプロピル−1,3−ジビニルジシロキサン、1,3−ジエトキシ−1,3−ジプロピル−1,3−ジビニルジシロキサン、1,3−ジプロポキシ−1,3−ジプロピル−1,3−ジビニルジシロキサン、1,3−ジイソプロポキシ−1,3−ジプロピル−1,3−ジビニルジシロキサン、1,3−ジヒドロキシ−1,3−ジイソプロピル−1,3−ジビニルジシロキサン、1−ヒドロキシ−3−メトキシ−1,3−ジイソプロピル−1,3−ジビニルジシロキサン、1−エトキシ−3−ヒドロキシ−1,3−ジイソプロピル−1,3−ジビニルジシロキサン、1−ヒドロキシ−3−プロポキシ−1,3−ジイソプロピル−1,3−ジビニルジシロキサン、1−ヒドロキシ−3−イソプロポキシ−1,3−ジイソプロピル−1,3−ジビニルジシロキサン、1,3−ジメトキシ−1,3−ジイソプロピル−1,3−ジビニルジシロキサン、1,3−ジエトキシ−1,3−ジイソプロピル−1,3−ジビニルジシロキサン、1,3−ジプロポキシ−1,3−ジイソプロピル−1,3−ジビニルジシロキサン、1,3−ジイソプロポキシ−1,3−ジイソプロピル−1,3−ジビニルジシロキサン等が挙げられる。 Specific examples of the compound represented by the general formula (2) include 1,3-dihydroxy-1,3-dimethyl-1,3-divinyldisiloxane and 1-hydroxy-3-methoxy-1,3-dimethyl. -1,3-divinyldisiloxane, 1-ethoxy-3-hydroxy-1,3-dimethyl-1,3-divinyldisiloxane, 1-hydroxy-3-propoxy-1,3-dimethyl-1,3-divinyl Disiloxane, 1-hydroxy-3-isopropoxy-1,3-dimethyl-1,3-divinyldisiloxane, 1,3-dimethoxy-1,3-dimethyl-1,3-divinyldisiloxane, 1,3- Diethoxy-1,3-dimethyl-1,3-divinyldisiloxane, 1,3-dipropoxy-1,3-dimethyl-1,3-divinyldisiloxane, 1,3-diisopropyl Xi-1,3-dimethyl-1,3-divinyldisiloxane, 1,3-dihydroxy-1,3-diethyl-1,3-divinyldisiloxane, 1-hydroxy-3-methoxy-1,3-diethyl- 1,3-divinyldisiloxane, 1-ethoxy-3-hydroxy-1,3-diethyl-1,3-divinyldisiloxane, 1-hydroxy-3-propoxy-1,3-diethyl-1,3-divinyldi Siloxane, 1-hydroxy-3-isopropoxy-1,3-diethyl-1,3-divinyldisiloxane, 1,3-dimethoxy-1,3-diethyl-1,3-divinyldisiloxane, 1,3-diethoxy -1,3-diethyl-1,3-divinyldisiloxane, 1,3-dipropoxy-1,3-diethyl-1,3-divinyldisiloxane, 1,3-diiso Roxy-1,3-diethyl-1,3-divinyldisiloxane, 1,3-dihydroxy-1,3-dipropyl-1,3-divinyldisiloxane, 1-hydroxy-3-methoxy-1,3-dipropyl- 1,3-divinyldisiloxane, 1-ethoxy-3-hydroxy-1,3-dipropyl-1,3-divinyldisiloxane, 1-hydroxy-3-propoxy-1,3-di-n-propyl-1, 3-divinyldisiloxane, 1-hydroxy-3-isopropoxy-1,3-dipropyl-1,3-divinyldisiloxane, 1,3-dimethoxy-1,3-dipropyl-1,3-divinyldisiloxane, , 3-Diethoxy-1,3-dipropyl-1,3-divinyldisiloxane, 1,3-dipropoxy-1,3-dipropyl-1,3-divinyldisi Loxane, 1,3-diisopropoxy-1,3-dipropyl-1,3-divinyldisiloxane, 1,3-dihydroxy-1,3-diisopropyl-1,3-divinyldisiloxane, 1-hydroxy-3- Methoxy-1,3-diisopropyl-1,3-divinyldisiloxane, 1-ethoxy-3-hydroxy-1,3-diisopropyl-1,3-divinyldisiloxane, 1-hydroxy-3-propoxy-1,3- Diisopropyl-1,3-divinyldisiloxane, 1-hydroxy-3-isopropoxy-1,3-diisopropyl-1,3-divinyldisiloxane, 1,3-dimethoxy-1,3-diisopropyl-1,3-divinyl Disiloxane, 1,3-diethoxy-1,3-diisopropyl-1,3-divinyldisiloxane, 1,3-dip Epoxy-1,3-diisopropyl-1,3-divinyl disiloxane, 1,3-diisopropoxy-1,3-diisopropyl-1,3-divinyl disiloxane and the like.
反応の際、一般式(1)で表されるジアルコキシアルキルビニルシラン化合物の反応溶媒中の濃度は特に限定されるものではなく、水層との分層性および製造効率を考慮すると0.01mol/l以上が好ましく、0.1〜10mol/lが特に好ましい。 During the reaction, the concentration of the dialkoxyalkylvinylsilane compound represented by the general formula (1) in the reaction solvent is not particularly limited, and is 0.01 mol / in consideration of the separation property with the aqueous layer and the production efficiency. l or more is preferable, and 0.1-10 mol / l is especially preferable.
用いる酸または塩基は特に限定されるものではなく、例えば、塩酸、硫酸、硝酸等の無機酸;トルエンスルホン酸等の有機酸;水酸化カリウム、水酸化ナトリウム等の無機塩基;ジエチルアミン等の有機塩基を用いることができる。これらの中でも、最終目的物である一般式(3)で表される環状シロキサン化合物の収率の観点から、無機酸が好ましく特に硫酸が好ましい。 The acid or base to be used is not particularly limited. For example, inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid; organic acids such as toluenesulfonic acid; inorganic bases such as potassium hydroxide and sodium hydroxide; organic bases such as diethylamine Can be used. Among these, from the viewpoint of the yield of the cyclic siloxane compound represented by the general formula (3) which is the final target product, an inorganic acid is preferable, and sulfuric acid is particularly preferable.
酸または塩基の添加量は、特に限定されるものではなく、収率の観点からジアルコキシアルキルビニルシラン化合物1モルに対し0.01〜10mol当量が好ましく、0.1〜1mol当量が特に好ましい。 The addition amount of the acid or base is not particularly limited, and is preferably 0.01 to 10 mol equivalents and particularly preferably 0.1 to 1 mol equivalents with respect to 1 mol of the dialkoxyalkylvinylsilane compound from the viewpoint of yield.
反応温度は、一般式(1)で表されるジアルコキシアルキルビニルシラン化合物の濃度との兼ね合いによるので特に限定されるものではなく、−50〜25℃の範囲が好ましく、−20〜0℃の範囲が特に好ましい。 The reaction temperature is not particularly limited because it depends on the concentration of the dialkoxyalkylvinylsilane compound represented by the general formula (1), and is preferably in the range of −50 to 25 ° C., and in the range of −20 to 0 ° C. Is particularly preferred.
反応時間は上述の酸または塩基の添加量および反応温度との兼ね合いにより、特に限定されるものではなく、0.5〜10時間が好ましく、0.5〜6時間が特に好ましい。 The reaction time is not particularly limited depending on the balance between the amount of acid or base added and the reaction temperature, and is preferably 0.5 to 10 hours, particularly preferably 0.5 to 6 hours.
反応の際に、反応溶媒を使用してもよく、または使用せずに無溶媒系でもよい。反応溶媒を使用する場合、その種類は特に限定されるものではなく、例えばn−ペンタン、i−ペンタン、n−ヘキサン、シクロヘキサン、n−ヘプタン、n−デカン等の飽和炭化水素類;トルエン、キシレン、デセン等の不飽和炭化水素類;ジエチルエーテル、ジプロピルエーテル、tert−ブチルメチルエーテル、ジブチルエーテル、シクロペンチルメチルエーテル等のエーテル類;またはこれらの混合溶媒も使用することができる。これらの中でも水層との分層性を考慮すると飽和炭化水素類が望ましい。 In the reaction, a reaction solvent may be used, or a solventless system may be used without using it. When using a reaction solvent, the kind is not specifically limited, For example, saturated hydrocarbons, such as n-pentane, i-pentane, n-hexane, cyclohexane, n-heptane, n-decane; Toluene, xylene , Unsaturated hydrocarbons such as decene; ethers such as diethyl ether, dipropyl ether, tert-butyl methyl ether, dibutyl ether, cyclopentyl methyl ether; or a mixed solvent thereof can also be used. Among these, saturated hydrocarbons are desirable in view of the layer separation with the aqueous layer.
次に、一般式(2)で表されるジシロキサン化合物を製造した後、いったん水層を除去した後、一般式(2)で表されるジシロキサン化合物を酸または塩基の共存下、反応させ下記一般式(3)で表される環状シロキサン化合物を製造する。 Next, after manufacturing the disiloxane compound represented by the general formula (2), once removing the aqueous layer, the disiloxane compound represented by the general formula (2) is reacted in the presence of an acid or a base. A cyclic siloxane compound represented by the following general formula (3) is produced.
一般式(3)におけるR1はエチル基、ノルマルプロピル基、イソプロピル基であり、好ましくはR1がイソプロピル基である。
R 1 in the general formula (3) is an ethyl group, a normal propyl group, or an isopropyl group, and preferably R 1 is an isopropyl group.
具体的な一般式(3)で表される化合物としては、例えば2,4,6,8−テトラメチル−2,4,6,8−テトラビニルシクロテトラシロキサン、2,4,6,8−テトラエチル−2,4,6,8−テトラビニルシクロテトラシロキサン、2,4,6,8−テトラプロピル−2,4,6,8−テトラビニルシクロテトラシロキサン、2,4,6,8−テトライソプロピル−2,4,6,8−テトラビニルシクロテトラシロキサン等が挙げられる。 Specific examples of the compound represented by the general formula (3) include 2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane, 2,4,6,8- Tetraethyl-2,4,6,8-tetravinylcyclotetrasiloxane, 2,4,6,8-tetrapropyl-2,4,6,8-tetravinylcyclotetrasiloxane, 2,4,6,8-tetra Examples include isopropyl-2,4,6,8-tetravinylcyclotetrasiloxane.
一般式(2)で表される化合物の濃度は、0.01mol/l以上が好ましく、0.1〜10mol/lが特に好ましい。 The concentration of the compound represented by the general formula (2) is preferably 0.01 mol / l or more, particularly preferably 0.1 to 10 mol / l.
用いられる酸または塩基は、前述の一般式(2)で表されるジシロキサン化合物製造に用いられる酸または塩基と同様のものを例示することができる。 Examples of the acid or base used include the same acids or bases used for producing the disiloxane compound represented by the general formula (2).
酸または塩基の濃度は、特に限定されるものではなく、収率の観点からジアルコキシアルキルビニルシラン化合物に対し0.01〜10mol当量が好ましく、0.1〜0.5mol当量が特に好ましい。 The concentration of the acid or base is not particularly limited, and is preferably 0.01 to 10 mol equivalents, particularly preferably 0.1 to 0.5 mol equivalents with respect to the dialkoxyalkylvinylsilane compound from the viewpoint of yield.
また、反応温度は10〜200℃の範囲が好ましく、反応時間は30分(0.5時間)以上、1ヶ月(720時間)以下が好ましく、特に好ましくは1時間以上、24時間以下である。 The reaction temperature is preferably in the range of 10 to 200 ° C., and the reaction time is preferably 30 minutes (0.5 hours) or longer and 1 month (720 hours) or shorter, particularly preferably 1 hour or longer and 24 hours or shorter.
反応溶媒は前述の一般式(2)で表されるジシロキサン化合物製造に用いられる溶媒と同様のものを例示することができる。 Examples of the reaction solvent include the same solvents as those used in the production of the disiloxane compound represented by the general formula (2).
このようにして得られた環状シロキサン化合物は、絶縁膜等の分子内ポア前駆体プロセスプリカーサーとして好適である。 The cyclic siloxane compound thus obtained is suitable as an intramolecular pore precursor process precursor for an insulating film or the like.
絶縁膜の製造方法としては、例えばCVD法により環状シロキサン化合物を原料として基板上に薄膜を製造することができる。その場合、環状シロキサン化合物の供給方法としては、加熱した環状シロキサン化合物に不活性キャリアガスを導入し、キャリアガスに同伴させて基板の置かれた反応槽に導く方法、環状シロキサン化合物または有機溶媒に環状シロキサン化合物を溶かした溶液を気化器に送って気化器内でガス化して基板の置かれた反応槽に導く方法等がある。 As a method for producing the insulating film, for example, a thin film can be produced on the substrate using a cyclic siloxane compound as a raw material by a CVD method. In that case, as a method for supplying the cyclic siloxane compound, an inert carrier gas is introduced into the heated cyclic siloxane compound, and the carrier gas is entrained in the reaction vessel where the substrate is placed. There is a method in which a solution in which a cyclic siloxane compound is dissolved is sent to a vaporizer, gasified in the vaporizer, and led to a reaction vessel on which a substrate is placed.
有機溶媒に溶かして溶液として用いる場合、有機溶媒としては、例えば、メタノール、エタノール、イソプロパノ−ル等のアルコール類;酢酸エチル、酢酸ブチル、酢酸イソアミル等のエステル類;エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノブチルエーテル等のグリコールエーテル類;グライム、ジグライム、トリグライム、テトラヒドロフラン等のエーテル類;メチルブチルケトン、メチルイソブチルケトン、エチルブチルケトン、ジプロピルケトン、ジイソブチルケトン、メチルアミルケトン、シクロヘキサノン等のケトン類;ヘキサン、シクロヘキサン、ヘプタン、オクタン、トルエン、キシレン等の炭化水素類;等が挙げられ、特に限定されるものではない。 When used as a solution by dissolving in an organic solvent, examples of the organic solvent include alcohols such as methanol, ethanol and isopropanol; esters such as ethyl acetate, butyl acetate and isoamyl acetate; ethylene glycol monomethyl ether and ethylene glycol mono Glycol ethers such as ethyl ether and ethylene glycol monobutyl ether; ethers such as glyme, diglyme, triglyme and tetrahydrofuran; methyl butyl ketone, methyl isobutyl ketone, ethyl butyl ketone, dipropyl ketone, diisobutyl ketone, methyl amyl ketone, cyclohexanone, etc. Ketones; hydrocarbons such as hexane, cyclohexane, heptane, octane, toluene, xylene; and the like, and the like are not particularly limited.
また、CVD法としては熱CVD、プラズマCVD、光CVD等一般に使用されるCVD法であれば特に限定されない。塗布熱分解法の原料塗布方法としては例えばスピンコート法、ディップ法、噴霧法等が挙げられ、加熱方法としてはオーブン、ホットプレート等が使用できるが、塗布方法、加熱方法およびその組み合せは特に限定されない。 The CVD method is not particularly limited as long as it is a commonly used CVD method such as thermal CVD, plasma CVD, or photo CVD. Examples of the raw material coating method of the coating pyrolysis method include a spin coating method, a dip method, a spraying method, and the like. As a heating method, an oven, a hot plate, or the like can be used, but the coating method, the heating method, and a combination thereof are particularly limited. Not.
このように得られた絶縁膜は、層間絶縁膜(Low−k膜)として優れたものであり、k値は2〜3が好ましく、特に好ましくは2.5〜2.9である。 The insulating film thus obtained is excellent as an interlayer insulating film (Low-k film), and the k value is preferably 2 to 3, particularly preferably 2.5 to 2.9.
本発明により、特に8員環構造を有する2,4,6,8−テトラアルキル−2,4,6,8−テトラビニルシクロテトラシロキサン化合物を、ジアルコキシアルキルビニルシランを原料に用いて、効率的に製造することができる。この8員環構造を有する環状シロキサン化合物は、分子内ポア前駆体プロセスのプレカーサーとして有用である、 According to the present invention, a 2,4,6,8-tetraalkyl-2,4,6,8-tetravinylcyclotetrasiloxane compound having an 8-membered ring structure can be efficiently produced using dialkoxyalkylvinylsilane as a raw material. Can be manufactured. The cyclic siloxane compound having this 8-membered ring structure is useful as a precursor for an intramolecular pore precursor process.
以下、本発明を実施例に基づいて更に具体的に説明するが、本発明はこれらに限定されるものではない。 EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these.
(実施例1)
[1,3−ジアルコキシジシロキサンの合成]
不活性雰囲気下、攪拌装置、温度計を備えた100mLの3つ口フラスコに、ジメトキシイソプロピルビニルシラン(一般式(1)の化合物)5.0g(31.4mmol)とヘキサン25mlを仕込み、ドライアイス/エタノールにより内温を−15℃に冷却した。硫酸3.1g(31.4mmol)および水1.7g(94.4mmol)を、内温を−10℃以下に保ったまま滴下し、その後30分間撹拌し、目的の1,3−ジメトキシ−1,3−ジイソプロピル−1,3−ジビニルジシロキサン、1−メトキシ−3−ヒドロキシ−1,3−ジイソプロピル−1,3−ジビニルジシロキサンおよび1,3−ジヒドロキシ−1,3−ジイソプロピル−1,3−ジビニルジシロキサン(一般式(2)の化合物)が生成していることをGC/MS(EI)で確認した。反応液をGC/MS(EI)で分析した結果は以下の通りであった。
1,3−ジメトキシ−1,3−ジイソプロピル−1,3−ジビニルジシロキサン(C12H26O3Si2) m/z:231(イソプロピル基脱離)、
1−メトキシ−3−ヒドロキシ−1,3−ジイソプロピル−1,3−ジビニルジシロキサン(C11H24O3Si2) m/z:217(イソプロピル基脱離)、
1,3−ジヒドロキシ−1,3−ジイソプロピル−1,3−ジビニルジシロキサン(C10H22O3Si2) m/z:203(イソプロピル基脱離)
1,3−ジメトキシ−1,3−ジイソプロピル−1,3−ジビニルジシロキサン、1−メトキシ−3−ヒドロキシ−1,3−ジイソプロピル−1,3−ジビニルジシロキサンおよび1,3−ジヒドロキシ−1,3−ジイソプロピル−1,3−ジビニルジシロキサンは単離せず、次工程へ進んだ。
Example 1
[Synthesis of 1,3-dialkoxydisiloxane]
Under an inert atmosphere, a 100 mL three-necked flask equipped with a stirrer and a thermometer was charged with 5.0 g (31.4 mmol) of dimethoxyisopropylvinylsilane (compound of general formula (1)) and 25 ml of hexane, and dried ice / The internal temperature was cooled to -15 ° C with ethanol. 3.1 g (31.4 mmol) of sulfuric acid and 1.7 g (94.4 mmol) of water were added dropwise while maintaining the internal temperature at −10 ° C. or lower, and then stirred for 30 minutes to obtain the desired 1,3-dimethoxy-1 , 3-Diisopropyl-1,3-divinyldisiloxane, 1-methoxy-3-hydroxy-1,3-diisopropyl-1,3-divinyldisiloxane and 1,3-dihydroxy-1,3-diisopropyl-1,3 -It confirmed with GC / MS (EI) that the divinyl disiloxane (compound of General formula (2)) was producing | generating. The result of analyzing the reaction solution by GC / MS (EI) was as follows.
1,3-dimethoxy-1,3-diisopropyl-1,3-divinyldisiloxane (C 12 H 26 O 3 Si 2 ) m / z: 231 (isopropyl group elimination),
1-methoxy-3-hydroxy-1,3-diisopropyl-1,3-divinyldisiloxane (C 11 H 24 O 3 Si 2 ) m / z: 217 (isopropyl group elimination),
1,3-dihydroxy-1,3-diisopropyl-1,3-divinyldisiloxane (C 10 H 22 O 3 Si 2 ) m / z: 203 (isopropyl group elimination)
1,3-dimethoxy-1,3-diisopropyl-1,3-divinyldisiloxane, 1-methoxy-3-hydroxy-1,3-diisopropyl-1,3-divinyldisiloxane and 1,3-dihydroxy-1, The 3-diisopropyl-1,3-divinyldisiloxane was not isolated and proceeded to the next step.
[シクロテトラシロキサンの合成]
上記反応液を分層して水層を除去したのち、硫酸1.5g(0.16mol)を加え、還流条件で1時間撹拌した。反応終了後、硫酸層を除去し、得られた有機層を炭酸水素ナトリウム水溶液で中和し硫酸マグネシウムで乾燥した。ロータリーエバポレーターで溶媒留去したのち、減圧蒸留にて目的の2,4,6,8−テトライソプロピル−2,4,6,8−テトラビニルシクロテトラシロキサン(一般式(3)の化合物)が主成分(GC面積%:54.0%)の液体が2.6g(2,4,6,8−テトライソプロピル−2,4,6,8−テトラビニルシクロテトラシロキサンの収量:1.4g=2.6g×0.54)得られた。一般式(3)の化合物の収率は39.7%であった。この蒸留精製物をGC/MS(EI)で分析した結果は以下の通りであった。
[Synthesis of cyclotetrasiloxane]
After separating the reaction solution and removing the aqueous layer, 1.5 g (0.16 mol) of sulfuric acid was added, and the mixture was stirred for 1 hour under reflux conditions. After completion of the reaction, the sulfuric acid layer was removed, and the obtained organic layer was neutralized with an aqueous sodium hydrogen carbonate solution and dried over magnesium sulfate. After distilling off the solvent with a rotary evaporator, the desired 2,4,6,8-tetraisopropyl-2,4,6,8-tetravinylcyclotetrasiloxane (compound of general formula (3)) is mainly produced by distillation under reduced pressure. 2.6 g of liquid of component (GC area%: 54.0%) (yield of 2,4,6,8-tetraisopropyl-2,4,6,8-tetravinylcyclotetrasiloxane: 1.4 g = 2) .6 g × 0.54). The yield of the compound of general formula (3) was 39.7%. The results of analysis of this distilled and purified product by GC / MS (EI) were as follows.
2,4,6,8−テトライソプロピル−2,4,6,8−テトラビニルシクロテトラシロキサン(C20H40O4Si4) m/z:370(イソプロピル基2個脱離)
(比較例1)
実施例1において、シクロテトラシロキサンの合成工程で分層・水層除去作業を行わないこと以外は、実施例1と同様の実験を行った。蒸留精製物(液体)は、収量2.6g、目的の2,4,6,8−テトライソプロピル−2,4,6,8−テトラビニルシクロテトラシロキサンは、GC面積%が2.4%であり、極微量しか(2.6g×0.024=0.062g、収率1.7%)生成しなかった。
2,4,6,8
(Comparative Example 1)
In Example 1, the same experiment as in Example 1 was performed except that the separation / aqueous layer removal operation was not performed in the cyclotetrasiloxane synthesis step. Distilled purified product (liquid) has a yield of 2.6 g, and the desired 2,4,6,8-tetraisopropyl-2,4,6,8-tetravinylcyclotetrasiloxane has a GC area percentage of 2.4%. There was only a very small amount (2.6 g × 0.024 = 0.062 g, yield 1.7%).
(実施例2)
[シクロテトラシロキサン選択率の向上]
実施例1において、シクロテトラシロキサンの合成工程での反応を、還流条件で6時間撹拌に変更した以外は、実施例1と同様の実験を行った。目的の2,4,6,8−テトライソプロピル−2,4,6,8−テトラビニルシクロテトラシロキサンへの転換率の経時変化をGC分析により確認した。反応終了後、実施例1と同様に処理を行った。一般式(3)の化合物の収率は69.2%であった。結果を図1および図2に示す。
(Example 2)
[Improvement of cyclotetrasiloxane selectivity]
In Example 1, the same experiment as in Example 1 was performed except that the reaction in the synthesis process of cyclotetrasiloxane was changed to stirring for 6 hours under reflux conditions. The time-dependent change in the conversion rate to the desired 2,4,6,8-tetraisopropyl-2,4,6,8-tetravinylcyclotetrasiloxane was confirmed by GC analysis. After completion of the reaction, the same treatment as in Example 1 was performed. The yield of the compound of general formula (3) was 69.2%. The results are shown in FIG. 1 and FIG.
(実施例3)
[シクロテトラシロキサン選択率の向上、室温(25℃)1ヶ月(720時間)]
実施例1において、シクロテトラシロキサンの合成工程での反応を、還流条件で30分撹拌後さらに室温で1ヶ月撹拌に変更した以外は、実施例1と同様の実験を行った。目的の2,4,6,8−テトライソプロピル−2,4,6,8−テトラビニルシクロテトラシロキサンへの転換率の経時変化をGC分析により確認した。反応終了後、実施例1と同様に処理を行った。一般式(3)の化合物の収率は77.0%であった。結果を図3および図4に示す。
(Example 3)
[Improvement of cyclotetrasiloxane selectivity, room temperature (25 ° C.) 1 month (720 hours)]
The same experiment as in Example 1 was performed except that the reaction in the synthesis process of cyclotetrasiloxane in Example 1 was changed to stirring for 1 month at room temperature after stirring for 30 minutes under reflux conditions. The time-dependent change in the conversion rate to the desired 2,4,6,8-tetraisopropyl-2,4,6,8-tetravinylcyclotetrasiloxane was confirmed by GC analysis. After completion of the reaction, the same treatment as in Example 1 was performed. The yield of the compound of general formula (3) was 77.0%. The results are shown in FIG. 3 and FIG.
(実施例4)
[2,4,6,8−テトライソプロピル−2,4,6,8−テトラビニルシクロテトラシロキサンを用いた絶縁膜の製造]
実施例1で得た2,4,6,8−テトライソプロピル−2,4,6,8−テトラビニルシクロテトラシロキサン(一般式(3)の化合物)が主成分の液体を蒸留精製した2,4,6,8−テトライソプロピル−2,4,6,8−テトラビニルシクロテトラシロキサンを原料として、図5の装置を用いて、原料温度120℃、キャリアガス(He)流量100sccm、原料容器内圧力22Torr、基板温度150℃、反応室内圧力100Paで、電源周波数13.56MHzのRF電源の出力を25Wに設定したPECVD法により、Si基板上に2分成膜を行った。成膜した絶縁膜について日本分光株式会社製のエリプソメーター(型式:MEL−30S)を用いて膜厚を測定したところ約150nmであった。この絶縁膜上に、アルミ電極を蒸着法によって成膜した後、Agilent社製の4284AプレシジョンLCRメータにより25℃、周波数1kHzの静電容量と誘電損失を測定し、比誘電率を計算したところ、k 2.69、tanδ=0.0004であった。測定部分の誘電体の面積は1.01×10−8m2であった。また、直流電流+40Vの条件でのリーク電流を測定したところ、8.8×10−10A/cm2の電流密度であった。
Example 4
[Production of insulating film using 2,4,6,8-tetraisopropyl-2,4,6,8-tetravinylcyclotetrasiloxane]
2,4,6,8-tetraisopropyl-2,4,6,8-tetravinylcyclotetrasiloxane (compound of general formula (3)) obtained in Example 1 was purified by distillation. Using 4,6,8-tetraisopropyl-2,4,6,8-tetravinylcyclotetrasiloxane as a raw material, using the apparatus of FIG. A film was formed on the Si substrate for 2 minutes by PECVD with a pressure of 22 Torr, a substrate temperature of 150 ° C., a reaction chamber pressure of 100 Pa, and an output of an RF power supply with a power supply frequency of 13.56 MHz set to 25 W. When the film thickness of the formed insulating film was measured using an ellipsometer (model: MEL-30S) manufactured by JASCO Corporation, it was about 150 nm. After forming an aluminum electrode on this insulating film by vapor deposition, the capacitance and dielectric loss at 25 ° C. and a frequency of 1 kHz were measured with an Agilent 4284A Precision LCR meter, and the relative dielectric constant was calculated. k 2.69 and tan δ = 0.0004. The area of the dielectric in the measurement part was 1.01 × 10 −8 m 2 . Further, when the leakage current was measured under the condition of DC current + 40V, the current density was 8.8 × 10 −10 A / cm 2 .
(実施例5)
[1,3−ジメトキシ−1,3−ジイソプロピル−1,3−ジビニルジシロキサン、1−メトキシ−3−ヒドロキシ−1,3−ジイソプロピル−1,3−ジビニルジシロキサンおよび1,3−ジヒドロキシ−1,3−ジイソプロピル−1,3−ジビニルジシロキサンの合成]
不活性雰囲気下、攪拌装置、温度計を備えた200mLの3つ口フラスコに、ジメトキシイソプロピルビニルシラン15.0g(93.6mmol)、ヘキサン90mlを仕込み、ドライアイス/エタノールにより内温を−20℃に冷却した。硫酸0.97g(9.9mmol)を添加し、水3.51g(195mmol)を内温−15℃以下に保ち30分かけて滴下した。内温を−10℃に保持したまま5時間撹拌後、トリエチルアミン2.7g(26.7mmol)を添加し、水層を除去し有機層を硫酸マグネシウムで乾燥した。ろ過後、ロータリーエバポレーターで溶媒留去したのち、減圧蒸留にて目的の1,3−ジメトキシ−1,3−ジイソプロピル−1,3−ジビニルジシロキサン、1−メトキシ−3−ヒドロキシ−1,3−ジイソプロピル−1,3−ジビニルジシロキサンおよび1,3−ジヒドロキシ−1,3−ジイソプロピル−1,3−ジビニルジシロキサンの混合物である液体2.7gが得られた。この混合物をシリカゲルカラムクロマトグラフィー(溶出溶媒:ヘキサン/酢酸エチル=9/1)により精製し、目的化合物である1,3−ジメトキシ−1,3−ジイソプロピル−1,3−ジビニルジシロキサンを0.51g、収率4.0%、1−メトキシ−3−ヒドロキシ−1,3−ジイソプロピル−1,3−ジビニルジシロキサンを1.78g、収率14.6%、1,3−ジヒドロキシ−1,3−ジイソプロピル−1,3−ジビニルジシロキサンを0.31g、収率2.7%で得た。それぞれの化合物をGC/MS(EI)(図6−8)および1H−NMRで分析した結果は以下の通りであった。
(Example 5)
[1,3-dimethoxy-1,3-diisopropyl-1,3-divinyldisiloxane, 1-methoxy-3-hydroxy-1,3-diisopropyl-1,3-divinyldisiloxane and 1,3-dihydroxy-1 Of 3,3-diisopropyl-1,3-divinyldisiloxane]
In an inert atmosphere, a 200 mL three-necked flask equipped with a stirrer and a thermometer was charged with 15.0 g (93.6 mmol) of dimethoxyisopropylvinylsilane and 90 ml of hexane, and the internal temperature was adjusted to −20 ° C. with dry ice / ethanol. Cooled down. 0.97 g (9.9 mmol) of sulfuric acid was added, and 3.51 g (195 mmol) of water was added dropwise over 30 minutes while maintaining the internal temperature at −15 ° C. or lower. After stirring for 5 hours while maintaining the internal temperature at −10 ° C., 2.7 g (26.7 mmol) of triethylamine was added, the aqueous layer was removed, and the organic layer was dried over magnesium sulfate. After filtration, the solvent was distilled off with a rotary evaporator, and then the desired 1,3-dimethoxy-1,3-diisopropyl-1,3-divinyldisiloxane, 1-methoxy-3-hydroxy-1,3- There were obtained 2.7 g of a liquid which was a mixture of diisopropyl-1,3-divinyldisiloxane and 1,3-dihydroxy-1,3-diisopropyl-1,3-divinyldisiloxane. This mixture was purified by silica gel column chromatography (eluent: hexane / ethyl acetate = 9/1), and 1,3-dimethoxy-1,3-diisopropyl-1,3-divinyldisiloxane, which is the target compound, was reduced to a concentration of 0. 51 g, 4.0% yield, 1.78 g 1-methoxy-3-hydroxy-1,3-diisopropyl-1,3-divinyldisiloxane, 14.6% yield, 1,3-dihydroxy-1, 0.31 g of 3-diisopropyl-1,3-divinyldisiloxane was obtained with a yield of 2.7%. The result of having analyzed each compound by GC / MS (EI) (FIGS. 6-8) and 1 H-NMR was as follows.
GC/MS(EI)
1,3−ジメトキシ−1,3−ジイソプロピル−1,3−ジビニルジシロキサン(C12H26O3Si2) m/z:231(イソプロピル基脱離)
1−メトキシ−3−ヒドロキシ−1,3−ジイソプロピル−1,3−ジビニルジシロキサン(C11H24O3Si2) m/z:217(イソプロピル基脱離)
1,3−ジヒドロキシ−1,3−ジイソプロピル−1,3−ジビニルジシロキサン(C10H22O3Si2) m/z:203(イソプロピル基脱離)
1H−NMR(500MHz,CDCl3,δppm)
1,3−ジヒドロキシ−1,3−ジイソプロピル−1,3−ジビニルジシロキサン
6.13−5.92(m,6H)、3.53(s,6H)、1.01(d,J=6.5Hz,12H)、0.94−0.87(m,2H)
1−メトキシ−3−ヒドロキシ−1,3−ジイソプロピル−1,3−ジビニルジシロキサン
6.13−5.90(m,6H)、3.52(s,3H)、2.31(s,1H)、1.00(dd,J=6Hz,J=2.5Hz,6H)、1.03(d,J=6Hz,6H)、0.96−0.88(m,2H)
1,3−ジヒドロキシ−1,3−ジイソプロピル−1,3−ジビニルジシロキサン
6.10−5.91(m,6H)、2.40(s,2H)、1.01(d,J=7.5Hz,12H)、0.97−0.89(m,2H)
(参考例1)
[2,4,6−トリイソプロピル−2,4,6−トリビニルシクロトリシロキサンを用いた絶縁膜の製造]
2,4,6−トリイソプロピル−2,4,6−トリビニルシクロトリシロキサンを原料として、図5の装置を用いて、原料温度83℃、キャリアガス(He)流量100sccm、原料容器内圧力22Torr、基板温度150℃、反応室内圧力100Paで、電源周波数13.56MHzのRF電源の出力を25Wに設定したPECVD法により、Si基板上に3分成膜を行った。成膜した絶縁膜について日本分光株式会社製のエリプソメーター(型式:MEL−30S)を用いて膜厚を測定したところ約210nmであった。この絶縁膜上に、アルミ電極を蒸着法によって成膜した後、Agilent社製の4284AプレシジョンLCRメータにより25℃、周波数1kHzの静電容量と誘電損失を測定し、比誘電率を計算したところ、k 2.74、tanδ=0.01であった。測定部分の誘電体の面積は9.88×10−7m2であった。また、直流電流+40Vの条件でのリーク電流を測定したところ、2.0×10−9A/cm2の電流密度であった。
GC / MS (EI)
1,3-dimethoxy-1,3-diisopropyl-1,3-divinyldisiloxane (C 12 H 26 O 3 Si 2 ) m / z: 231 (isopropyl group elimination)
1-methoxy-3-hydroxy-1,3-diisopropyl-1,3-divinyldisiloxane (C 11 H 24 O 3 Si 2 ) m / z: 217 (isolation of isopropyl group)
1,3-dihydroxy-1,3-diisopropyl-1,3-divinyldisiloxane (C 10 H 22 O 3 Si 2 ) m / z: 203 (isopropyl group elimination)
1 H-NMR (500 MHz, CDCl 3 , δ ppm)
1,3-dihydroxy-1,3-diisopropyl-1,3-divinyldisiloxane 6.13-5.92 (m, 6H), 3.53 (s, 6H), 1.01 (d, J = 6 .5Hz, 12H), 0.94-0.87 (m, 2H)
1-methoxy-3-hydroxy-1,3-diisopropyl-1,3-divinyldisiloxane 6.13-5.90 (m, 6H), 3.52 (s, 3H), 2.31 (s, 1H ), 1.00 (dd, J = 6 Hz, J = 2.5 Hz, 6H), 1.03 (d, J = 6 Hz, 6H), 0.96-0.88 (m, 2H)
1,3-dihydroxy-1,3-diisopropyl-1,3-divinyldisiloxane 6.10-5.91 (m, 6H), 2.40 (s, 2H), 1.01 (d, J = 7 .5Hz, 12H), 0.97-0.89 (m, 2H)
(Reference Example 1)
[Production of insulating film using 2,4,6-triisopropyl-2,4,6-trivinylcyclotrisiloxane]
Using 2,4,6-triisopropyl-2,4,6-trivinylcyclotrisiloxane as a raw material, using the apparatus of FIG. 5, the raw material temperature is 83 ° C., the carrier gas (He) flow rate is 100 sccm, and the raw material container pressure is 22 Torr. A film was formed on the Si substrate for 3 minutes by PECVD with a substrate temperature of 150 ° C., a reaction chamber pressure of 100 Pa, and an RF power output of 13.56 MHz set to 25 W. When the film thickness of the formed insulating film was measured using an ellipsometer (model: MEL-30S) manufactured by JASCO Corporation, it was about 210 nm. After forming an aluminum electrode on this insulating film by vapor deposition, the capacitance and dielectric loss at 25 ° C. and a frequency of 1 kHz were measured with an Agilent 4284A Precision LCR meter, and the relative dielectric constant was calculated. k 2.74, tan δ = 0.01. The area of the dielectric in the measurement portion was 9.88 × 10 −7 m 2 . Further, when the leakage current was measured under the condition of direct current +40 V, it was a current density of 2.0 × 10 −9 A / cm 2 .
実施例4の環状8員環である2,4,6,8−テトライソプロピル−2,4,6,8−テトラビニルシクロテトラシロキサンからなる膜は、参考例1の環状6員環である2,4,6−トリイソプロピル−2,4,6−トリビニルシクロトリシロキサンからなる膜よりも、よりk値が小さく、絶縁膜として好適である。 A film made of 2,4,6,8-tetraisopropyl-2,4,6,8-tetravinylcyclotetrasiloxane, which is a cyclic 8-membered ring of Example 4, is a cyclic 6-membered ring of Reference Example 2 , 4,6-triisopropyl-2,4,6-trivinylcyclotrisiloxane has a smaller k value and is suitable as an insulating film.
1.PECVDチャンバー
2.基板
3.上部電極
4.下部電極
5.恒温槽
6.原料容器
7.真空ポンプ
8.マッチング回路
9.RF電源
10.アース
11.ヒーター
12.マスフローコントローラー
13.ヘリウムガス
1. PECVD chamber Substrate 3.
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JP3079939B2 (en) * | 1994-08-25 | 2000-08-21 | 信越化学工業株式会社 | Method for producing low molecular weight organosiloxane having silanol group |
JP3252642B2 (en) * | 1995-03-06 | 2002-02-04 | 信越化学工業株式会社 | Method for producing low molecular weight organosilane or siloxane having silanol group |
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JP2008274365A (en) * | 2007-05-01 | 2008-11-13 | Shin Etsu Chem Co Ltd | MATERIAL FOR FORMING Si-CONTAINING FILM, Si-CONTAINING FILM, MANUFACTURING METHOD THEREFOR, AND SEMICONDUCTOR DEVICE |
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