WO2003011945A2 - Siloxane resins - Google Patents
Siloxane resins Download PDFInfo
- Publication number
- WO2003011945A2 WO2003011945A2 PCT/US2002/019283 US0219283W WO03011945A2 WO 2003011945 A2 WO2003011945 A2 WO 2003011945A2 US 0219283 W US0219283 W US 0219283W WO 03011945 A2 WO03011945 A2 WO 03011945A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- siloxane
- group
- carbon atoms
- groups
- resin
- Prior art date
Links
- 239000011347 resin Substances 0.000 title claims abstract description 182
- 229920005989 resin Polymers 0.000 title claims abstract description 181
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 title claims abstract description 121
- 238000000576 coating method Methods 0.000 claims abstract description 87
- 239000000203 mixture Substances 0.000 claims abstract description 52
- -1 siloxane units Chemical group 0.000 claims abstract description 47
- 239000000758 substrate Substances 0.000 claims abstract description 45
- 239000011248 coating agent Substances 0.000 claims abstract description 44
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 40
- 239000001257 hydrogen Substances 0.000 claims abstract description 34
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 34
- 238000010438 heat treatment Methods 0.000 claims abstract description 33
- 125000000962 organic group Chemical group 0.000 claims abstract description 31
- 239000011342 resin composition Substances 0.000 claims abstract description 30
- 229910014307 bSiO Inorganic materials 0.000 claims abstract description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 68
- 239000002904 solvent Substances 0.000 claims description 64
- 238000000034 method Methods 0.000 claims description 63
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 39
- 229910000077 silane Inorganic materials 0.000 claims description 39
- 230000015572 biosynthetic process Effects 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 230000000694 effects Effects 0.000 claims description 23
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 23
- 150000002431 hydrogen Chemical class 0.000 claims description 21
- 150000004756 silanes Chemical class 0.000 claims description 21
- 229910001868 water Inorganic materials 0.000 claims description 21
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 20
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- 239000008199 coating composition Substances 0.000 claims description 10
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 9
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 125000001309 chloro group Chemical group Cl* 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract description 3
- 230000002277 temperature effect Effects 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 99
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 44
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 37
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 36
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 28
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 28
- 229910052710 silicon Inorganic materials 0.000 description 28
- 239000010703 silicon Substances 0.000 description 25
- 235000012431 wafers Nutrition 0.000 description 23
- 229910052757 nitrogen Inorganic materials 0.000 description 22
- 238000006243 chemical reaction Methods 0.000 description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 18
- 229910052786 argon Inorganic materials 0.000 description 14
- 239000000047 product Substances 0.000 description 14
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 14
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 13
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 13
- 238000004458 analytical method Methods 0.000 description 13
- 239000000463 material Substances 0.000 description 13
- 229940043265 methyl isobutyl ketone Drugs 0.000 description 13
- 239000011541 reaction mixture Substances 0.000 description 12
- 239000010409 thin film Substances 0.000 description 12
- 238000005259 measurement Methods 0.000 description 11
- 239000012528 membrane Substances 0.000 description 11
- 238000010926 purge Methods 0.000 description 10
- 239000010453 quartz Substances 0.000 description 10
- 238000004528 spin coating Methods 0.000 description 10
- 238000001704 evaporation Methods 0.000 description 9
- 239000010408 film Substances 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- 239000012299 nitrogen atmosphere Substances 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- 125000003545 alkoxy group Chemical group 0.000 description 8
- 239000006227 byproduct Substances 0.000 description 8
- 230000008020 evaporation Effects 0.000 description 8
- 239000011148 porous material Substances 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 7
- 125000001424 substituent group Chemical group 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000000151 deposition Methods 0.000 description 6
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadec-1-ene Chemical compound CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 229920003209 poly(hydridosilsesquioxane) Polymers 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 229910052814 silicon oxide Inorganic materials 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- 125000004423 acyloxy group Chemical group 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 239000012300 argon atmosphere Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 238000005229 chemical vapour deposition Methods 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 5
- 238000000197 pyrolysis Methods 0.000 description 5
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 238000006386 neutralization reaction Methods 0.000 description 4
- 230000003472 neutralizing effect Effects 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 229920006009 resin backbone Polymers 0.000 description 4
- 230000000717 retained effect Effects 0.000 description 4
- 238000002411 thermogravimetry Methods 0.000 description 4
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 3
- 229910004726 HSiO3/2 Inorganic materials 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 125000002252 acyl group Chemical group 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 150000004820 halides Chemical group 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 239000001307 helium Substances 0.000 description 3
- 229910052734 helium Inorganic materials 0.000 description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 3
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 239000002198 insoluble material Substances 0.000 description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 125000004430 oxygen atom Chemical group O* 0.000 description 3
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 3
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 125000001731 2-cyanoethyl group Chemical group [H]C([H])(*)C([H])([H])C#N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 238000003491 array Methods 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 2
- 125000004063 butyryl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 150000004292 cyclic ethers Chemical class 0.000 description 2
- 239000010432 diamond Substances 0.000 description 2
- 229910003460 diamond Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 125000003104 hexanoyl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 2
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical compound [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000002230 thermal chemical vapour deposition Methods 0.000 description 2
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 2
- 125000003774 valeryl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- GJWHXWMUGWZNTO-UHFFFAOYSA-N 2,2-dimethylpropane Chemical compound [CH2]C(C)(C)C GJWHXWMUGWZNTO-UHFFFAOYSA-N 0.000 description 1
- 125000006176 2-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
- 125000003229 2-methylhexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000005916 2-methylpentyl group Chemical group 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000005046 Chlorosilane Substances 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- 229910004721 HSiCl3 Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910008051 Si-OH Inorganic materials 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 229910020487 SiO3/2 Inorganic materials 0.000 description 1
- 229910020175 SiOH Inorganic materials 0.000 description 1
- 229910006358 Si—OH Inorganic materials 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- DZPJVKXUWVWEAD-UHFFFAOYSA-N [C].[N].[Si] Chemical compound [C].[N].[Si] DZPJVKXUWVWEAD-UHFFFAOYSA-N 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- UBMXAAKAFOKSPA-UHFFFAOYSA-N [N].[O].[Si] Chemical compound [N].[O].[Si] UBMXAAKAFOKSPA-UHFFFAOYSA-N 0.000 description 1
- UMVBXBACMIOFDO-UHFFFAOYSA-N [N].[Si] Chemical compound [N].[Si] UMVBXBACMIOFDO-UHFFFAOYSA-N 0.000 description 1
- OPARTXXEFXPWJL-UHFFFAOYSA-N [acetyloxy-bis[(2-methylpropan-2-yl)oxy]silyl] acetate Chemical compound CC(=O)O[Si](OC(C)=O)(OC(C)(C)C)OC(C)(C)C OPARTXXEFXPWJL-UHFFFAOYSA-N 0.000 description 1
- 239000002156 adsorbate Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- MQTOSJVFKKJCRP-BICOPXKESA-N azithromycin Chemical compound O([C@@H]1[C@@H](C)C(=O)O[C@@H]([C@@]([C@H](O)[C@@H](C)N(C)C[C@H](C)C[C@@](C)(O)[C@H](O[C@H]2[C@@H]([C@H](C[C@@H](C)O2)N(C)C)O)[C@H]1C)(C)O)CC)[C@H]1C[C@@](C)(OC)[C@@H](O)[C@H](C)O1 MQTOSJVFKKJCRP-BICOPXKESA-N 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 235000010216 calcium carbonate Nutrition 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical class Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- DLHSCEYJQODJPQ-UHFFFAOYSA-N dichloro-bis[(2-methylpropan-2-yl)oxy]silane Chemical compound CC(C)(C)O[Si](Cl)(Cl)OC(C)(C)C DLHSCEYJQODJPQ-UHFFFAOYSA-N 0.000 description 1
- WLIGPBOVYTVHKD-UHFFFAOYSA-N dihydroxy-bis[(2-methylpropan-2-yl)oxy]silane Chemical compound CC(C)(C)O[Si](O)(O)OC(C)(C)C WLIGPBOVYTVHKD-UHFFFAOYSA-N 0.000 description 1
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- GQUUKQQWGMHLQK-UHFFFAOYSA-N ditert-butyl diethyl silicate Chemical compound CCO[Si](OCC)(OC(C)(C)C)OC(C)(C)C GQUUKQQWGMHLQK-UHFFFAOYSA-N 0.000 description 1
- YGHXHELPFKLYNJ-UHFFFAOYSA-N ditert-butyl dimethyl silicate Chemical compound CC(C)(C)O[Si](OC)(OC)OC(C)(C)C YGHXHELPFKLYNJ-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000005566 electron beam evaporation Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 238000001912 gas jet deposition Methods 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- DKAGJZJALZXOOV-UHFFFAOYSA-N hydrate;hydrochloride Chemical compound O.Cl DKAGJZJALZXOOV-UHFFFAOYSA-N 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 238000002459 porosimetry Methods 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 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
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 125000005389 trialkylsiloxy group Chemical group 0.000 description 1
- 239000005052 trichlorosilane Substances 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- 125000000725 trifluoropropyl group Chemical group [H]C([H])(*)C([H])([H])C(F)(F)F 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
-
- 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
-
- 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
- H01L21/02203—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 porous
-
- 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
- H01L21/02205—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
-
- 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
- H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
- H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
- H01L21/02282—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process liquid deposition, e.g. spin-coating, sol-gel techniques, spray coating
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/12—Polysiloxanes containing silicon bound to hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
- C08G77/16—Polysiloxanes containing silicon bound to oxygen-containing groups to hydroxyl groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
- C08G77/18—Polysiloxanes containing silicon bound to oxygen-containing groups to alkoxy or aryloxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/24—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen halogen-containing groups
Definitions
- This invention pertains to a siloxane resin composition
- a siloxane resin composition comprising R.1 Si ⁇ 3/2 siloxane units, R2siO3/2 siloxane units and (R ⁇ O ⁇ SiO (A-b)/2 siloxane units wherein R is independently selected from the group consisting of alkyl having 1 to 5 carbon atoms, hydrogen, and mixtures thereof; R ⁇ is independently selected from the group consisting of monovalent organic groups having 6 to 30 carbon atoms and monovalent substituted organic groups having 6 to 30 carbon atoms; R ⁇ is independently selected from the group consisting of branched alkyl groups having 3 to 30 carbon atoms and branched substituted alkyl groups having 3 to 30 carbon atoms, and b is from 1 to 3.
- This invention further pertains to insoluble porous resins and insoluble porous coatings produced from the siloxane resin composition.
- Semiconductor devices often have one or more arrays of patterned interconnect levels that serve to electrically couple the individual circuit elements forming an integrated circuit (IC).
- the interconnect levels are typically separated by an insulating or dielectric coating.
- a silicon oxide coating formed using chemical vapor deposition (CVD) or plasma enhanced techniques (PECVD) was the most commonly used material for such dielectric coatings.
- CVD chemical vapor deposition
- PECVD plasma enhanced techniques
- dielectric coatings formed from siloxane-based resins have found use.
- An example of such coatings are those formed from hydrogen silsesquioxane resins as described for example in Collins et al., U.S. Patent No. 3,615,272 and Haluska et al. U.S. Patent No. 4,756,977. While such coatings provide lower dielectric constants than CVD or PECVD silicon oxide coatings and also provide other benefits such as enhanced gap filling and surface planarization, typically the dielectric constants of such coatings are limited to approximately 3 or greater.
- a porous coating typically has a lower density than a corresponding solid coating.
- U.S. Patent No. 5,446,088 describes a method of co-hydrolyzing silanes of the formulas HSi(OR)3 and Si(OR)4 to form co-hydrolysates useful in the formation of coatings.
- the R group is an organic group containing 1-20 carbon atoms, which when bonded to silicon through the oxygen atom, forms a hydrolyzable substituent.
- Especially preferred hydrolyzable groups are methoxy and ethoxy.
- the hydrolysis with water is carried out in an acidified oxygen containing polar solvent.
- the co-hydrolyzates in a solvent are applied to a substrate, the solvent evaporated and the coating heated to 50 to 1000°C to ⁇ convert the coating to silica.
- Haluska does not disclose silanes having branched alkoxy groups.
- a porous network is formed by depositing a coating on a substrate with a solution comprising a hydrogen silsesquioxane resin and a solvent in a manner in which at least 5 volume % of the solvent remains in the coating after deposition.
- the coating is then exposed to an environment comprising a basic catalyst and water; the solvent is evaporated from the coating to form a porous network with a dielectric constant in the range of 1.5 to 2.4.
- WO 98/49721 describe a process for forming a nanoporous dielectric coating on a substrate.
- the process comprises the steps of blending an alkoxysilane with a solvent composition and optional water; depositing the mixture onto a substrate while evaporating at least a portion of the solvent; placing the substrate in a sealed chamber and evacuating the chamber to a pressure below atmospheric pressure; exposing the substrate to water vapor at a pressure below atmospheric pressure and then exposing the substrate to base vapor.
- Mikoshiba et al. U.S.'Patent 6,022,814, describe a process for forming silicon oxide films on a substrate from hydrogen or methyl siloxane-based resins having organic substituents that are removed at a temperature ranging from 250°C to the glass transition point of the resin.
- Silicon oxide film properties reported include a density of 0.8 to 1.4 g/cm ⁇ , an average pore diameter of 1 to 3 nm, a surface area of 600 to 1,500 m ⁇ /g and a dielectric constant in the range of 2.0 to 3.0.
- the useful organic substituents that can be oxidized at a temperature of 250°C or higher include substituted and unsubstituted alkyl or alkoxy groups exemplified by 3,3,3-triflouropropyl, ⁇ -phenethyl group, t-butyl group, 2-cyanoethyl group, benzyl group, and vinyl group.
- (trisiloxysilyl) units were spin-coated on to a substrate and heated at 250°C to provide rigid siloxane matrices. The coatings were then heated at 450°C to 500°C to remove thermally labile groups and holes were left corresponding to the size of the substituents, having a dielectric constant of about 2.3. Trifluoropropyl, cyanoethyl, phenylethyl, and propyl groups were investigated as the thermally labile substituents.
- siloxane resin composition having improved storage stability. It is also an object of this invention to show a method for making siloxane resins and a method for curing these resins to produce insoluble porous coatings having a dielectric constant of 1.5 to 3.0, a porosity from 1 to 60 volume percent and a modulus from 1.0 to 10 GPa. These coatings have the advantage that they may be formed using conventional thin film processing.
- the total amount of components (A), (B) and (C) is 100 mole parts and the sum of components (A), (B) and (C) is at least 50 percent of the total siloxane units in the resin composition.
- This invention also pertains to a method for making siloxane resins by reacting a silane or a mixture of silanes of the formula RIS1X3, a silane or a mixture of silanes of the formula R2S 3, and a silane or a mixture of silanes of the formula (R3 ⁇ ) c SiX(4_ c ) where
- R! is independently selected from the group consisting of alkyl groups having 1 to 5 carbon atoms, hydrogen, and mixtures thereof;
- R ⁇ is independently selected from the group consisting of monovalent organic groups having 6 to 30 carbon atoms and substituted monovalent organic groups having 6 to 30 carbon atoms;
- R ⁇ is independently selected from the group consisting of branched alkyl groups and substituted branched alkyl groups having 3 to 30 carbon atoms;
- c is from 1 to 3 and
- X is a hydrolyzable group or a hydroxy group.
- the insoluble porous coatings have a dielectric constant in the range of 1.5 to 3.0, a porosity of 1 to 60 volume percent and a modulus in the range of 1.0 to 10 GPa.
- DETAILED DESCRIPTION OF THE INVENTION [0015]
- the siloxane resin composition comprises:
- R2siO3/2 siloxane units wherein R 2 is independently selected from the group consisting of monovalent organic groups having 6 to 30 carbon atoms and monovalent substituted organic groups having 6 to 30 carbon atoms;
- the total amount of components (A), (B) and (C) is 100 mole parts and the sum of components (A), (B) and (C) is at least 50 percent of the total siloxane units in the resin composition.
- the siloxane resin contains an average of 30 to 60 mole parts component (A), 10 to 25 mole parts component (B) and 20 to 50 mole parts (C) where the total amount of components (A), (B) and (C) combined is 100 mole parts and the sum of (A), (B) and (C) is at least 70 percent of the total siloxane units in the resin composition.
- the structure of the siloxane resin is not specifically limited.
- the siloxane resins may be essentially fully condensed or may be only partially reacted (i.e., containing less than 10 mole % Si-OR and/or less than 30 mole % Si-OH).
- the partially reacted siloxane resins may be exemplified by, but not limited to, siloxane units such as RlSi(X) ( jOn_ ( i/2);
- R 2 Si(X)dO(3_d /2); and Si(X)d (OR )f 0(4-d-f/2)l in which R 1 , R 2 , and R 3 are defined above; each X is independently a hydrolyzable group or a hydroxy group, and d and f are from 1 to 2.
- the hydrolyzable group is an organic group attached to a silicon atom through an oxygen atom (Si-OR) forming a silicon bonded alkoxy group or a silicon bonded acyloxy group.
- R is exemplified by, but not limited to, linear alkyl groups having 1 to 6 carbon atoms 'such as methyl, ethyl, propyl, butyl, pentyl, or hexyl and acyl groups having 1 to 6 carbon atoms such as formyl, acetyl, propionyl, butyryl, valeryl or hexanoyl.
- the siloxane resin may also contain less than about 10 mole percent Si ⁇ 4/2 units.
- the siloxane resins have a weight average molecular weight in a range of 400 to 160,000 and preferably in a range of 5,000 to 100,000. [0018] R!
- alkyl group can be a linear alkyl group having 1 to 5 carbon atoms, hydrogen and mixtures thereof.
- the alkyl group is exemplified by, but not limited to, methyl, ethyl, propyl, butyl, and pentyl. It is preferred that R is methyl, hydrogen or mixtures thereof.
- R 2 can be a substituted or unsubstituted linear, branched or cyclic monovalent organic group having 6 to 30 carbon atoms.
- the substituted organic group can be substituted with substituents in place of a carbon bonded hydrogen atom (C-H).
- Substituted R 2 groups are exemplified by, but not limited to, halogen such as chlorine or fluorine, ether, poly(oxyalkylene) groups described by formula CH3O(CH2) m O)p(CH2)q- where m, p and q are positive integers and preferably a positive integer of 1 to 9, alkoxy, acyloxy, acyl, alkoxycarbonyl and trialkylsiloxy groups.
- R 2 examples include, but are not limited to, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, hexadecyl, triisobutyl, tetraisobutyl, trimethylsiloxyhexadecyl, octadecyl, CH 3 (CH 2 )i ⁇ OCH 2 CH 2 -, CH 3 O(CH2CH2O)7_9(CH 2 )3-, (CH3)3CCH 2 (CH3) 2 C(CH3)3CCH2CHCH2-, CF 3 (CF2)5CH 2 CH2-, phenylethyl, p- methylphenylethyl, p-methoxyphenylethyl, and p-bromophenyl ethyl.
- R 2 is preferably a substituted or unsubstituted alkyl group having 10 to 20 carbon atoms.
- R 3 is a substituted or unsubstituted branched alkyl group having 3 to 30 carbon atoms.
- the substituted branched alkyl group can be substituted with substituents in place of a carbon bonded hydrogen atom (C-H).
- Substituted R 2 groups are exemplified by, but not limited to, halogen such as chlorine and fluorine, alkoxycarbonyl such as described by formula -(CH2) a C(O)O(CH2) CH3, alkoxy substitution such as described by formula
- R 3 groups are exemplified by, but not limited to, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, 2-methylbutyl, 2-methylpentyl, 2-methylhexyl, 2-ethylbutyl, 2-ethylpentyl, 2-ethylhexyl, etc.
- R 3 is a tertiary alkyl having 4 to 18 carbon atoms and more preferably R 3 is t-butyl.
- the method for preparing the siloxane resin comprises: combining (a) a silane or a mixture of silanes of the formula RIS X3, where each R* is independently selected from the group consisting of alkyl having 1 to 5 carbon atoms, hydrogen and mixtures thereof, X is independently a hydrolyzable group or a hydroxy group;
- R 3 is independently selected from the group consisting of branched alkyl groups having 3 to 30 carbon atoms and branched substituted alkyl groups having 3 to 30 carbon atoms, c is from 1 to 3 inclusive, X is independently a hydrolyzable group or a hydroxy group;
- Silane (a) is a silane or a mixture of silanes of the formula R! S1X3, where each R is independently selected from the group consisting of alkyl having 1 to 5 carbon atoms described above, hydrogen and mixtures thereof. It is preferred that R! is methyl, hydrogen or mixtures thereof.
- X is a hydrolyzable group or a hydroxy group. By “hydrolyzable group” it is meant that greater than 80 mole percent of X reacts with water (hydrolyzes) under the conditions of the reaction to effect formation of the siloxane resin.
- the hydroxy group is a condensable group in which at least 70 mole percent reacts with another X group bonded to a different silicon atom to condense and form a siloxane bond (Si-O-Si).
- the hydrolyzable group is a halide group such as chloride, an amino group, or an organic group attached to a silicon atom through an oxygen atom (Si-OR) forming a silicon bonded alkoxy group or a silicon bonded acyloxy group.
- X is an amino group, it is generally limited to compositions where R is alkyl or contains less than 10 mole percent hydrogen, since amino may be detrimental to the stability of hydrogen containing siloxane resins.
- X is amino
- it is typically used at less than about 30 mole percent because the resulting siloxane resin may contain greater than 30 mole percent SiOH.
- R is exemplified by, but not limited to, linear alkyl groups having 1 to 6 carbon atoms such as methyl, ethyl, propyl, butyl, pentyl, or hexyl and acyl groups having 1 to 6 carbon atoms such as formyl, acetyl, propionyl, butyryl, valeryl or hexanoyl.
- silane (a) be trichlorosilane, methyltrichlorsilane, trimethoxysilane, triethoxysilane, methyltrimethoxysilane or methyltriethoxysilane because of their easy availability.
- silane (a) is present in an amount from 2.5 to 85 mole parts per 100 mole parts total of silane (a), silane (b) and silane (c) combined and preferably 30 to 60 mole parts on the same basis.
- Silane (b) is a silane or a mixture of silanes of the formula R 2 SiX3, where R 2 is independently selected from the group consisting of monovalent organic groups having 6 to 30 carbon atoms and substituted monovalent organic groups having 6 to 30 carbon atoms as described above.
- X is independently a hydrolyzable group or a hydroxy group as described above.
- silane (b) be R SiCl , R 2 Si(OMe)3 and R Si(OEt)3 where Me stands for methyl and Et stands for ethyl because of their easy availability.
- silane (b) is present in an amount from 2.5 to 50 mole parts per 100 mole parts total of silane (a), silane (b) and silane (c) combined and preferably 10 to 25 mole parts on the same basis.
- Silane (c) is a silane or a mixture of silanes of the formula (R 3 O) c SiX(4_ c y where
- R 3 is independently selected from the group consisting of branched alkyl groups having 3 to 30 carbon atoms and substituted branched alkyl groups having 3 to 30 carbon atoms as described above, c is from 1 to 3, and X is independently a hydrolyzable group or a hydroxy group as described above.
- silane (c) be di-t-butoxydichlorosilane, di-t- butoxydihydroxysilane, di-t-butoxydimethoxysilane, di-t-butoxydiethoxysilane, and di-t- butoxydiacetoxysilane because of their easy availability.
- silane (c) is present in an amount from 5 to 95 mole parts per 100 mole parts total of silane (a), silane (b) and silane (c) combined and preferably 20 to 50 mole parts on the same basis.
- Water is present in an amount to effect hydrolysis of the hydrolyzable group, X. Typically water is present in an amount of 0.5 to 2.0 moles of water per mole of X in silanes (a), (b) and (c) and more preferably 0.8 to 1.2 moles on the same basis.
- the reaction to effect formation of the siloxane resin can be carried out in the liquid state with or without a solvent. If a solvent is used, it can include any suitable organic solvent that does not contain functional groups which may participate in the reaction and is a solvent for silanes (a), (b) and (c).
- the solvent is exemplified by, but not limited to, saturated aliphatics such as n-pentane, hexane, n-heptane, isooctane and dodecane; cycloaliphatics such as cyclopentane and cyclohexane; aromatics such as benzene, toluene, xylene and mesitylene; cyclic ethers such as tetrahydrofuran (THF) and dioxane; ketones such as methylisobutyl ketone (MIBK); halogen substituted alkanes such as trichloroethane; halogenated aromatics such as bromobenzene and chlorobenzene; and alcohols such as methanol, ethanol, propanol, butanol.
- saturated aliphatics such as n-pentane, hexane, n-heptane, isooctane and do
- solvents may be used in combination of two or more as co solvents.
- Preferred solvents are aromatic compounds and cyclic ethers, with toluene, mesitylene and tetrahydrofuran being most preferred.
- a solvent is generally used within a range of 40 to 95 weight percent solvent based on the total weight of solvent and silanes (a), (b) and (c). More preferred is 70 to 90 weight percent solvent on the same basis.
- Combining components (a), (b), (c), (d) and optionally a solvent (if it is used) may be done in any order as long as there is contact between any hydrolyzable groups (X) and water, so that the reaction proceed to effect formation of the siloxane resin.
- a solvent if it is used
- the silanes are dissolved in the solvent and then the water is added to the solution.
- Some reaction usually occurs when the above components are combined.
- various facilitating measures such as temperature control and/or agitation are utilized.
- the temperature at which the reaction is carried out is not critical as long as it does not cause significant gelation or cause curing of the siloxane resin product.
- the temperature can be in a range of 20°C to 150°C, with a temperature of 20°C to 100°C being preferred.
- X is an acyloxy group such as acetoxy
- the time to form the siloxane resin is dependent upon a number of factors such as, but not limited to, the specific silanes being used, the temperature and the mole ratio of Rl, R 2 and R 3 desired in the siloxane resin product of the reaction. Typically, the reaction time is from several minutes to several hours. To increase the molecular weight of the siloxane resin prepared and to improve the storage stability of the siloxane resin it is preferred to carry out a bodying step subsequent to or as part of the above reaction.
- bodying it is meant that the reaction is carried out over several hours with heating from 40°C up to the reflux temperature of the solvent to effect the increase in weight average molecular weight. It is preferred that the reaction mixture be heated such that the siloxane resin after heating has a weight average molecular weight in the range of about 5,000 to 100,000.
- X is an acyloxy group such as acetoxy
- the corresponding acid such as acetic acid is produced as a by-product of the reaction. Since the presence of acetic acid may adversely affect the stability of the siloxane resin product, it is desirable that any acetic acid be neutralized.
- Neutralization of the by-product acetic acid may be effected by contacting the reaction mixture with a neutralizing agent or by removal via distillation.
- the distillation is generally accomplished by the addition of solvent such as toluene (if it is not already present) and removing the acetic acid under reduced pressure and heat (i.e. up to 50°C) as an azeotrope with the solvent.
- solvent such as toluene (if it is not already present) and removing the acetic acid under reduced pressure and heat (i.e. up to 50°C) as an azeotrope with the solvent.
- a neutralizing agent it must be sufficiently basic to neutralize any remaining acetic acid and yet insufficiently basic so that it does not catalyze rearrangement of the siloxane resin product.
- suitable bases include calcium carbonate, sodium carbonate, sodium bicarbonate, ammonium carbonate, ammonia, calcium oxide or calcium hydroxide.
- Neutralization may be accomplished by any suitable means such as stirring in a powdered neutralizing agent followed by filtration or by passing the reaction mixture and any additional solvent over or through a bed of particulate neutralizing agent of a size which does not impede flow.
- the bodying step described herein above is generally carried out after neutralization and/or removal of the by-product acetic acid.
- X is a halide group
- HX is formed as a by-product of the reaction. Since the presence of HX may adversely affect the stability of the siloxane resin product, it is desirable that the HX be neutralized or removed using methods known in the art for neutralization or removal.
- HC1 when HC1 is produced as a by-product it may be removed by providing a gas sweep in the reaction vessel. Or the HC1 may be neutralized using the process described above. Or the HC1 may be removed by washing the siloxane resin solution with water until neutral.
- siloxane resin composition comprising (A) and (B) siloxane units and additionally Si ⁇ 4/2 units.
- the siloxane resin may be recovered in solid form by removing the solvent if a solvent was used.
- the method of solvent removal is not critical and numerous approaches are well known in the art. For example, a process comprising removing the solvent by distillation under vacuum and heat (i.e. 50°C to 120°C) may be used.
- a solvent exchange may be done by adding a secondary solvent and distilling off the first solvent.
- Siloxane resins containing greater than 10 weight percent silicon bonded hydrogen (Si-H) are generally kept as solutions, while those with less Si-H may be stored in solid form.
- An insoluble porous resin may be obtained by heating the siloxane resin for a time and temperature sufficient to effect curing of the siloxane resin and removal of the R 2 and
- R 3 O groups thereby forming an insoluble porous resin.
- “removal” it is meant that greater than about 80 mole percent of the R 2 and R 3 O groups bonded to silicon atoms have been removed as volatile hydrocarbon and hydrocarbon fragments which generate voids in the coating, resulting in the formation of an insoluble porous resin.
- the heating may be conducted in a single-step process or in a two-step process. In the two-step heating process the siloxane resin is first heated for a time and temperature sufficient to effect curing without significant removal of the R 2 and R 3 O groups. Generally this temperature can be in a range of from greater than 20°C to 350°C for several minutes to several hours.
- the cured siloxane resin is further heated for a time and temperature (for several minutes to several hours) within a range of greater than 350°C up to the lesser of the decomposition of the siloxane resin backbone or R* groups bonded to silicon atoms described herein above to effect removal of the R 2 and R 3 O groups from the silicon atoms.
- the removal step is conducted at a temperature in a range of greater than 350°C to 600°C, with a temperature range of 400°C to 550°C being preferred .
- the porosity in the final insoluble porous resin can be controlled by the mole percent of R 2 and R 3 O groups in the siloxane resin and how the siloxane resin is heated.
- the insoluble porous resins formed from siloxane resins containing both R 2 and R 3 O groups incorporated into the siloxane resin generally result in an increase in porosity, typically about 10 volume percent, when compared with siloxane resins cured under similar conditions which contain only R 2 or R 3 O groups incorporated into the siloxane resin of similar compositions (i.e. the mol % of total R 2 or R 3 O leaving groups is approximately the same).
- R 3 O groups are effected simultaneously by heating for a time and temperature within a range of greater than 20°C up to the lesser of the decomposition of the siloxane resin backbone or the R! groups bonded to silicon atoms described herein above to effect removal of the R 2 and
- R 3 O groups from the cured siloxane resin is preferred.
- the curing/removal step be conducted at a temperature in a range of greater than 350°C to 600°C, with a temperature in a range of 400°C to 550°C being most preferred.
- the heating takes place in an inert atmosphere, although other atmospheres may be used.
- Inert atmospheres useful herein include, but are not limited to, nitrogen, helium and argon with an oxygen level less than 50 parts per million and preferably less than 15 parts per million.
- Heating may also be conducted at any effective atmospheric pressure from vacuum to above atmospheric and under any effective oxidizing or non- oxidizing gaseous environment such as those comprising air, O2, oxygen plasma, ozone, ammonia, amines, moisture, N2O, hydrogen, etc.
- any effective oxidizing or non- oxidizing gaseous environment such as those comprising air, O2, oxygen plasma, ozone, ammonia, amines, moisture, N2O, hydrogen, etc.
- the insoluble porous resins may be useful as porous materials with controllable porosity and high temperature stability up to 600°C such as shape selective gas or liquid permeable membranes, catalyst supports, energy storage systems such as batteries and molecular separation and isolation.
- porous it is meant an insoluble porous resin having a porosity in a range of from 1 to 60 volume percent. Porosity in the range of 10 to 60 volume percent is preferred.
- the modulus of the insoluble porous resins ranges from 1.0 to 10 GPa.
- the siloxane resins may be used to prepare a porous coating on a substrate by:
- R 2 Si ⁇ 3/2 siloxane units wherein R 2 is selected from the group consisting of monovalent organic groups having 6 to 30 carbon atoms and monovalent substituted organic groups having 6 to 30 carbon atoms as described herein above, and
- the siloxane resin contains an average of 30 to 60 mole parts (a), 10 to 25 mole parts (b) and 20 to 50 mole (c) per 100 mole parts total amount of (a), (b) and (c) and the sum of (a), (b) and (c) is at least 70 percent of total siloxane units in the resin composition.
- the siloxane resin is typically applied to a substrate as a solvent dispersion.
- Solvents which may be used include any agent or mixture of agents which will dissolve or disperse the siloxane resin to form a homogeneous liquid mixture without affecting the resulting coating or the substrate.
- the solvent can generally be any organic solvent that does not contain functional groups which may participate in a reaction with the siloxane resin, such as hydroxyl, exemplified by those discussed herein above for the reaction of the silane mixture with water.
- the solvent is present in an amount sufficient to dissolve the siloxane resin to the concentration desired for a particular application. Typically the solvent is present in an amount of 40 to 95 weight percent, preferably from 70 to 90 weight percent based on the weight of the siloxane resin and solvent. If the siloxane resin has been retained in a solvent described herein above, the solvent may be used in coating the substrate, or if desired a simple solvent exchange may be performed by adding a secondary solvent and distilling off the first solvent. [0040] Specific methods for application of the siloxane resin to a substrate include, but are not limited to spin coating, dip coating, spray coating, flow coating, screen printing or others. The preferred method for application is spin coating.
- the solvent is allowed to evaporate from the coated substrate resulting in the deposition of the siloxane resin coating on the substrate.
- Any suitable means for evaporation may be used such as simple air drying by exposure to an ambient environment, by the application of a vacuum, or mild heat (up to 50°C) or during the early stages of the curing process.
- spin coating the additional drying method is minimized since the spinning drives off the solvent.
- the siloxane resin coating is heated at a temperature sufficient to effect cure of the siloxane resin and removal of the R 2 and R 3 O groups bonded to silicon atoms, thereby forming an insoluble porous coating.
- cured coating composition it is meant that the coating is essentially insoluble in the solvent from which the siloxane resin was deposited onto the substrate or any solvent delineated above as being useful for the application of the siloxane resin.
- removable it is meant that greater than 80 mole percent of the R 2 and R 3 O groups bonded to silicon atoms have been removed as volatile hydrocarbon and hydrocarbon fragments which generate voids in the coating, resulting in the formation of a porous resin.
- the heating may be conducted in a single-step process or in a two-step process. In the two-step heating process the siloxane resin is first heated at a temperature sufficient to effect curing without significant removal of the R 2 and R 3 O groups.
- this temperature can be in a range of from greater than 20°C to 350°C.
- the cured siloxane resin coating is further heated at a temperature within a range of greater than 350°C up to the lesser of the decomposition of the siloxane resin backbone or the R! groups bonded to silicon atoms described herein above to effect removal of the R 2 and R 3 O groups (leaving groups) from the silicon atoms.
- the removal step be conducted at a temperature in a range of greater than 350°C to
- the curing of the siloxane resin and removal of the R 2 and O groups are effected simultaneously by heating at a temperature within a range of greater than 20°C up to the lesser of the decomposition of the siloxane resin backbone or the R! groups bonded to silicon atoms described herein above to effect removal of the R 2 and R 3 O groups from the cured coating composition.
- the curing/removal step be conducted at a temperature in a range of greater than 350°C to 600°C, with a temperature in a range of 400°C to 550°C being most preferred.
- the porosity in the final insoluble porous resin can be controlled by the mole percent of R 2 and R 3 O groups in the siloxane resin and how the siloxane resin is heated.
- heating be conducted in an inert atmosphere, although other atmospheres may be used.
- Inert atmospheres useful herein include, but are not limited to, nitrogen, helium and argon with an oxygen level less than 50 parts per million and preferably less than 15 parts per million. Heating may also be conducted at any effective atmospheric pressure from vacuum to above atmospheric and under any effective oxidizing or non- oxidizing gaseous environment such as those comprising air, O2, oxygen plasma, ozone, ammonia, amines, moisture, N2O, hydrogen, etc.
- the insoluble porous coatings have a thickness of 0.3 to 2.5 ⁇ m and a thickness of 0.5 to 1.2 ⁇ m being more preferable.
- the coating smoothes the irregular surfaces of the various substrates and has excellent adhesion properties.
- any method of heating such as the use of a quartz tube furnace, a convection oven, or radiant or microwave energy is generally functional herein. Similarly, the rate of heating is generally not a critical factor, but it is most practical and preferred to heat the coated substrate as rapidly as possible.
- the insoluble porous coatings produced herein may be produced on any substrate. However, the coatings are particularly useful on electronic substrates.
- electronic substrate it is meant to include silicon based devices and gallium arsenide based devices intended for use in the manufacture of a semiconductor component including focal plane arrays, optoelectronic devices, photovoltaic cells, optical devices, transistor-like devices, 3-D devices, silicon-on-insulator devices, super lattice devices and the like.
- Additional coatings may be applied over the insoluble porous coating if desired.
- These can include, for example SiO coatings, silicon containing coatings, silicon carbon containing coatings, silicon nitrogen containing coatings, silicon oxygen nitrogen containing coatings, silicon nitrogen carbon containing coatings and/or diamond like coatings produced from deposition (i.e. CVD, PECVD, etc.) of amorphous SiC:H, diamond, silicon nitride. Methods for the application of such coatings are known in the art.
- the method of applying an additional coating is not critical, and such coatings are typically applied by chemical vapor deposition techniques such as thermal chemical vapor deposition (TCVD), photochemical vapor deposition, plasma enhanced chemical vapor deposition (PECVD), electron cyclotron resonance (ECR), and jet vapor deposition.
- the additional coatings can also be applied by physical vapor deposition techniques such as sputtering or electron beam evaporation. These processes involve either the addition of energy in the form of heat or plasma to a vaporized species to cause the desired reaction, or they focus energy on a solid sample of the material to cause its deposition.
- the insoluble porous coatings formed by this method are particularly useful as coatings on electronic devices such is integrated circuits.
- the dielectric constant of the insoluble porous coatings made by this method range from 1.5 to 3, with a range from 1.5 to 2.5 being more preferred for interlayer dielectric coatings.
- porous it is meant an insoluble porous coating having a porosity of 1 to 60 volume percent. Porosity in the range of 10 to 60 volume percent is preferred.
- the modulus of the insoluble porous coatings ranges from 1.0 to 10 GPa.
- Skeletal density represents the true density of the siloxane resin solid structure without including any interior voids, cracks or pores in the measurement.
- the percent porosity was calculated from the skeletal density and the total pore volume.
- Refractive Index (RI) and coating thickness were measured using a Woollam M-88 Spectroscopic Ellipsometer. [0050] In the following examples Me stands for methyl and tBu stands for tertiary-butyl, AcO stands for acetoxy, and Et stands for ethyl. In the following tables, n.m. indicates the specified property was not measured.
- Example 1 Me stands for methyl and tBu stands for tertiary-butyl, AcO stands for acetoxy, and Et stands for ethyl.
- Me stands for methyl
- tBu stands for tertiary-butyl
- AcO stands for acetoxy
- Et stands for ethyl.
- n.m. indicates the specified property was not measured
- This example illustrates the formation of siloxane resin compositions where RI is hydrogen, R 2 is an organic group having 8 to 22 carbon atoms and R 3 is a t-butyl group.
- HSi(OEt) (A), (AcO) 2 Si(OtBu) 2 (B) and R 2 Si(OMe) 3 (C) were added to 75 g of tetrahydrofuran (THF) in a flask under an argon atmosphere in the amounts described in Table 1.
- Deionized water (D) was then added to the flask and the mixture was stirred at room temperature for 1 hour. Then 75 g of toluene was added to the mixture. The solvent was removed using a rotary evaporator to yield a siloxane resin as a viscous oil, which was immediately dissolved into 150 g of toluene.
- Example 2a This example illustrates the formation of siloxane resin compositions where R! is hydrogen, R 2 is octadecyl and R 3 is a t-butyl group.
- (MeO)2SiCl2 was prepared by mixing
- (MeO)2Si(OtBu)2 was prepared by adding 119.0 g of fraction 2 above to 1.5 L (1.5 mol, in excess) of a 1M solution of Potassium t-butoxide/THF, under nitrogen at 0°C. Next 500 ml of anhydrous THF was added to the reaction mixture while stirring for 4 hours at reflux (65°C). The solvent was evaporated at 20°C under a vacuum of 100 mm Hg. The reaction product was washed several times with a pentane/diethyl ether mixture, filtered and distilled (92°C, 75 mm Hg) to give 79.5 grams of a colorless liquid characterized by ⁇ Si
- a mixture of 5.48 g of the reaction product from example 2b, 8.70 g of CH 3 (CH 2 )i7Si(OMe)3 and 7.62 g of HSi(OEt) 3 were added to 40 ml of MIBK followed by dropwise addition to a mixture comprising 80 ml MIBK, 40 ml toluene and 60 ml deionized water under a nitrogen atmosphere.
- the reaction mixture was refluxed at 120°C overnight. After cooling, the reaction mixture was separated into 2 phases, water/insoluble materials and an organic phase. The organic phase was separated from the water/insoluble materials phase and dried using a dean stark trap.
- the solvent was evaporated using a rotovap giving 7.2 grams of a waxy solid, which was identified by 2 ⁇ Si NMR to be
- This example illustrates the formation of siloxane resin compositions where R! is hydrogen, R 2 is a substituted phenylethyl group and R 3 is a t-butyl group under conditions similar to Example 1.
- ZC6H4CH2CH2Si(OEt)3 were added to 37 g of tetrahydrofuran (THF) in a flask under an argon atmosphere in the amounts described in Table 4.
- Deionized water (D) was then added to the solution and the mixture was stirred at room temperature overnight.
- 50 g of toluene was added to the reaction mixture.
- the solvent was removed using a rotary evaporator at 35 to 40°C to yield a viscous liquid, which was immediately dissolved into 80 g of toluene. Residual acetic acid was removed as an azeotrope with toluene (azeotrope boiling point at 38°C).
- the viscous liquid was added to 120 g toluene, 10 weight % as viscous liquid (based on total weight of toluene and viscous liquid), which was heated under reflux for 30 minutes and azeotropically dried and refluxed for lh. The solution was filtered and the solvent removed by evaporation to yield the final resin product.
- a summary of the resin synthesis is shown in Table 4. Analysis of the resin is shown in Table 5.
- This example illustrates the formation of insoluble porous resins where R! is hydrogen, R 2 is an organic group having 8 to 22 carbon atoms and R 3 is a t-butyl group.
- Resins prepared in Example 1 and Example 2 (2 to 3 grams) were weighed into an alumina crucible and transferred into a quartz tube furnace. The furnace was evacuated to ⁇ 20 mmHg ( ⁇ 2666 Pa) and backfilled with argon. The samples were heated to the temperatures shown in Table 6 at a rate of 50°C to 60°C/minute and held at temperature for 2 hours before cooling to room temperature while under an argon purge.
- the cured materials obtained were transparent or slightly opaque thick films Pyrolysis conditions, char yields, TGA (Thermogravimetric Analysis) yields and porosity data by nitrogen absorption measurements are shown in Tables 6 and 7. Char Yield and TGA Yield are expressed as weight % retained after analysis at a specified temperature.
- This example illustrates the formation of insoluble porous coatings on a substrate where R! is hydrogen, R 2 is an organic group having 8 to 22 carbon atoms and R 3 is a t- butyl group.
- Resins prepared in Examples 1,2 and 3 (2 to 3g) were dissolved in MIBK to form a clear solution containing 25 weight % as resin. The solution was filtered through a 1.0 ⁇ m syringe membrane filter, then a 0.2 ⁇ m syringe membrane filter to remove any large particles. The solution was applied to a silicon wafer by spin coating at 2000 rpm for 20 seconds. The coated silicon wafers were put into a quartz tube furnace and the furnace was purged with nitrogen.
- the furnace was quickly heated to 450°C (50°C to 60°C /minute) and held at 450°C for 2 hours, then cooled to room temperature while maintaining the nitrogen purge.
- the coated wafers were stored under a nitrogen atmosphere before the property measurements. Properties of the thin films are shown in Table 8.
- This example illustrates the formation of insoluble porous coatings on a substrate where Rl is hydrogen, R 2 is an organic group having 8 to 22 carbon atoms, and R 3 is a t- butyl group under various cure temperatures.
- Resins prepared in Example 1 (2 to 3g) were dissolved in MIBK to form a clear solution containing 25 weight % as resin.
- the solution was filtered through a 1.0 ⁇ m syringe memberane filter, followed by a 0.2 ⁇ m syringe membrane filter to remove any large particles.
- the solution was applied to a silicon wafer by spin coating at 2000 rpm for 20 seconds.
- the coated silicon wafers were put into a quartz tube furnace and the furnace was purged with nitrogen.
- the furnace was heated 250, 390 and 450°C and held at each temperature for 1 hour, respectively, then cooled to room temperature while maintaining the nitrogen purge.
- the coated wafers were stored under a nitrogen atmosphere before the property measurements. Properties of the thin films are shown in Table 9.
- This example illustrates the formation of siloxane resin compositions where Rl is methyl, R 2 is octadecyl and R 3 is a t-butyl group.
- MeSi(OMe)3 (A), (AcO)2Si(OtBu)2 (B) and CH3(CH2)i7Si(OMe)3 (C) were added to 75 g of THF in a flask under an argon atmosphere in the amounts described in Table 9.
- Deionized water (D) was then added to the solution and the mixture was stirred at room temperature for 1 hour. 75 g of toluene was added to the reaction mixture.
- This example illustrates the formation of insoluble porous resins where Rl is methyl, R 2 is octadecyl and R 3 is a t-butyl group.
- Resins prepared in Example 7 (2 to 3g) were weighed into an alumina crucible and transferred into a quartz tube furnace. The furnace was evacuated to ⁇ 20 mmHg ( ⁇ 2666 Pa) and backfilled with argon. The samples were heated to the temperatures shown in Table 12 at a rate of 50°C to 60°C/minute and held at temperature for 2 hours before cooling to room temperature while under an argon purge. The cured materials obtained were transparent or slightly opaque thick. Pyrolysis conditions, char yields, TGA yields and porosity data by nitrogen absorption measurements are shown in Tables 12 and 13.
- Example 9 This example illustrates the formation of insoluble porous coatings on a substrate where R* is methyl, R 2 is octadecyl and R 3 is a t-butyl group.
- Resins prepared in Example 7 (2 to 3g) were dissolved in MIBK to form a clear solution containing 25 weight % as resin.
- the solution was filtered through a 1.0 ⁇ m syringe membrane filter followed by a 0.2 ⁇ m syringe membrane filter to remove any large particles.
- the solution was applied to a silicon wafer by spin coating at 2000 rpm for 20 seconds.
- the coated silicon wafers were put into a quartz tube furnace and the furnace was purged with nitrogen.
- the furnace was quickly heated to 450°C (50°C to 60°C/minute) and held at 450°C for 2 hours, then cooled to room temperature while maintaining the nitrogen purge.
- the coated wafers were stored under a nitrogen atmosphere before the property measurements. Modulus and dielectric constants (Dk) of the thin films are shown in Table 14.
- the resin films were loaded into an QTF furnace and quickly heated to 450°C under nitrogen. The films were heated at 450°C for 2 hours, then cool to room temperatures. All the coated wafers were stored under a nitrogen atmosphere before the property measurements.
- Comparative Example 1 This example illustrates the formation of siloxane resin compositions where R is hydrogen, R 2 is not present and R 3 is a t-butyl group.
- the resin was again dissolved into 110 g of toluene and azeotropically dried and heated in refluxing toluene for lh. The solution was filtered and the solvent removed by evaporation to yield the siloxane resin product.
- a summary of the resin synthesis is shown in Table 21.
- the molecular weight information for the resins is shown in Table 22.
- This example illustrates the formation of siloxane resin compositions where R is methyl, R 2 is not present and R 3 is a t-butyl group.
- MeSi(OMe)3 (A), (AcO)2Si(OtBu)2 (B) and THF were added to a flask under an argon atmosphere in the amounts described in Table 17.
- AcO stands for acetoxy
- Me stands for methyl
- tBu stands for tertiary-butyl.
- Deionized water was then added to the flask and the mixture was stirred at room temperature for 1 hour. 75 g of toluene was added to the reaction mixture.
- This example illustrates the formation of siloxane resin compositions where Rl is hydrogen, R 2 is octadecyl and R 3 is not present.
- Two solutions of a hydrogen silsesquioxane resin having a weight average molecular weight of 70,000, prepared by the method of Collins et al., U.S. Patent No 3,615,272, dissolved in toluene were reacted with 1-octadecene at
- Table 29 shows the weight parts of solvent and 1-octadecene used per 1 weight part of hydrogen silsesquioxane resin, porosity and dielectric constant for each sample.
- Sample C3-3 is the hydrogen silsesquioxane resin solution in toluene which was not reacted with 1-octadecene.
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- General Physics & Mathematics (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Silicon Polymers (AREA)
- Paints Or Removers (AREA)
- Formation Of Insulating Films (AREA)
Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU2002322250A AU2002322250A1 (en) | 2001-07-26 | 2002-06-18 | Siloxane resins |
EP02756227A EP1412435A2 (en) | 2001-07-26 | 2002-06-18 | Siloxane resins |
KR10-2004-7000882A KR20040043160A (en) | 2001-07-26 | 2002-06-18 | Siloxane resins |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US91589901A | 2001-07-26 | 2001-07-26 | |
US09/915,899 | 2001-07-26 | ||
US10/121,971 US6596404B1 (en) | 2001-07-26 | 2002-04-15 | Siloxane resins |
US10/121,971 | 2002-04-15 |
Publications (2)
Publication Number | Publication Date |
---|---|
WO2003011945A2 true WO2003011945A2 (en) | 2003-02-13 |
WO2003011945A3 WO2003011945A3 (en) | 2003-05-01 |
Family
ID=26820023
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2002/019283 WO2003011945A2 (en) | 2001-07-26 | 2002-06-18 | Siloxane resins |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP1412435A2 (en) |
CN (1) | CN1535301A (en) |
TW (1) | TW591057B (en) |
WO (1) | WO2003011945A2 (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001187821A (en) * | 1999-10-25 | 2001-07-10 | Dow Corning Corp | Silicone resin composition having good solubility and stability |
JP2008524374A (en) * | 2004-12-17 | 2008-07-10 | ダウ・コーニング・コーポレイション | Siloxane resin coating |
JP2019507750A (en) * | 2016-02-12 | 2019-03-22 | シースター ケミカルズ ユーエルシー | Organometallic compounds and methods |
JP2019085367A (en) * | 2017-11-07 | 2019-06-06 | 国立研究開発法人産業技術総合研究所 | Method for producing halosilane |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7989030B2 (en) * | 2006-08-04 | 2011-08-02 | Dow Corning Corporation | Silicone resin and silicone composition |
EP3633262A1 (en) * | 2018-10-04 | 2020-04-08 | ZKW Group GmbH | Projection device for a motor vehicle headlight module and method for producing a projection device |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1125138C (en) * | 1997-07-15 | 2003-10-22 | 旭化成株式会社 | Alkoxysilane/organic polymer composition for thin insulating film prodution and use thereof |
US6231989B1 (en) * | 1998-11-20 | 2001-05-15 | Dow Corning Corporation | Method of forming coatings |
EP1095958B1 (en) * | 1999-10-25 | 2006-02-08 | Dow Corning Corporation | Soluble silicone resin compositions |
-
2002
- 2002-06-18 WO PCT/US2002/019283 patent/WO2003011945A2/en not_active Application Discontinuation
- 2002-06-18 CN CNA028147286A patent/CN1535301A/en active Pending
- 2002-06-18 EP EP02756227A patent/EP1412435A2/en not_active Withdrawn
- 2002-06-26 TW TW091114016A patent/TW591057B/en active
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001187821A (en) * | 1999-10-25 | 2001-07-10 | Dow Corning Corp | Silicone resin composition having good solubility and stability |
JP2008524374A (en) * | 2004-12-17 | 2008-07-10 | ダウ・コーニング・コーポレイション | Siloxane resin coating |
US8129491B2 (en) | 2004-12-17 | 2012-03-06 | Dow Corning Corporation | Siloxane resin coating |
JP2019507750A (en) * | 2016-02-12 | 2019-03-22 | シースター ケミカルズ ユーエルシー | Organometallic compounds and methods |
US11802134B2 (en) | 2016-02-12 | 2023-10-31 | Seastar Chemicals Ulc | Organometallic compound and method |
JP2019085367A (en) * | 2017-11-07 | 2019-06-06 | 国立研究開発法人産業技術総合研究所 | Method for producing halosilane |
Also Published As
Publication number | Publication date |
---|---|
CN1535301A (en) | 2004-10-06 |
TW591057B (en) | 2004-06-11 |
EP1412435A2 (en) | 2004-04-28 |
WO2003011945A3 (en) | 2003-05-01 |
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