CN1535300A - 硅氧烷树脂 - Google Patents
硅氧烷树脂 Download PDFInfo
- Publication number
- CN1535300A CN1535300A CNA028146980A CN02814698A CN1535300A CN 1535300 A CN1535300 A CN 1535300A CN A028146980 A CNA028146980 A CN A028146980A CN 02814698 A CN02814698 A CN 02814698A CN 1535300 A CN1535300 A CN 1535300A
- Authority
- CN
- China
- Prior art keywords
- silicone resin
- sio
- resin
- coating
- carbon atom
- 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.)
- Pending
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- 229920005989 resin Polymers 0.000 title claims abstract description 78
- 239000011347 resin Substances 0.000 title claims abstract description 78
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 title abstract description 9
- 238000000576 coating method Methods 0.000 claims abstract description 80
- 239000011248 coating agent Substances 0.000 claims abstract description 75
- -1 siloxane units Chemical group 0.000 claims abstract description 49
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 42
- 229910014307 bSiO Inorganic materials 0.000 claims abstract description 23
- 238000010438 heat treatment Methods 0.000 claims abstract description 20
- 239000011342 resin composition Substances 0.000 claims abstract description 15
- 239000000758 substrate Substances 0.000 claims abstract description 13
- 229920002050 silicone resin Polymers 0.000 claims description 88
- 229910052799 carbon Inorganic materials 0.000 claims description 42
- 238000000034 method Methods 0.000 claims description 40
- 239000000463 material Substances 0.000 claims description 32
- 229910000077 silane Inorganic materials 0.000 claims description 31
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 27
- 239000000203 mixture Substances 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 230000015572 biosynthetic process Effects 0.000 claims description 13
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 239000008199 coating composition Substances 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims 9
- 229910020487 SiO3/2 Inorganic materials 0.000 abstract 2
- 230000002277 temperature effect Effects 0.000 abstract 1
- 239000002904 solvent Substances 0.000 description 48
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 35
- 150000001721 carbon Chemical group 0.000 description 28
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 27
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 23
- 229910052710 silicon Inorganic materials 0.000 description 23
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 22
- 239000010703 silicon Substances 0.000 description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 18
- 239000000047 product Substances 0.000 description 17
- 239000000243 solution Substances 0.000 description 17
- 238000003723 Smelting Methods 0.000 description 12
- 239000012298 atmosphere Substances 0.000 description 12
- 229910052786 argon Inorganic materials 0.000 description 11
- 239000000377 silicon dioxide Substances 0.000 description 11
- 239000007789 gas Substances 0.000 description 9
- 238000009413 insulation Methods 0.000 description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- 238000010926 purge Methods 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 9
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 8
- 239000012528 membrane Substances 0.000 description 8
- 238000004528 spin coating Methods 0.000 description 8
- 125000003545 alkoxy group Chemical group 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 238000005229 chemical vapour deposition Methods 0.000 description 7
- 239000011148 porous material Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 6
- 238000003763 carbonization Methods 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 125000004423 acyloxy group Chemical group 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 239000000428 dust Substances 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 238000006386 neutralization reaction Methods 0.000 description 4
- 230000003472 neutralizing 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
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000001704 evaporation Methods 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
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 125000000962 organic group Chemical group 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229920003209 poly(hydridosilsesquioxane) Polymers 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- AUHZEENZYGFFBQ-UHFFFAOYSA-N 1,3,5-trimethylbenzene Chemical compound CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 2
- 125000001731 2-cyanoethyl group Chemical group [H]C([H])(*)C([H])([H])C#N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- 229910004283 SiO 4 Inorganic materials 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
- 125000002252 acyl group Chemical group 0.000 description 2
- 239000003570 air Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003153 chemical reaction reagent 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
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 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 2
- 238000002955 isolation Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- CFHIDWOYWUOIHU-UHFFFAOYSA-N oxomethyl Chemical compound O=[CH] CFHIDWOYWUOIHU-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 229960001866 silicon dioxide Drugs 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 238000002230 thermal chemical vapour deposition Methods 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
- 238000005406 washing Methods 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-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
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- SGVYKUFIHHTIFL-UHFFFAOYSA-N Isobutylhexyl Natural products CCCCCCCC(C)C SGVYKUFIHHTIFL-UHFFFAOYSA-N 0.000 description 1
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 240000005373 Panax quinquefolius Species 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 229910008051 Si-OH Inorganic materials 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 229910004298 SiO 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
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000003491 array Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000009835 boiling Methods 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
- 238000012512 characterization method Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005566 electron beam evaporation Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 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
- 230000005484 gravity Effects 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000001788 irregular Effects 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
- 150000002576 ketones Chemical class 0.000 description 1
- 235000012204 lemonade/lime carbonate Nutrition 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000005055 methyl trichlorosilane Substances 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
- 229910021421 monocrystalline silicon Inorganic materials 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
- 230000003287 optical effect Effects 0.000 description 1
- 238000000399 optical microscopy Methods 0.000 description 1
- GEVPUGOOGXGPIO-UHFFFAOYSA-N oxalic acid;dihydrate Chemical compound O.O.OC(=O)C(O)=O GEVPUGOOGXGPIO-UHFFFAOYSA-N 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 238000007789 sealing 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
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 125000005372 silanol group Chemical group 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
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 238000005507 spraying Methods 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
- 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
- JLGNHOJUQFHYEZ-UHFFFAOYSA-N trimethoxy(3,3,3-trifluoropropyl)silane Chemical compound CO[Si](OC)(OC)CCC(F)(F)F JLGNHOJUQFHYEZ-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 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
-
- 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
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/312—Organic layers, e.g. photoresist
- H01L21/3121—Layers comprising organo-silicon compounds
- H01L21/3122—Layers comprising organo-silicon compounds layers comprising polysiloxane compounds
-
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Abstract
本发明涉及包含R1SiO3/2硅氧烷单元和(R2O)bSiO(4-b)/2硅氧烷单元的硅氧烷树脂组合物,其中,R1为具有1-5个碳原子的烷基;R2为具有3-30个碳原子的支链烷基,b为1-3。所述硅氧烷树脂包含摩尔比为1∶99 to 99∶1的R1SiO3/2单元和(R2O)bSiO(4-b)/2单元。所述硅氧烷树脂可用于制备不溶性多孔树脂和不溶性多孔涂层。以除去R2O基团足够的温度对涂布有硅氧烷树脂的基材进行加热,从而形成不溶性多孔涂层,其介电常数在2.1-3的范围内,孔隙率在2-40%体积的范围内,模量为1.9-20GPa。
Description
技术领域
本发明涉及一种包含R1SiO3/2硅氧烷单元和(R2O)bSiO(4-b)/2硅氧烷单元的硅氧烷树脂组合物,其中,R1独立地选自具有1-5个碳原子的烷基;R2独立地选自具有3-30个碳原子的支链烷基和具有3-30个碳原子的取代的支链烷基,并且b为1-3。本发明还涉及由所述硅氧烷树脂组合物生产的不溶性的多孔树脂和不溶性的多孔涂层。
背景技术
半导体器件常常具有一排或多排构图互连触点(levels),其起电偶联各电路元件形成集成电路(IC)的作用。互连触点通常被绝缘涂层或介电涂层分开。以前,用于上述的介电涂层,最常用的材料是利用化学气相沉积(CVD)或等离子体增强技术(PECVD)形成的二氧化硅涂层。然而,当电路元件的尺寸和上述元件之间的间距减小时,上述二氧化硅涂层的相对高的介电常数(即约4)将不适于提供适当的电绝缘。
为了提供低于二氧化硅的介电常数,业已发现可使用由硅氧烷基树脂形成的介电涂层。上述涂层的例子为由例如描述于Collins等人的US3,615,272和Haluska等人的US4,756,977中的氢倍半硅氧烷树脂所形成的那些。尽管上述涂层提供了低于CVD或PECVD二氧化硅涂层的介电常数,并且还提供了其它的益处如增强的间隙填充性和表面平整性,但上述涂层的介电常数通常还局限于约3或更大。
众所周知,绝缘涂层的介电常数是其中要求具有低的电耗、串话、和信号延迟的IC的一个重要因素。由于IC的尺寸持续缩小,因此,该因素的重要性增加。因此,人们想要的是能够提供介电常数在3以下的电绝缘涂层的硅氧烷基树脂材料以及所述材料的制备方法。另外,人们还想要提供具有高耐裂性涂层的硅氧烷基树脂以及所述树脂的制备方法。此外,人们所希望的是通过标准加工技术如旋涂加工上述硅氧烷基树脂来提供涂层。众所周知,实心涂层的介电常数随涂料密度的减小而减小。多孔涂层的密度通常低于相应的实心涂层。
Haluska的US5,446,088描述了通式HSi(OR)3和Si(OR)4的共水解硅烷以形成对形成涂层有用的共水解产物的方法。R基团是包含1-20个碳原子的有机基团,当通过氧原子连接至硅上时,所述基团形成可水解的取代基。尤其优选的可水解基团是甲氧基和乙氧基。用水的水解在包含酸化氧的极性溶剂中进行。将溶剂中的共水解产物施加至基材上,蒸发掉溶剂并将涂层加热至50-1000℃,从而使涂层转变成二氧化硅。Haluska没有披露带有支链烷氧基的硅烷。
Chung等人的US6,231,989描述了一种由氢倍半硅氧烷树脂形成多孔涂层的方法。以沉积之后至少5%体积的溶剂留在涂层内的方式,用包含氢倍半硅氧烷树脂和溶剂的溶液在基材上沉积涂层而形成多孔网络。然后,将涂层暴露至包含碱性催化剂和水的环境中;从涂层中蒸发掉溶剂,从而形成介电常数在1.5-2.4范围内的多孔网络
Smith等人的WO98/49721描述了一种在基材上形成纳米多孔介电涂层的方法。该方法包括如下步骤:将烷氧基硅烷与溶剂成分和非必需的水混合;在蒸发至少部分溶剂的同时使该混合物沉积至基材上;将基材置于密封室中并对该室抽真空至压力低于大气压;在低于大气压的压力下使该基材暴露至水蒸汽中和然后暴露至碱性蒸汽中。
Mikoshiba等人的US6,022,814描述了一种由带有有机取代基的氢或甲基硅氧烷基树脂在基材上形成二氧化硅薄膜的方法,其中所述取代基在250℃至该树脂的玻璃化转变点的温度范围内将被除去。所报道的二氧化硅薄膜的性能包括:0.8-1.4g/cm3的密度,1-3纳米的平均孔径,600-1500m2/g的表面积和2.0-3.0的介电常数。所披露的在250℃或更高的温度能被氧化的有用的有机取代基包括取代的和未被取代的烷基或烷氧基,例如,3,3,3-三氟丙基,β-苯乙基,叔丁基,2-氰乙基,苯甲基,和乙烯基。
Mikoskiba等人在J.Mat.Chem.,1999,9,591-598中报道了一种在甲基倍半硅氧烷树脂涂层中建立埃级大小孔以降低涂层的密度和介电常数的方法。将带有甲基(三甲硅烷氧基甲硅烷基)单元和烷基(三甲硅烷氧基甲硅烷基)单元的共聚物旋涂至基材上并在250℃进行加热,从而提供刚性的硅氧烷基体。然后,在450-500℃对涂层进行加热,以除去热不稳定基团,由此留下了相应于取代基尺寸的孔,其介电常数约为2.3。作为热不稳定基团,对三氟丙基,氰乙基,苯乙基,和丙基进行了研究。
Ito等人的日本公开特许(HEI)5-333553描述了在质子受体的存在下,通过二乙酰氧基二(叔丁氧基)硅烷的水解而制备包含烷氧基和硅烷醇官能度的硅氧烷树脂的方法。在光酸存在下使所述树脂幅射固化,随后进行加热处理以形成类似SiO2的涂层,并且其可用作IC制造的光刻胶材料。
业已发现,将其中R2为具有3-30个碳原子烷基的支链烷氧基(SiOR2)引入硅氧烷树脂中将提供如下优点:即固化树脂改善的储存稳定性,增加的模量和增加的孔隙率,同时介电常数保持在2.1-3.0的范围内。因此,本发明的目的在于提供一种具有改善储存稳定性的硅氧烷树脂组合物。本发明的另一个目的在于提供硅氧烷树脂的制备方法和固化这些树脂从而生产不溶性的多孔树脂和不溶性的多孔涂层的方法,其中,所述多孔涂层的介电常数为2.1-3.0,孔隙率为2-40%体积,和模量为1.9-20GPa。这些不溶性的多孔涂层的优点在于它们可以用常规的薄膜加工来形成。
发明概述
本发明涉及包含R1SiO3/2硅氧烷单元和(R2O)bSiO(4-b)/2硅氧烷单元的硅氧烷树脂组合物,其中:R1独立地选自具有1-5个碳原子的烷基;R2独立地选自具有3-30个碳原子支链烷基和具有3-30个碳原子的取代的支链烷基,b为1-3。该硅氧烷树脂包含平均摩尔比为1∶99至99∶1的R1SiO3/2单元和(R2O)bSiO(4-b)/2单元。R1SiO3/2单元和(R2O)bSiO(4-b)/2单元之和为树脂组合物中总硅氧烷单元的至少50%。
本发明还涉及通过使通式R1SiX3的硅烷或其混合物和通式(R2O)cSiX(4-c)的硅烷或其混合物进行反应而制备硅氧烷树脂的方法,其中,R1独立地选自具有1-5个碳原子的烷基,R2独立地选自具有3-30个碳原子的支链烷基和具有3-30个碳原子的取代的支链烷基,并且c为1-3并且X为可水解的基团或羟基。
本发明还涉及形成不溶性多孔树脂的方法以及在基材上形成不溶性多孔涂层的方法。 不溶性多孔涂层的介电常数在2.1-3.0的范围内。不溶性多孔树脂和不溶性多孔涂层的孔隙率为2-40%体积。不溶性多孔涂层的模量在1.9-20GPa的范围内。
发明详述
所述硅氧烷树脂组合物包含R1SiO3/2硅氧烷单元和(R2O)bSiO(4-b)/2硅氧烷单元,其中,R1独立地选自具有1-5个碳原子的烷基;R2独立地选自具有3-30个碳原子支链烷基和具有3-30个碳原子的取代的支链烷基,b为1-3。该硅氧烷树脂包含R1SiO3/2单元和(R2O)bSiO(4-b)/2单元的摩尔比为1∶99至99∶1。R1SiO3/2单元和(R2O)bSiO(4-b)/2单元之和为树脂组合物中总硅氧烷单元的至少50%。优选的是,R1SiO3/2单元与(R2O)bSiO(4-b)/2单元的摩尔比为40∶60至98∶2,更优选为50∶50至85∶15。优选的是,R1SiO3/2单元和(R2O)bSiO(4-b)/2单元之和为硅氮烷树脂组合物中硅氧烷单元总量的至少70%。
对硅氧烷树脂的结构没有特别的限制。硅氧烷树脂可以基本上完全缩合的或可以仅仅部分反应的(即包含低于10%摩尔Si-OR和/或低于30%摩尔Si-OH)。部分反应的硅氧烷树脂例如包括但不局限于硅氧烷单元,如RlSi(X)dO(3-d/2)和Si(X)d(OR2)fO(4-d-f/2);式中R1和R2如上定义;每个X独立地为可水解基团或羟基,并且d和f为1-2。可水解基团为通过氧原子连接至硅原子上(Si-OR)从而形成硅连接的烷氧基或硅连接的酰氧基的有机基团。可列举的R(但不局限于)为:具有1-6个碳原子的线型烷基,如甲基,乙基,丙基,丁基,戊基,或己基,以及具有1-6个碳原子的酰基,如甲酰基,乙酰基,丙酰基,丁酰基,戊酰基,或己酰基。硅氧烷树脂另外还可以包含低于约10%摩尔的SiO4/2单元。
硅氧烷树脂的重均分子量在5000-150,000、优选在10,000-50,000的范围内。
R1可为具有1-5个碳原子的线型烷基。可列举的烷基包括但不局限于:甲基,乙基,丙基,丁基,和戊基。优选的是,R1是甲基。
R2为具有3-30个碳原子的取代或未取代的支链烷基。取代的支链烷基可用取代基取代碳键合的氢原子(C-H)。可以列举的取代的R2基团包括但不局限于:卤素如氯和氟,如由式-(CH2)aC(O)O(CH2)bCH3所描述的烷氧羰基,如由式-(CH2)aO(CH2)bCH3描述的烷氧基取代,和如由式-(CH2)aC(O)(CH2)bCH3描述的羰基取代,其中,a0并且b0。可列举的未被取代的R2基团包括但不局限于:异丙基,异丁基,仲丁基,叔丁基,异戊基,新戊基,叔戊基,2-甲基丁基,2-甲基戊基,2-甲基己基,2-乙基丁基,2-乙基戊基,2-乙基己基,等等。优选R2是具有4-18个碳原子的叔烷基,更优选R2为叔丁基。
所述硅氧烷树脂的制备方法包括:
以足以形成硅氧烷树脂的时间和温度,将下列物质混合:
(a)式RlSiX3的硅烷或硅烷的混合物,其中,各R1独立地选自具有1-5个碳原子的烷基,X独立地为可水解的基团或羟基;
(b)式(R2O)cSiX(4-c),其中,R2独立地选自如上所述具有3-30碳原子的支链烷基和具有3-30烷基的取代的支链烷基,c为1-3,X为可水解的基团或羟基;和
(c)水。
硅烷(a)为式R1SiX3的硅烷或硅烷混合物,其中每个R1独立地选自如上所述具有1-5个碳原子的烷基。优选的是,R1是甲基。X是可水解基团或羟基。“可水解基团”指的是大于80%摩尔的X在形成硅氧烷树脂的反应条件下与水反应(水解)。羟基为其中至少70%摩尔与连接至不同硅原子上的另一X基团反应从而缩合和形成硅氧烷键(Si-O-Si)的可缩合基团。可水解基团为氨基或通过氧原子连接至硅原子上(Si-OR)从而形成硅连接的烷氧基或硅连接的酰氧基的有机基团。当X为氨基时,通常以低于约30%摩尔使用,这是因为得到的硅氧烷树脂可能包含大于30%摩尔的SiOH。可列举的R(但不局限于)为:具有1-6个碳原子的线型烷基,如甲基,乙基,丙基,丁基,戊基,或己基,以及具有1-6个碳原子的酰基,如甲酰基,乙酰基,丙酰基,丁酰基,戊酰基,或己酰基。优选的是,硅烷(a)是甲基三甲氧基硅烷或甲基三乙氧基硅烷,这是因为其易得性的缘故。
硅烷(b)为式(R2O)cSiX(4-c)的硅烷或硅烷混合物,其中如上所述,R2独立地选自具有3-30个碳原子支链烷基和具有3-30个碳原子的取代的支链烷基,c为1-3,并且如上所述,X独立地为可水解基团或羟基。优选的是,硅烷(b)是二叔丁氧基二羟基硅烷,二叔丁氧基二甲氧基硅烷,二叔丁氧基二乙氧基硅烷、二叔丁氧基二氨基硅烷和二叔丁氧基二乙酰氧基硅烷,这是因为其易得性的缘故。硅烷(a)和硅烷(b)以1∶99至99∶1的摩尔比存在。优选的是,以相同的基准,硅烷(a)和硅烷(b)以40∶60至98∶2且更优选为50∶50至85∶15的摩尔比而存在。
水以使可水解基团X进行水解的量存在。典型地,水的含量是硅烷(a)和(b)中每摩尔X为0.5-2.0摩尔,更优选0.8-1.2摩尔。
形成硅氧烷的反应可在有或者没有溶剂的液态中进行。如果使用溶剂的话,其可包括不含参与水解/缩合反应的官能团并且是用于硅烷(a)和(b)的溶剂的任何合适的有机溶剂。可列举的溶剂包括但不局限于:饱和脂族烃如正戊烷,己烷,正庚烷,异辛烷和十二烷;脂环族烃,如环戊烷和环己烷;芳族烃,如苯,甲苯,二甲苯和均三甲苯;环醚,如四氢呋喃(THF)和二噁烷;酮,如甲基异丁基甲酮(MIBK));卤素取代的烷烃,如三氯乙烷;卤化芳香族物质,如溴苯和氯苯;和醇,如甲醇,乙醇,丙醇,丁醇。另外,上述溶剂可以共溶剂的形式结合使用。优选的溶剂是芳族化合物和环醚,其中最优选的是甲苯,均三甲苯,和四氢呋喃。当使用溶剂时,以溶剂和硅烷(a)和(b)的总重量计,其用量通常在40-95%重量的范围内,更优选的用量为70-90%重量。
可以任何顺序将组分(a),(b),(c)和非必需的溶剂(如果使用的话)混合,只要可水解基团(X)和水发生接触,以便进行反应从而形成硅氧烷树脂即可。通常,将硅烷溶解于溶剂中,然后将水添加至该溶液中。当将上述组分混合时,通常将发生某种反应。然而,为了增加反应速率和程度,采用了各种促进措施,如温度控制和/或搅拌。
进行反应的温度并不重要,只要它不使硅氧烷树脂产物发生明显的凝胶化或产生固化即可。所述温度通常在20-150℃,优选20-100℃。当X为酰氧基如乙酰氧基时,优选在85℃或以下的温度进行反应。形成硅氧烷树脂的时间取决于许多因素,例如但不局限于:所用的特定的硅烷,温度以及R1和R2O在反应的硅氧烷树脂产物中希望的摩尔比。典型地,反应时间从几分钟至几小时。为了增加所制备硅氧烷树脂的分子量并改善硅氧烷树脂的储存稳定性,优选的是,在上述反应之后或作为上述反应的一部分,进行加重步骤。“加重”指的是通过从40℃加热至溶剂的回流温度进行几小时的反应,从而增加重均分子量。优选的是,加热反应混合物使得加热后硅氧烷树脂的重均分子量在约5,000至150,000的范围内。
当X为酰氧基如乙酰氧基时,作为反应副产物,将产生相应的酸如乙酸。由于乙酸的存在可能会对硅氧烷树脂产物的稳定性产生负面影响,因此理想的是中和任何乙酸。副产物乙酸的中和可以借助使反应混合物与中和剂接触而进行,或者通过蒸馏除去而进行。通常,通过添加溶剂如甲苯(如果不已经存在的话)来完成蒸馏,并在减压和加热(即至多50℃)下以与溶剂共沸物的形式除去乙酸。如果使用中和剂的话,它必须具有中和任何残留乙酸足够的碱性,但它还必须具有不足的碱性使得不会使硅氧烷树脂产物催化重排。合适碱的例子包括碳酸钙,碳酸钠,碳酸氢钠,碳酸铵,氨水,氧化钙或氢氧化钙。中和可通过任何合适的手段来完成,如在粉末中和剂中进行搅拌,然后通过过滤或使反应混合物和任何额外的溶剂通过其大小不妨碍流动的颗粒状中和剂的床。
通过除去溶剂,可以固体形式回收硅氧烷树脂。溶剂的除去方法并不重要,许多方法均是本领域中熟知的。例如,可以采用在真空和加热(即50-120℃)下,借助蒸馏除去溶剂的方法。或者,如果希望硅氧烷树脂处于特定的溶剂中,那么可通过添加第二溶剂并馏出第一溶剂而进行溶剂交换。另外,硅氧烷树脂还可以固体形式储存。
通过对硅氧烷树脂进行加热可获得不溶性多孔树脂,其加热时间和温度足以使硅氧烷树脂固化并除去R2O基团,并由此形成不溶性多孔树脂。“固化”指的是树脂基本上不溶于硅氧烷树脂沉积至基材上的溶剂中,或如上所述对硅氧烷树脂应用有用的如上所述的任何溶剂中。“除去”指的是大于约80%摩尔键合至硅原子上的R2O基团以挥发性烃和烃碎片的形式被除去,这将在涂层中形成空隙,从而形成不溶性多孔树脂。加热可以用一步法或两步法进行。在两步加热法中,首先对硅氧烷树脂进行加热,其加热时间和温度足以进行固化但不明显除去R2O基团。通常,所述温度可在大于20℃至350℃的范围内保持几分钟至几小时。然后,在大于350℃至低于硅氧烷树脂骨架或如上所述键合至R1SiO3/2硅氧烷单元的硅原子上的R1的分解温度的温度范围内对固化的树脂进行进一步加热(加热时间为几分钟至几小时),从而从硅原子上除去R2O。通常,该除去步骤在大于350℃至800℃的温度范围内进行。优选的是,在大于350至600℃的温度范围内进行除去步骤,更优选的温度为400-550℃。在最终不溶性多孔树脂中的孔隙率可通过硅氧烷树脂中OR2的摩尔百分数和如何对硅氧烷树脂进行加热来控制。
在一步法中,通过在大于20℃至低于硅氧烷树脂骨架或如上所述键合至硅原子上的R1基团的分解温度的范围内进行加热,而同时进行硅氧烷树脂的固化以及R2O基团的除去,从而从固化的硅氧烷树脂上除去R2O。通常优选的是,在大于350至600℃的温度范围内进行固化/除去步骤,最优选的温度范围是400-550℃。
优选的是,在惰性气氛中进行加热,但也可以使用其它气氛。在此有用的惰性气氛包括但不局限于氮,氦和氩气氛,其中氧含量低于50ppm,优选低于15ppm。另外,还可以在真空至大气压以上的任何有效压力下和在任何有效的氧化或非氧化气体环境如包含空气,氧气,氧等离子体,臭氧,氨水,胺,水汽,N2O,氢等等的气体环境下进行加热。
不溶性多孔树脂可用作具有可控孔隙率和高达550℃的高温稳定性的多孔材料,如选择性气体或液体可渗透的成形膜,催化剂载体,储能体系例如电池以及分子分离和隔离。术语“多孔”指的是不溶性多孔树脂的孔隙率在2-40%体积的范围内。不溶性多孔树脂的模量在1.9-20GPa的范围内。
可通过如下步骤用硅氧烷树脂在基材上制备不溶性多孔涂层:
(A)用包括含R1SiO3/2硅氧烷单元和(R2O)bSiO(4-b)/2硅氧烷单元的硅氧烷树脂组合物的涂料组合物涂布基材,其中,R1独立地选自具有1-5个碳原子的烷基并且R2独立地选自如上所述的具有3-30个碳原子支链烷基和具有3-30个碳原子的取代的支链烷基,b为1-3;该硅氧烷树脂包含平均摩尔比为1∶99至99∶1的R1SiO3/2硅氧烷单元和(R2O)bSiO(4-b)/2硅氧烷单元;R1SiO3/2硅氧烷单元和(R2O)bSiO(4-b)/2硅氧烷单元之和为树脂组合物中硅氧烷单元总量的至少50%;
(B)加热涂布的基材到足以使涂料组合物固化的时间和温度,和
(C)进一步加热涂布的基材到足以从固化的涂料组合物中除去R2O基团的时间和温度,由此在基材上形成不溶性多孔涂层。
通常以溶剂分散体的形式将硅氧烷树脂施加至基材上。可以使用的溶剂包括不影响所得涂层或基材的能溶解或分散硅氧烷树脂以形成均匀的液体混合物的任何试剂或试剂的混合物。通常,所述溶剂可为不包含可参与与硅氧烷树脂反应(例如上面所讨论的硅烷混合物与水的反应)的官能团如羟基的任何有机溶剂。
溶剂的含量为足以溶解硅氧烷树脂至对于特定应用所希望浓度。通常,以硅氧烷树脂和溶剂的重量计,溶剂的含量为40-95%重量,优选70-90%重量。如果硅氧烷树脂已经保留在上面所述的溶剂中,那么该溶剂可以在涂布基材中使用,或者如果需要,可以通过添加第二溶剂并蒸馏掉第一溶剂而进行简单的溶剂交换。
硅氧烷树脂施加至基材上的具体方法包括但不局限于旋涂,浸涂,喷涂,流涂,丝网印刷等等。优选的施加方法为旋涂。当使用溶剂时,使溶剂从涂布基材蒸发,从而使硅氧烷树脂涂层沉积至基材上。就蒸发而言,可以采用任何合适的方法,如通过暴露至周围环境中而进行简单的风干,通过施加真空,或加热(至多50℃),或在固化的早期进行蒸发。当采用旋涂时,由于旋转驱走溶剂,因此,额外的干燥方法被最小化。
在施加至基材上之后,在足以使硅氧烷树脂固化并除去键合至硅原子上的R2O基团的温度下对硅氧烷树脂涂层进行加热,由此形成不溶性的多孔涂层。“固化涂层”指的是涂层基本上不溶于借此硅氧烷树脂沉积至基材上的溶剂中或用于施加硅氧烷树脂的上述任何溶剂中。“除去”指的是大于80%摩尔的键合至硅原子上的R2O基团以挥发性烃和烃碎片的形式被除去,这将在涂层中产生空隙,从而形成不溶性多孔树脂。加热可以用一步法或两步法进行。在两步加热法中,首先在不明显除去R2O基团的情况下在足以进行固化的温度下进行加热。通常,所述温度可在大于20℃至350℃的范围内。然后在大于350℃至低于硅氧烷树脂骨架或如上所述键合至硅原子上的R1基团的分解的温度范围内,对固化的硅氧烷树脂涂层进一步加热,以便从硅原子上除去R2O基团。通常在350-800℃的温度下进行除去步骤。优选的是,在大于350℃至600℃的温度范围内进行除去步骤,最优选的温度范围在400-550℃。在固化和加热步骤期间,大于90%摩尔的R1基团通常保留在硅氧烷树脂上。
在一步法中,通过在大于20℃至低于硅氧烷骨架或如上所述键合至硅原子上的R1基团的分解温度下进行加热而同时进行硅氧烷树脂的固化和除去R2O基团,从而从固化的涂料组合物中除去R2O基团。通常优选的是,固化/除去步骤在大于350℃至600℃的温度范围内进行,最优选的温度范围在400-550℃。
优选的是,在惰性气氛中进行加热,但也可以使用其它气氛。在此使用的惰性气氛包括但不局限于氮,氦和氩气氛,其中氧含量低于50ppm,优选低于15ppm。另外,还可以在真空至大气压以上任何的有效大气压力下并且在任何有效的氧化或非氧化气体环境如包含空气、氧气,氧等离子体,臭氧,氨水,胺,水汽,N2O,氢等等的气体环境中进行加热。
在本发明中,通常可采用任何加热方法,如利用石英管炉,对流加热炉或辐散或微波能的加热方法。同样地,加热速度通常并不重要,但是最实用且优选的是尽可能快地对涂布基材进行加热。
在本发明中生产的不溶性多孔涂层可以在任何基材上生产。然而,特别是将涂层用于电子基材上。“电子基材”指的是包括用于制造半导体元件的硅基器件和砷化镓基器件,包括焦平面阵列,光电子设备,光电池,光学装置,类似晶体管的装置,3-D装置,在绝缘体上的硅装置,超点阵装置等等。
通过上述方法,在基材上形成了薄的(小于5微米)不溶性多孔涂层。优选的是,所述涂层的厚度为0.3-2.5微米,更优选的厚度为0.5-1.2微米。该涂层将使各种基材的不规则表面变平滑,并具有优异的粘结性能。
如果需要,可以将额外的涂层施加至不溶性多孔涂层上。这些额外涂层可包括例如二氧化硅涂层,含硅涂层,含硅碳涂层,含硅氮涂层,含硅氧氮涂层,含硅氮碳涂层和/或通过沉积(即CVD,PECVD等等)无定形SiC:H、金刚石、氮化硅而产生的金刚石似的涂层。所述涂层的施加方法在本领域中是已知的。额外涂层的施加方法并不重要,并且所述涂层通常通过化学气相沉积技术例如热化学气相沉积(TCVD),光化学气相沉积,等离子体增强的化学气相沉积(PECVD),电子回旋共振(ECR),和喷射气相沉积来施加。另外,额外的涂层还可通过物理气相淀积技术例如溅射或电子束蒸发来施加。这些方法包括以热或等离子体的形式将能量施加至挥发物上从而引起希望的反应,或者将能量聚集在材料的固体试样上,从而进行沉积。
通过所述方法形成的不溶性多孔涂层尤其可用作电子器件如集成电路上的涂层。对于层间绝缘涂层,通过所述方法制得的不溶性多孔涂层的介电常数在2.1-3的范围内,更优选在2.1-2.5的范围内。术语“多孔”指的是不溶性多孔涂层的孔隙率为2-40%体积。不溶性多孔涂层的模量在1.9-20GPa的范围内,优选4-13GPa。
实施例
提供如下非限定性实施例,以便使本领域熟练技术人员可以更容易地理解本发明。在实施例中,重量以克(g)表示。分子量以借助凝胶渗透色谱法测量的重均分子量(Mw)和数均分子量(Mn)来表示。利用29Si核磁共振(NMR),对硅氧烷树脂组合物进行分析。利用QuantaChrome Autosorb 1MP系统进行氮吸附孔隙率测定。在置于试样池中之前,将固化的硅氧烷树脂研磨成细粉,进行几小时的脱气,并加载至分析装置中。通过Brunauer-Emmett-Teller法测量表面积。假定孔填满吸附物,在接近一致的相对压力(P/P0=0.995)下,根据吸入孔中的蒸汽量测量总的孔体积。 利用氦气比重瓶测量骨架密度。骨架密度表示硅氧烷树脂实体结构的真密度,在测量中没有包括任何内部空隙、裂缝或孔。根据骨架密度和总的孔体积计算百分孔隙率。利用Woollam M-88分光椭圆光度仪测量折射率(RI)和涂层厚度。
在下列实施例中,Me表示甲基,tBu表示叔丁基,Ac表示乙酰氧基,而Et表示乙基。在下列表中,n.m.表示没有测量特定的性能。
实施例1
本实施例阐明硅氧烷树脂组合物的形成,式中R1为Me,R2为叔丁基。将10.00g(HO)2Si(OtBu)2和6.44g MeSi(OMe)3添加至在氩气氛下烧瓶中的22.20gTHF中。然后在室温下,将1.75克去离子水慢慢添加至反应混合物中。在室温搅拌1小时之后,对反应混合物回流加热6小时。利用旋转蒸发器除去溶剂从而得到粘性油状的硅氧烷树脂。在150℃,在真空下,对该油状物加热12小时;将温度升至200℃,并在真空下再保持5小时。结果得到9.37克的固体树脂,其Mw为13,100,Mn为4,900。通过29Si NMR测定的成分为(MeSiO3/2)0.36((ZO)SiO3/2)0.14((tBuO)bSiO4-b/2)0.5,其中ZO=OH或OMe。
实施例2
本实施例阐明不溶性多孔树脂的形成。将实施例1制备的硅氧烷树脂试样(1.9744克)称量加入氧化铝坩埚中并转移至石英管熔炉中。将熔炉抽真空至小于20毫米汞柱(小于2666Pa)并回填氩气。以10℃/分钟的速率将试样加热至450℃,并450℃保温1小时,之后在氩气吹洗的同时冷却到室温。固化物质的得率为47.2%重量(9319克)。用29Si NMR测量的成分为(MeO3/2)0.47(SiO4/2)0.53。BET表面积为584m2/g且孔体积为0.40cc/g。
实施例3
本实施例阐明硅氧烷树脂组合物的形成,式中R1为Me,R2为叔丁基。以表1所述的用量,将MeSi(OMe)3(A),(H2N)2Si(OtBu)2(B)和THF添加至氩气氛下的烧瓶中。然后,慢慢地将去离子水添加至该烧瓶中并在室温对该混合物搅拌1小时,然后将该混合物加热至65℃。在65℃保温两小时,然后冷却至室温。在室温真空下(1mmHg),利用旋转蒸发器除去挥发性组分。将产物溶解于甲苯中并进行共沸干燥,保持溶液回流30分钟,冷却并通过0.45微米注射器过滤器进行过滤。在25℃使溶剂真空(1mmHg)蒸发,从而得到硅氧烷树脂。硅氮烷树脂结构和分子量的分析列于表2中。
表1.树脂合成的概述
实施例号 | (A)(g) | (B)(g) | THF(g) | H2O(g) | 回流步骤中的甲苯(g) | 收率(g) | 外观 |
3-1 | 20.0 | 15 | 303 | 11.1 | 50 | 11.8 | 蜡状 |
3-2 | 20.1 | 3.0 | 30.2 | 11.6 | 50 | 12.8 | 油状 |
3-3 | 20.0 | 7.6 | 29.9 | 13.2 | 50 | 16.8 | 油状 |
3-4 | 20.0 | 12.0 | 30.0 | 14.8 | 50 | 21.7 | 油状 |
表2.(MeSiO3/2)f((tBuO)bSi4-b/2)g树脂的分析
实施例 | 基于反应物的f/g摩尔比 | f/g摩尔比(29SiNMR) | Mn | Mw | Tg(℃) |
3-1 | 95.3/4.7 | 96.0/4.0 | 109,700 | 2,460 | -43.9 |
3-2 | 91.0/9.0 | n.m. | >100,000* | n.m. | -13.4 |
3-3 | 80.0/20.0 | 80.0/20.0 | 17,600 | 1,480 | -28.9 |
3-4 | 71.8/28.2 | 75.0/25.0 | 7,310 | 1,090 | -39.4 |
*由于所述物质呈凝胶状,因此其分子量数据不确定的,然而,它仍然能再溶解于溶剂中。
实施例4
本实施例阐明不溶性多孔树脂的形成。将实施例3制备的树脂(2-3克)称量加入氧化铝坩埚并转移至石英管熔炉中。将熔炉抽真空至小于20毫米汞柱(小于2666Pa)并回填氩气。以10℃/分钟的速率将试样加热至表3所示的温度,并该温度保温1小时,然后冷却至室温,同时用氩气进行吹洗。热解温度,炭化收率和孔隙率数据示于表3中。炭化收率(char yield)用在规定温度分析之后所保留的重量百分数来表示,并用作膨松硅氧烷树脂在加热后的收缩率的量度。
表3.固化树脂的孔隙率和炭化收率
实施例号 | 树脂样品号 | 温度℃ | 炭化得率重量% | 孔体积cm3/g | 表面积BETm2/g |
4-1 | 3-1 | 400 | 80.2 | 0.157 | 142 |
4-2 | 3-1 | 450 | 79.7 | 0.161 | 160 |
4-3 | 3-2 | 400 | 79.3 | n.m. | n.m. |
4-4 | 3-2 | 450 | 76.8 | 0.265 | 413 |
4-5 | 3-3 | 380 | 71.4 | 0.214 | 272 |
4-6 | 3-3 | 400 | 66.3 | n.m. | n.m. |
4-7 | 3-3 | 450 | 62.6 | 0.295 | 486 |
4-8 | 3-4 | 380 | 69.4 | 0.056 | 35 |
4-9 | 3-4 | 400 | 60.9 | 0.227 | 277 |
4-10 | 3-4 | 450 | 49.5 | 0.213 | 348 |
实施例5
本实施例阐明硅氧烷树脂组合物的形成,其中R1为Me,R2为叔丁基。以表4所述的用量,将MeSi(OMe)3(A),(AcO)2Si(OtBu)2(B)和THF添加至氩气氛下的烧瓶中。然后将去离子水添加至该烧瓶中并在室温对该混合物搅拌1小时。将75克甲苯添加至该反应混合物中。利用旋转蒸发器除去溶剂,以得到粘性油状的产物,立即将产物溶解于150甲苯中。在减压下,以与甲苯共沸物的形式除去剩余的乙酸(共沸物沸点在38℃)。再次将树脂溶解于110克甲苯中,进行共沸干燥并回流1小时。对溶液进行过滤,并通过蒸发除去溶剂,从而得到最终的树脂产物。树脂合成的概要示于表4中。树脂的分子量信息示于表5中。
表4树脂合成的概要
实施例号 | (A)(g) | (B)(g) | THF(g) | H2O(g) | 收率(g) | 外观 |
5-1 | 18.6 | 40.0 | 72.0 | 11.1 | 23.6 | 固体 |
5-2 | 27.9 | 40.0 | 80.0 | 14.5 | 26.0 | 固体 |
5-3 | 43.5 | 40.3 | 90.0 | 20.0 | 40.0 | 固体 |
5-4 | 92.9 | 39.9 | 120.3 | 28.3 | 67.3 | 蜡状 |
表5.(MeSiO3/2)f((tBuO)bSiO4-b/2)g树脂的分析
实施例 | 基于反应物的f/g摩尔比 | 基于29SiNMR的f/g摩尔比 | Mn | Mw |
5-1 | 0.50/0.50 | 0.44/0.56 | 2,990 | 17,700 |
5-2 | 0.60/0.40 | 0.55/0.44 | 2,010 | 46,000 |
5-3 | 0.70/0.30 | 0.69/0.31 | n.m. | >100,000* |
5-4 | 0.85/0.15 | 0.83/0.17 | 3,400 | 32,100 |
*由于所述物质呈凝胶状,因此其分子量数据不确定的,然而,它仍然能再溶解于溶剂中。
实施例6
本实施例阐明不溶性多孔树脂的形成。将实施例5制备的树脂(2-3克)称量加入氧化铝坩埚并转移至石英管熔炉中。将熔炉抽真空至小于20毫米汞柱(小于2666Pa)并回填氩气。以10℃/分钟的速率将试样加热至450℃,并在450℃保温1小时,然后冷却至室温,同时用氩气进行吹洗。以透明或稍稍不透明的厚薄膜的形式获得了固化的硅氧烷树脂。热解温度,炭化收率和孔隙率数据示于表6中。炭化收率用在规定温度分析之后所保留的重量百分数来表示。
表6.固化树脂的多孔性和炭化收率
实施例号 | 树脂样品号 | 骨架密度g/cm3 | 炭化得率重量% | 孔体积cm3/g | 孔隙率,% | 表面积,BET.m2/g |
6-1 | 5-1 | 1.693 | 60.5 | 0.271 | 31.4 | 461 |
6-2 | 5-2 | 1.624 | 72.5 | 0.280 | 31.3 | 481 |
6-3 | 5-3 | 1.505 | 78.0 | 0.249 | 27.2 | 425 |
6-4 | 5-4 | 1.398 | 76.5 | 0.125 | 14.9 | 168 |
实施例7
本实施例阐明不溶性多孔涂层的形成。将实施例5制备的树脂(2-3克)溶解于MIBK中,形成包含25%重量树脂的透明溶液。使溶液过滤通过1.0微米的注射膜滤器,然后通过0.2微米的注射膜滤器,从而除去任何大的颗粒。通过以2000rpm旋涂20秒,将该溶液施加至硅片上。将涂布的硅片放入石英管熔炉中并用氮气对该熔炉进行吹洗。将熔炉加热至400℃,425℃或450℃(50-60℃/分钟),并在所述温度保温2小时,然后在保持氮气吹洗的同时冷却至室温。在进行性能测量之前,将涂布的硅片储存在氮气氛下。该薄膜的模量和介电常数(DK)示于表7中。
表7.在硅片上树脂的薄膜性能
实施例号 | 树脂样品号 | 温度℃ | Dk | 模量GPa | 硬度GPa | 厚度埃 | RI |
7-1 | 5-1 | 450 | 2.32 | 7.9 | 0.91 | 6,300 | 1.273 |
7-2 | 5-1 | 425 | 2.36 | 9.0 | 1.11 | 6,728 | 1.276 |
7-3 | 5-1 | 400 | 2.48 | 8.7 | 0.95 | 6,826 | 1.271 |
7-4 | 5-2 | 450 | 2.16 | 3.5 | 0.51 | 6,199 | 1.252 |
7-5 | 5-2 | 425 | 2.48 | 5.5 | 0.65 | 6,374 | 1.307 |
7-6 | 5-2 | 400 | 2.55 | 4.8 | 0.53 | 6,333 | 1.338 |
7-7 | 5-3 | 450 | 2.61 | 7.4 | 1.11 | 8,551 | 1.347 |
7-8 | 5-3 | 425 | 2.52 | 6.9 | 1.08 | 9,025 | 1.350 |
7-9 | 5-3 | 400 | 2.38 | 7.4 | 1.19 | 9,413 | 1.336 |
7-10 | 5-4 | 450 | 2.88 | 7.8 | 1.4 | 10,500 | 1.368 |
7-11 | 5-4 | 425 | 2.71 | 6.0 | 1.19 | 10,525 | 1.383 |
7-12 | 5-4 | 400 | 2.63 | 7.1 | 1.25 | 10,892 | 1.375 |
对比例1
本对比例阐明根据US6,022,814制得的(MeO3/2)h(CF3CH2CH2)SiO3/2)i树脂的制备以及由该树脂形成薄膜。在烧瓶中对0.5克三氟丙基三甲氧基硅烷,9.5克甲基三乙氧基硅烷,10克异丙醇,3.4克丁醇和0.10克草酸二水合物进行混合。然后,通过注射器将3.4克水加入该反应烧瓶中。观察到温度从24℃稍微升高至30℃。将反应混合物加热至70℃,并在70℃保温2小时,然后冷却至室温。然后,在35℃于真空下除去溶剂,得到4.98克产物。
将得到的产物溶解于10克丁醇和2.56克异丙醇中,形成溶液。通过在1500、2000、和3000rpm下的旋涂,将该溶液施加至单晶硅片上,得到薄膜质量差的硅片,所述薄膜将得不到任何特征化数据。所述薄膜饱含许多分散在硅片整个表面上的不同大小的圆形缺陷。利用光学显微术,还在薄膜表面之下发现了所述的这些缺陷。
将回收到的所制备产物的另一试样溶解于MIBK中,形成25%重量的溶液。使溶液过滤通过1.0微米的注射膜滤器,然后通过0.2微米的注射膜滤器,从而除去任何大的颗粒。通过在2000rpm下旋涂20秒,将该溶液施加至硅片上。将涂布的硅片放入石英管熔炉中并用氮气对该熔炉进行吹洗。将熔炉加热至450℃(25℃/分钟),并在所述温度保温2小时,然后在保持氮气吹洗的同时冷却至室温。在进行性能测量之前,将涂布的硅片储存在氮气氛下。该薄膜的模量和介电常数示于表8中。
表8.在硅片上树脂的薄膜性能
实施例号 | Dk | 模量GPa | 厚度埃 | RI |
C1-1 | n.m. | n.m. | 5632 | 1.3738 |
C1-2 | 2.58 | 1.50 | 5149 | 1.3878 |
C1-3 | 2.63 | 1.60 | 5202 | 1.3736 |
由(MeO3/2)h(CF3CH2CH2)SiO3/2)i树脂制备的薄膜具有高于US6,022,814中报道的树脂薄膜的DK。其模量比本发明不溶性多孔涂层的模量低得多。
对比例2
本实施例阐明(MeSiO3/2)树脂的形成以及由该树脂形成薄膜。将2560克(140摩尔)去离子水和1536克(15.4摩尔)(MIBK)添加至烧瓶中。搅拌下将该混合物冷却至-4℃。在搅拌的同时,在4小时内,以5.5克/分钟的速率,将512克(5.12摩尔)MIBK和817克甲基三氯硅烷(5.46摩尔)添加至烧瓶中。在添加期间,温度升高至约8℃。在添加结束之后,用2小时使温度升高至56℃,并在56℃再保温2小时。在56℃时反应液是透明的。将反应液冷却至30℃以下,这时将观察到相分离。包含盐酸的水层通过烧瓶的底阀排掉。包含硅氧烷树脂产物的溶剂层在搅拌下用1L去离子水进行洗涤,然后除去水。重复该洗涤步骤4次,直至洗涤水的pH值约为4。于40℃,利用旋转蒸发器除去MIBK溶剂,水,和任何剩余的盐酸,留下甲苯倍半硅氧烷树脂产物,然后将其溶解于甲苯中。利用旋转蒸发器除去甲苯。在室温下,进一步使硅氧烷树脂产物真空干燥过夜。将树脂放在冷藏器中,用于进一步的表征和薄膜评估。所得树脂的GPC分析表明,其Mw为13,500,Mn为3,500。
将甲基倍半硅氧烷树脂产物(2-3克)溶解于MIBK中,形成包含25%重量树脂的透明溶液。使溶液过滤通过1.0微米的注射膜滤器,然后通过0.2微米的注射膜滤器,从而除去任何大的颗粒。通过在2000rpm下旋涂20秒,将该溶液施加至硅片上。将涂布的硅片放入石英管熔炉中并用氮气对该熔炉进行吹洗。将熔炉加热至450℃(25℃/分钟)并在该温度下保温2小时,然后在保持氮吹洗的同时冷却至室温。在进行性能测量之前,将涂布的硅片储存在氮气氛下。该薄膜的模量和介电常数示于表9中。
表9.在硅片上树脂的薄膜性能
实施例号 | Dk | 模量GPa | 硬度GPa | 厚度埃 | RI |
C2-1 | 2.50 | 1.50 | 0.26 | 9402 | 1.3652 |
C2-2 | 2.51 | 1.50 | 0.30 | 9286 | 1.3787 |
C2-3 | n.m. | n.m. | n.m. | 9707 | 1.3842 |
该对比例阐明,由(MeSiO3/2)树脂制得的非多孔薄膜的介电常数与本发明的薄膜类似,然而模量却低得多(小于2GPa)。
Claims (9)
1.一种硅氧烷树脂组合物,包含R1SiO3/2硅氧烷单元和(R2O)bSiO(4-b)/2硅氧烷单元,其中R1独立地选自具有1-5个碳原子的烷基;R2独立地选自具有3-30个碳原子的支链烷基和具有3-30个碳原子的取代的支链烷基,b为1-3,该硅氧烷树脂包含摩尔比为1∶99至99∶1的R1SiO3/2单元和(R2O)bSiO(4-b)/2单元,并且R1SiO3/2单元和(R2O)bSiO(4-b)/2单元之和为树脂组合物中硅氧烷单元总量的至少50%。
2.权利要求1的硅氧烷树脂组合物,其中R2为叔丁基。
3.一种制备硅氧烷树脂的方法,所述氧烷树脂包含R1SiO3/2硅氧烷单元和(R2O)bSiO(4-b)/2硅氧烷单元,其中b为1-3,所述方法包括以足以形成硅氧烷树脂的时间和温度混合下述物质:
(a)式R1SiX3的硅烷或硅烷的混合物,其中,各R1独立地选自具有1-5个碳原子的烷基,X独立地为可水解的基团或羟基;
(b)式(R2O)cSiX(4-c)的硅烷或硅烷的混合物,其中,R2独立地选自具有3-30个碳原子的支链烷基和具有3-30个碳原子的取代的支链烷基,c为1-3,X为可水解的基团或羟基,和
(c)水;
其中,硅烷(a)与硅烷(b)的摩尔比为1∶99至99∶1。
4.权利要求3的方法,其中R1甲基,和R2为叔丁基。
5.一种不溶性多孔树脂的形成方法,包括如下步骤:
(A)以足以使权利要求1或2的硅氧烷树脂固化的时间和温度加热所述硅氧烷树脂,
(B)以足以从固化硅氧烷树脂中除去R2O基团的时间和温度进一步加热所述硅氧烷树脂,从而形成不溶性多孔树脂。
6.一种在基材上形成不溶性多孔涂层的方法,包括如下步骤:
(A)用包括含R1SiO3/2硅氧烷单元和(R2O)bSiO(4-b)/2硅氧烷单元的硅氧烷树脂组合物的涂料组合物涂布基材,其中,R1独立地选自具有1-5个碳原子的烷基,和R2独立地选自具有3-30个碳原子的支链烷基和具有3-30个碳原子的取代的支链烷基,b为1-3,该硅氧烷树脂组合物包含摩尔比为1∶99至99∶1的R1SiO3/2单元和(R2O)bSiO(4-b)/单元,并且R1SiO3/2单元和(R2O)bSiO(4-b)/2单元之和为树脂组合物中硅氧烷单元总量的至少50%;
(B)以足以使所述涂料组合物固化的时间和温度加热涂布的基材,和
(C)以足以从固化涂料组合物中除去R2O基团的时间和温度进一步加热涂布的基材,由此在基材上形成不溶性多孔涂层。
7.权利要求5或6的方法,其中,在一个步骤中进行硅氧烷树脂的固化和从固化的硅氧烷树脂中除去R2O基团。
8.权利要求5或6的方法,其中,不溶性多孔树脂的介电常数为2.1-3.0,孔隙率为2-40%体积,模量为1.9-20Gpa。
9.一种具有通过权利要求6的方法制得的不溶性多孔涂层的电子基材。
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US09/915,902 US6872456B2 (en) | 2001-07-26 | 2001-07-26 | Siloxane resins |
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CN (1) | CN1535300A (zh) |
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CN101945880A (zh) * | 2008-02-20 | 2011-01-12 | 瓦克化学股份公司 | 可固化聚合物混合物 |
CN101048704B (zh) * | 2004-11-02 | 2011-04-13 | 陶氏康宁公司 | 抗蚀剂组合物 |
CN101501139B (zh) * | 2006-08-04 | 2011-08-17 | 陶氏康宁公司 | 硅氧烷树脂和硅氧烷组合物 |
CN103534296A (zh) * | 2011-05-11 | 2014-01-22 | 汉高股份有限公司 | 具有改善的阻隔性的聚硅氧烷树脂 |
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- 2002-07-16 CN CNA028146980A patent/CN1535300A/zh active Pending
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Cited By (4)
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CN101048704B (zh) * | 2004-11-02 | 2011-04-13 | 陶氏康宁公司 | 抗蚀剂组合物 |
CN101501139B (zh) * | 2006-08-04 | 2011-08-17 | 陶氏康宁公司 | 硅氧烷树脂和硅氧烷组合物 |
CN101945880A (zh) * | 2008-02-20 | 2011-01-12 | 瓦克化学股份公司 | 可固化聚合物混合物 |
CN103534296A (zh) * | 2011-05-11 | 2014-01-22 | 汉高股份有限公司 | 具有改善的阻隔性的聚硅氧烷树脂 |
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TW593548B (en) | 2004-06-21 |
US6872456B2 (en) | 2005-03-29 |
KR20040023683A (ko) | 2004-03-18 |
EP1412434B1 (en) | 2008-07-02 |
WO2003010246A1 (en) | 2003-02-06 |
JP4411067B2 (ja) | 2010-02-10 |
US20030087082A1 (en) | 2003-05-08 |
EP1412434A1 (en) | 2004-04-28 |
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ATE399822T1 (de) | 2008-07-15 |
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