CN1543664A - 有机硅树脂和由其生产的多孔材料 - Google Patents
有机硅树脂和由其生产的多孔材料 Download PDFInfo
- Publication number
- CN1543664A CN1543664A CNA028161130A CN02816113A CN1543664A CN 1543664 A CN1543664 A CN 1543664A CN A028161130 A CNA028161130 A CN A028161130A CN 02816113 A CN02816113 A CN 02816113A CN 1543664 A CN1543664 A CN 1543664A
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- Prior art keywords
- organic siliconresin
- cetyl
- group
- hydroxyl
- solvent
- 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
Links
- 229920002050 silicone resin Polymers 0.000 title abstract description 3
- 239000011148 porous material Substances 0.000 title description 7
- 229920005989 resin Polymers 0.000 claims abstract description 37
- 239000011347 resin Substances 0.000 claims abstract description 37
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 26
- 239000002904 solvent Substances 0.000 claims description 45
- 238000000576 coating method Methods 0.000 claims description 31
- 239000000203 mixture Substances 0.000 claims description 31
- 239000011248 coating agent Substances 0.000 claims description 30
- 239000000758 substrate Substances 0.000 claims description 22
- 229910052799 carbon Inorganic materials 0.000 claims description 20
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 18
- 229910000077 silane Inorganic materials 0.000 claims description 18
- 229910052710 silicon Inorganic materials 0.000 claims description 18
- -1 chloro octyl group Chemical group 0.000 claims description 17
- 239000010703 silicon Substances 0.000 claims description 17
- 150000001721 carbon Chemical group 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000000919 ceramic Substances 0.000 claims description 8
- 239000000463 material Substances 0.000 claims 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 claims description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 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 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 125000002511 behenyl 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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 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 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 150000004292 cyclic ethers Chemical class 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 239000003849 aromatic solvent Substances 0.000 claims 2
- 125000002723 alicyclic group Chemical group 0.000 claims 1
- 125000001931 aliphatic group Chemical group 0.000 claims 1
- 239000004210 ether based solvent Substances 0.000 claims 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims 1
- 230000026030 halogenation Effects 0.000 claims 1
- 238000005658 halogenation reaction Methods 0.000 claims 1
- 239000004065 semiconductor Substances 0.000 abstract description 6
- 239000010409 thin film Substances 0.000 abstract description 5
- 229910004726 HSiO3/2 Inorganic materials 0.000 abstract 1
- 125000004432 carbon atom Chemical group C* 0.000 abstract 1
- 229910010293 ceramic material Inorganic materials 0.000 abstract 1
- 238000005336 cracking Methods 0.000 description 26
- 239000010408 film Substances 0.000 description 25
- 239000000523 sample Substances 0.000 description 22
- RXGUIWHIADMCFC-UHFFFAOYSA-N 2-Methylpropyl 2-methylpropionate Chemical compound CC(C)COC(=O)C(C)C RXGUIWHIADMCFC-UHFFFAOYSA-N 0.000 description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-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 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 8
- 238000001723 curing Methods 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 238000004528 spin coating Methods 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 230000007062 hydrolysis Effects 0.000 description 6
- 238000006460 hydrolysis reaction Methods 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 125000000962 organic group Chemical group 0.000 description 5
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 4
- 229910020175 SiOH Inorganic materials 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 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 4
- 239000012528 membrane Substances 0.000 description 4
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- XLYOFNOQVPJJNP-DYCDLGHISA-N deuterium hydrogen oxide Chemical compound [2H]O XLYOFNOQVPJJNP-DYCDLGHISA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 239000007788 liquid Substances 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
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 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 2
- 230000035515 penetration Effects 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical class CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- UHOPWFKONJYLCF-UHFFFAOYSA-N 2-(2-sulfanylethyl)isoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(CCS)C(=O)C2=C1 UHOPWFKONJYLCF-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 150000001334 alicyclic compounds Chemical class 0.000 description 1
- 150000007824 aliphatic compounds Chemical class 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013068 control sample 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
- 238000000354 decomposition reaction Methods 0.000 description 1
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 1
- 150000002012 dioxanes Chemical class 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- YGUFXEJWPRRAEK-UHFFFAOYSA-N dodecyl(triethoxy)silane Chemical compound CCCCCCCCCCCC[Si](OCC)(OCC)OCC YGUFXEJWPRRAEK-UHFFFAOYSA-N 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 150000004820 halides Chemical group 0.000 description 1
- YCOZIPAWZNQLMR-UHFFFAOYSA-N heptane - octane Natural products CCCCCCCCCCCCCCC YCOZIPAWZNQLMR-UHFFFAOYSA-N 0.000 description 1
- RSKGMYDENCAJEN-UHFFFAOYSA-N hexadecyl(trimethoxy)silane Chemical compound CCCCCCCCCCCCCCCC[Si](OC)(OC)OC RSKGMYDENCAJEN-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 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 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- SLYCYWCVSGPDFR-UHFFFAOYSA-N octadecyltrimethoxysilane Chemical compound CCCCCCCCCCCCCCCCCC[Si](OC)(OC)OC SLYCYWCVSGPDFR-UHFFFAOYSA-N 0.000 description 1
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 description 1
- MSRJTTSHWYDFIU-UHFFFAOYSA-N octyltriethoxysilane Chemical compound CCCCCCCC[Si](OCC)(OCC)OCC MSRJTTSHWYDFIU-UHFFFAOYSA-N 0.000 description 1
- 229960003493 octyltriethoxysilane Drugs 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 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
- 229920003209 poly(hydridosilsesquioxane) Polymers 0.000 description 1
- 238000002459 porosimetry Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 125000005389 trialkylsiloxy group Chemical group 0.000 description 1
- RYPYGDUZKOPBEL-UHFFFAOYSA-N trichloro(hexadecyl)silane Chemical compound CCCCCCCCCCCCCCCC[Si](Cl)(Cl)Cl RYPYGDUZKOPBEL-UHFFFAOYSA-N 0.000 description 1
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 1
- 239000005052 trichlorosilane Substances 0.000 description 1
- OYGYKEULCAINCL-UHFFFAOYSA-N triethoxy(hexadecyl)silane Chemical compound CCCCCCCCCCCCCCCC[Si](OCC)(OCC)OCC OYGYKEULCAINCL-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
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
- H01L21/02123—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon
- H01L21/02126—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material containing Si, O, and at least one of H, N, C, F, or other non-metal elements, e.g. SiOC, SiOC:H or SiONC
-
- C—CHEMISTRY; METALLURGY
- 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
- 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
-
- 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
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Abstract
有机硅树脂,具有式(R1SiO3/2)x(HSiO3/2)y,其中R1为具有8-24个碳原子的烷基,x为0.05-0.7的值,y为0.3-0.95的值并且x+y=1。该树脂用于形成多孔陶瓷材料和在半导体器件上形成多孔薄膜。
Description
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。所述涂层可以通过化学蒸汽淀积或者旋涂技术形成。例如,US4,756,977披露了利用氢倍半硅氧烷树脂在电子器件上形成涂层。
由于电路元件尺寸和所述元件之间的空间持续减小,因此,需要具有更低介电常数的绝缘材料。特别希望的是能够提供介电常数低于3的材料。介电常数低于3的涂层的一种生产方法是利用旋涂(spin-on)材料,该材料是硅基材料并且当固化时将在薄膜中产生气孔。
含硅旋涂材料描述于US 5,010,159(Bank等人),US 6,022,814(Mikoshiba等人),和US 6,143,855和6,177,199(Hacker等人)中。
业已发现,具有式(R1SiO3/2)x(HSiO3/2)y(R1为具有8-24个碳原子的烷基)的树脂可用来生产在电子器件尤其是在半导体器件上的图层。这些树脂可用来生产介电常数为1.5-2.3的薄膜。
本发明涉及具有通式(R1SiO3/2)x(HSiO3/2)y的有机硅树脂,其中R1为具有8-24个碳原子的烷基。通过将所述树脂施加至半导体器件上并将树脂加热至足以使树脂固化并产生多孔涂层的温度,所述树脂可用来在半导体器件上形成多孔薄膜。其中所生产的这些涂层的介电常数为1.5-2.3。
所述有机硅树脂具有通式(R1SiO3/2)x(HSiO3/2)y,其中R1为具有8-24个碳原子的烷基;x为0.05-0.7的值;y为0.3-0.95的值并且x+y=1。优选的是,x为0.1-0.3,和y为0.7-0.9。
所述有机硅树脂可以是基本上完全缩合的或可以具有一些残余的SiOH或SiOR2官能团。基本上完全缩合指的是有机硅树脂包含≤1%摩尔(以有机硅树脂计)的SiOH或者SiOR2单元,式中,R2为具有1-6个碳原子的线型烷基基团。非必需地,残余SiOH或者SiOR2官能团的总量可高达15%摩尔。优选的是,所述硅树脂包含<0.5%摩尔的SiOH或者SiOR2单元,以获得更好的使用寿命。可以列举R2包括但不限于甲基,乙基,丙基,丁基,戊基,或己基。
所述硅树酯的重均分子量为1,500-400,000,优选为20,000-200,000。
在有机硅树脂中,R1是具有8-24个碳原子的烷基。所述烷基可以是线型或支链的。所述烷基可以是取代或未取代的烷基。在被取代的烷基上的取代基可以列举但不限于吸电子基团、卤素、酰基、三烷基甲硅烷氧基、以及其混合物或复合物。
合适的吸电子基团包括:具有式-OR3的烷氧基,其中R3为具有1-4个碳原子的烷基;羟基(-OH);和具有式-OC(O)R4的羧基,其中R4为具有1-6个碳原子的烷基。优选的吸电子基团为甲氧基或者乙氧基或者羟基。
优选的R1基团为在烷基链的侧位中包含吸电子基团的具有8-24个碳原子的支链烷基;更优选的是在烷基链的侧位中包含羟基或烷氧基的具有8-24个碳原子的支链烷基。
R1的具体例子包括但不局限于辛基、氯代辛基、三甲基甲硅烷氧基十六烷基、十八烷基、二十二烷基、3,7,11,15-四甲基-3-羟基-十六烷基、3,7,11,15-四甲基-3-甲氧基十六烷基、4-庚基-4-乙氧基癸基、和3,7-二乙基-3-羟基十二烷基及其混合物。
在(C)溶剂、(D)水和(E)水解催化剂的存在下,通过将(A)具有式R1SiX3的硅烷和(B)具有式HSiX3的硅烷进行混合来生产具有式(R1SiO3/2)x(HSiO3/2)y的有机硅树脂,其中,R1,x和y如上所定义,其中各X选自可水解基团或羟基。优选的是,硅烷(A)和(B)与溶剂(C)混合,并将水(D)和水解催化剂(E)添加至混合物中。
在硅烷(A)和(B)中,X可以是可水解基团或羟基。“可水解基团”指的是在反应条件下、在水存在下、能够从硅原子上水解的基团(即X基团被-OH置换);并且当水解时,所述基团不会对有机硅树脂的溶解性或最终用途产生负面影响。可列举的可水解基团包括:卤化物基团如氯化物;和烷氧基,如甲氧基和乙氧基。优选的是,X为烷氧基,更优选的是,X为乙氧基。
以(A)和(B)的用量计,硅烷(A)的用量通常为5-70%摩尔,或者10-30%摩尔,或者14-20%摩尔。可以列举的硅烷A包括但不限于:3,7,11,15-四甲基-3-羟基-十六烷基三乙氧基硅烷,3,7,11,15-四甲基-3-甲氧基十六烷基三乙氧基硅烷,3,7,11,15-四甲基-3-羟基-十六烷基三氯硅烷,3,7,11,15-四甲基-3-甲氧基十六烷基三氯硅烷,辛基三甲氧基硅烷,辛基三乙氧基硅烷,十八烷基三甲氧基硅烷,十六烷基三甲氧基硅烷,十二烷基三乙氧基硅烷,及其混合物。
以(A)和(B)的用量计,硅烷(B)的用量通常为30-95%摩尔,或者70-90%摩尔,或者80-86%摩尔。可以列举的硅烷(B)有三氯硅烷,三甲氧基硅烷,三乙氧基硅烷及其混合物。
溶剂(C)为不包含可参与反应的官能团的任何合适的有机溶剂或有机硅溶剂,并且为对于硅烷(A)和(B)是足够的溶剂。通常,溶剂的用量以溶剂和硅烷(A)和(B)的总重量计为40-98%重量,或者是70-90%重量。可以列举的有机溶剂包括但不局于:饱和的脂族化合物,如正-戊烷,己烷,正-庚烷,和异辛烷;脂环族化合物,如环戊烷和环己烷;芳族化合物,如苯,甲苯,二甲苯,均三甲苯;环醚,如四氢呋喃,和二恶烷;酮,如甲基异丁基甲酮(MIBK)和环己酮;卤素取代的烷烃,如三氯乙烷;卤化芳香族物质,如溴化苯和氯苯;酯,如异丁酸异丁酯和丙酸丙酯。可以列举的有用的有机硅溶剂包括但不局限于:环状硅氧烷,如八甲基环四硅氧烷和十甲基环五硅氧烷。可以使用单一的溶剂或使用溶剂的混合物。优选的溶剂是甲基异丁基甲酮和异丁酸异丁酯的混合物。
组分(D)为水。优选的是,在不过量至导致无效反应速率的情况下,以足以使硅烷(A)和(B)中的X基本上完全水解的用量添加水。通常,水的用量为相对每摩尔硅烷(A)和(B)中的X为0.5-2摩尔,或者为0.8-1.5摩尔。
组分(E)为水解催化剂,并且可是本领域中已知的那些水解催化剂的任一种,以在水的存在下使硅烷(A)和(B)上的X发生水解。已知的水解催化剂包括无机碱,如氢氧化铵,氢氧化钾和氢氧化钠;有机碱,如三甲胺;无机酸,如氢氯酸,硫酸和硝酸;以及有机酸,如三氟乙酸。水解催化剂(E)含量为足以催化X水解的量,和最佳用量将取决于催化剂的化学成分以及水解反应的温度。通常,水解催化剂的用量为相对每摩尔硅烷(A)和(B)为约0.00001-0.5摩尔,或者为0.1-0.3摩尔份。
在有机硅树脂的制备方法中,优选的是将硅烷(A)和(B)与溶剂(C)混合。然后,单独地或以混合物的形式,将水(D)和水解催化剂(E)添加至第一混合物中。只要不使有机硅树脂产生明显的凝胶化或固化,反应可以在任何温度下进行。通常,反应在15-100℃的范围内进行,建议在室温下进行。
形成有机硅树脂的时间取决于许多因素:如温度,硅烷(A)和(B)的具体用量,以及催化剂的用量。通常,反应时间从几分钟至几小时。本领域技术人员将能够容易地确定完成反应所需的时间。
反应完成之后,可以非必需地除去催化剂。催化剂的除去方法在本领域中是熟知的,并且可包括中和,汽提或水洗,或其结合。催化剂对有机硅树脂的使用寿命可产生负面影响,尤其是当在溶液中时,因此建议将催化剂除去。
在有机硅树脂制备方法中,在反应完成之后,挥发性组分可在减压下从有机硅树脂中除去。所述挥发性组分包括醇副产物,过量的水,催化剂和溶剂。挥发性组分的除去方法在本领域中是已知的,并且包括例如蒸馏。
为了增加有机硅树脂的分子量和/或改善有机硅树脂的储存稳定性,可以从40℃加热至溶剂的回流温度来延长时间进行反应(“增重步骤”)。增重步骤可以在反应步骤之后或作为反应步骤的一部分而进行。优选的是,增重步骤在30分钟至6小时,更优选在1-3小时的时间内进行。
在生产有机硅树脂的反应和非必需的增重步骤之后,还可以进行许多非必需的步骤,以便获得希望形式的有机硅树脂。例如,通过除去溶剂,可以固态回收有机硅树脂。溶剂的除去方法并不关键,许多方法在本领域中是熟知的(例如在加热和/或真空下的蒸馏)。一旦以固态回收有机硅树脂,为了特殊的用途,该树脂可非必需地再溶解于相同的溶剂或另外的溶剂中。或者,如果对于最终产品而言,除反应中使用的溶剂以外的不同的溶剂是理想的,则可通过添加第二溶剂来进行溶剂交换,并且例如通过蒸馏除去第一溶剂。另外,溶剂中的树脂浓度可通过除去一些溶剂或添加附加量的溶剂而进行调节。
在此生产的有机硅树脂在形成多孔陶瓷材料、陶瓷膜或者在基片上特别是在电子基片上的多孔涂层中是特别有用的。电子基片指的是包括打算用来制造半导体元件的硅基装置和砷化镓基装置。特别是,有机硅树脂可用来形成集成电路中的多孔涂层。有机硅树脂可用于生产介电常数在1.5-2.2范围内的薄涂层,从而使有机硅树脂特别适用于形成中间层绝缘膜。
通过如下步骤,硅树脂可用来制备于基片上的多孔涂层:
(I)用具有式(R1SiO3/2)x(HSiO3/2)y的有机硅树脂涂布基片,其中R1为具有8-24个碳原子的烷基;x为0.05-0.7的值;y为0.3-0.95的值并且x+y=1;
(II)在足以使有机硅树脂固化的温度下,对涂布的基片进行加热,并形成固化的树脂涂层,和
(III)在足以从固化的树脂涂层中除去R1基团的温度下,进一步对固化的树脂涂层进行加热,从而在基片上形成多孔涂层。
有机硅树脂通常以溶剂分散体的形式被施加至基片上。可以使用的溶剂包括能够溶解或分散硅树脂以形成基本上均匀液体混合物的任何溶剂或溶剂的混合物。所述溶剂通常是如上所述的在反应中使用的用来生产有机硅树脂的溶剂或溶剂的混合物。优选的溶剂包括环己酮,异丁酸异丁酯和均三甲苯。
对溶剂的用量没有特别的限制,但以有机硅树脂和溶剂的总重量计,其用量通常为40-98%重量,优选70-90%重量。
将有机硅树脂施加至基片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。优选的施加方法是旋涂。
当使用溶剂时,在施加之后,从涂布的基片中将溶剂除去。可以使用任何合适的除去方法,如干燥,施加真空和/或加热(如使涂布的晶片通过加热板)。当使用旋涂时,由于旋转去除了大多数溶剂,因此附加的干燥方法将被最小化。
在施加至基片上之后,在使有机硅树脂固化的温度下对涂布的基片进行加热(“固化步骤”)。固化的有机硅树脂基本上不溶于可以用于施加至基片上的溶剂中。通常,将涂布的基片加热至20-350℃的温度,以使有机硅树脂固化。
然后,再将基片上固化的有机硅树脂加热至足以从固化的树脂涂层中除去R1基团的温度,从而在基片上形成多孔涂层(“除去步骤”)。通常,固化树脂被加热到350℃至树脂骨架分解温度的范围内的某个温度。通常,固化树脂被加热到350-600℃,或400-550℃,或425-475℃的范围内的某个温度。在该步骤中,分解了基本上所有的R1基团。然而,由R1基团产生的残余的低级烷基基团如甲基或乙基可留在涂层中。所除去的R1基团的百分数将对薄膜的介电常数以及孔隙率产生影响。建议以足以除去绝大多数R1基团,如从固化树脂中除去90%重量R1基团的时间对其进行加热。例如,可通过FTIR确定所除去R1基团的量。
固化步骤和除去步骤可以分开进行或在一个步骤中进行,其中,在一步法中,固化在涂布基片被加热至除去温度时进行。
优选的是,固化步骤和除去步骤在惰性环境中进行。在此有用的惰性气氛包括但不局限于氮和氩。“惰性”指的是所述环境包含低于50ppm,优选低于10ppm的氧。进行固化和除去步骤的压力并不重要。然而,固化和除去步骤通常在大气压下进行,但也可以在亚或超大气压下进行。
在固化和除去步骤期间,可以使用任何加热方法。例如,可以将基片置于石英管炉,对流加热炉中,或者将其置于加热板上。
通过该方法,可在基片上形成多孔涂层。优选的是,多孔涂层的厚度为0.3-2.5微米,更优选为0.5-1.2微米。多孔涂层的介电常数在1.5-2.3范围内。薄膜中的孔隙率取决于原料树脂中R1基团的数量以及它们的除去程度。通常,多孔涂层的孔隙率为20-60%。
通过在足以使有机硅树脂固化的温度下对有机硅树脂进行加热,并在足以从固化树脂涂层中除去R1基团的温度下对固化有机硅树脂进行进一步加热,从而形成多孔陶瓷或者多孔陶瓷膜,来生产多孔陶瓷或者陶瓷膜。其加工条件类似于如上所述的在没有用有机硅树脂对基片进行涂布的情况下用于在基片上生产多孔涂层的那些条件。然而,在R1基团的除去步骤中,温度将更高,如800℃,并且可利用氧化气氛使残余烷基最少化。
提供如下非限定性实施例,以便本领域技术人员可更容易地理解本发明。
实施例
实施例1
通过以表1中所述量混合来制备试样1-1至1-4:
(A)三乙氧基硅烷,
(B)有机三烷氧基硅烷,R1Si(OR2)3,和
(C)足以使所得树脂的浓度为9%的甲基异丁基甲酮(MIBK)和异丁酸异丁酯(6∶4重量比)的混合物。
向该混合物中添加(D)水和(E)盐酸的混合物,其用量如表1所述。然后,在减压下,于60℃对所得反应产物汽提挥发性组分,直至固含量变成20-22%为止。添加异丁酸异丁酯,以使固含量为20%。然后,对溶液回流加热1小时,并连续除去所产生的水。将所得树脂液旋涂至适于介电常数测量的硅片上,并在470℃、在氮气流中固化1小时。测量介电常数并示于表1中。
表1
试样 | R1 | R2 | 重量份 | 摩尔比A∶B | 介电常数 | |||||
编号 | (A) | (B) | (C) | (D) | (E) | (A) | (B) | |||
1-1 | 3,7,11,15-四甲基-3-羟基十六烷基 | Et | 1 | 0.89 | 8.65 | 0.48 | 0.04 | 76 | 24 | 1.77 |
1-2 | 3,7,11,15-四甲基-3-甲氧基十六烷基 | Me | 1 | 0.83 | 8.99 | 0.48 | 0.04 | 76 | 24 | 1.85 |
1-3 | 十二烷基 | Et | 1 | 0.64 | 6.16 | 0.48 | 0.04 | 76 | 24 | 2.0 |
1-4 | 十八烷基 | Me | 1 | 0.72 | 7.88 | 0.48 | 0.04 | 76 | 24 | 1.97 |
对比例2
通过以表2中描述的用量混合来制备对比试样C2-1至C2-3:
(A)三乙氧基硅烷
(B)有机三烷氧基硅烷,R5Si(OR2)3,和
(C)足以使所得树脂的浓度为9%的甲基异丁基甲酮(MIBK)和异丁酸异丁酯(6∶4重量比)的混合物。
向该混合物中添加(D)水和(E)盐酸的混合物,其用量如表2所述。然后,在减压下,于60℃对所得反应产物汽提挥发性组分,直至固含量变成20-22%为止。添加异丁酸异丁酯,以使固含量为20%。将所得的树脂液旋涂至适于介电常数测量的硅片上,并在470℃、在氮气流中固化1小时。测量介电常数并示于表2中。
表2
试样 | R5 | R2 | 重量份 | 摩尔比A∶B | 介电常数 | |||||
编号 | (A) | (B) | (C) | (D) | (E) | (A) | (B) | |||
C2-1 | 异丁基 | Et | 1 | 0.42 | 3.98 | 0.48 | 0.04 | 76 | 24 | 3.05 |
C2-2 | 异丁基 | Et | 1 | 2.01 | 10.67 | 0.90 | 0.08 | 40 | 60 | 2.82 |
C2-3 | 三氟丙基 | Me | 1 | 1.99 | 14.75 | 0.90 | 0.08 | 40 | 60 | 3.03 |
实施例3
将实施例1的试样旋涂至硅片上。硅片的一半适于介电常数测量,而另一半适于FTIR测量。在1200-1800RPM的范围内选择旋转速率,以获得7500-9100埃的旋涂厚度。在氮气氛下,在石英管炉中,于不同的温度对涂布的硅片加热1小时。24小时之后,对所有固化的薄膜检查其开裂性,并且对于无裂缝的薄膜,测量其介电常数,折射率和FTIR光谱。表3示出了开裂薄膜和无裂缝薄膜的介电常数。表4示出了所有无裂缝薄膜和旋涂薄膜的折射率。表5示出了在薄膜固化1小时之后R1基团损失的百分数。这些值由固化前后每单位厚度FTIR C-H峰强度计算得到。
表3的数据表明:带有支链有机基团如3,7,11,15-四甲基-3-羟基-十六烷基或者3,7,11,15-四甲基-3-甲氧基-十六烷基的有机氢化硅氧烷(organohydridosiloxane),与带有线型有机基团如十八烷基或十二烷基的那些相比,在更低的固化温度将形成具有超低介电常数(等于或小于2.0)的无裂缝薄膜。
如表4所示,所有在较低温度下固化的无裂缝薄膜(试样1-2为395℃,试样1-3和1-4为395℃和410℃)具有与旋涂薄膜实质上相同的折射率,这表明这些固化薄膜没有孔隙率;与旋涂薄膜相比,所有在较高温度下固化的所有无裂缝薄膜均具有明显更低的折射率,这表明在这些固化薄膜中具有明显的孔隙率。表4的数据表明:带有支链有机基团如3,7,11,15-四甲基-3-羟基-十六烷基或者3,7,11,15-四甲基-3-甲氧基-十六烷基的有机氢化硅氧烷(organohydridosiloxane)树脂,与带有线型有机基团如十八烷基或十二烷基的那些相比,在更低的固化温度将形成无裂缝多孔薄膜。
如表5所示,带有支链有机基团如3,7,11,15-四甲基-3-羟基-十六烷基的有机氢化硅氧烷树脂,与带有线型基团如十八烷基或者十二烷基的那些相比,在相对低的温度下(410℃),将开始损失其大多数的R1基团。
表3
试样 | 395℃ | 410℃ | 425℃ | 440℃ | 455℃ | 470℃ |
1-1 | 开裂 | 1.97 | 1.75 | 1.78 | 1.73 | 1.77 |
1-2 | 2.61 | 开裂 | 1.96 | 1.88 | 1.85 | 1.85 |
1-3 | 2.52 | 2.51 | 开裂 | 开裂 | 开裂 | 2.0 |
1-4 | 2.43 | 2.42 | 开裂 | 开裂 | 开裂 | 1.97 |
表4
试样 | 旋涂 | 395℃ | 410℃ | 425℃ | 440℃ | 455℃ | 470℃ |
1-1 | 1.45 | 开裂 | 1.25 | 1.20 | 1.20 | 1.20 | 1.20 |
1-2 | 1.45 | 1.45 | 开裂 | 1.30 | 1.27 | 1.26 | 1.26 |
1-3 | 1.45 | 1.44 | 1.44 | 开裂 | 开裂 | 开裂 | 1.28 |
1-4 | 1.45 | 1.45 | 1.45 | 开裂 | 开裂 | 开裂 | 1.28 |
表5
试样 | 395℃ | 410℃ | 425℃ | 440℃ | 455℃ | 470℃ |
1-1 | 开裂 | 76% | 85% | 89% | 92% | 93% |
1-2 | 8% | 开裂 | 65% | 84% | 87% | 89% |
1-3 | 8% | 8% | 开裂 | 开裂 | 开裂 | 88% |
1-4 | 8% | 8% | 开裂 | 开裂 | 开裂 | 87% |
实施例4
通过实施例1中所述用于试样1-1的方法形成带有3,7,11,15-四甲基-3-羟基-十六烷基基团的有机氢化硅氧烷,所不同的是,A/B之比为84∶16。对该树脂溶液的试样进行加热,从而使之多孔,并测量孔隙率和孔径大小。将另一试样涂布至硅片上并测量基片上涂层的物理特性。
将该树脂溶液的试样置于坩埚中并首先在150℃进行加热从而除去溶剂,然后在氮气氛下于425℃加热1小时。利用MicrometricsASAP 2000 Accelerated Surface Area and Porosimetry System(Micrometrics Instrument Corporation,Norcross,GA),在77°K对所得固体的氮吸附进行测试。测得的BET表面积为875m2/g。吸附数据的H-K分析(Horvath,J Chem.Eng.Jpn.,1983,Vol.16,p.476)表明:固化的微孔体积为0.402cc/g,具有窄的孔径分布,并且中值孔径为0.94纳米。
用树脂溶液的另一试样对硅片进行旋涂。在氮气氛下,于425℃下,对涂布的硅片加热1小时。所得薄膜的厚度为0.44微米,其厚度变差为0.7%,折射率为1.225,并且介电常数为1.95。
实施例4表明,其中R1为含约8-24个碳原子烃基的或含约8-24个碳原子烃链的取代的烃基的有机氢化硅氧烷将形成纳米多孔固体,在加热之后,其中值孔径小于1纳米。
实施例5
通过以表1所述量混合来制备试样5-1至5-7(相对于每重量份A的重量份):
(A)三乙氧基硅烷
(B)3,7,11,15-四甲基-3-羟基-十六烷基三乙氧基硅烷,和
(C)足以使所得树脂的浓度为9%的甲基异丁基甲酮(MIBK)和异丁酸异丁酯(6∶4重量比)的混合物。
向该混合物中添加(D)水和(E)盐酸的混合物,其用量如表1所述(相对于每重量份A的重量份)。然后,在减压下,于60℃对所得反应产物汽提挥发性组分,直至固含量变成20-22%为止。添加异丁酸异丁酯,以使固含量为20%。然后,对溶液回流加热1小时,并利用迪安-斯达克榻分水器连续除去所产生的水。
使各树脂溶液的试样过滤通过1.0微米的玻璃纤维针筒式滤器和0.2微米的聚四氟乙烯针筒式滤器,旋涂至硅片上,并在氮气氛下于425℃固化1小时。选择旋转速度,以使固化薄膜的厚度在600-800纳米的范围内。测量薄膜的模量和介电常数,并将结果示于表6中。通过用10%渗透深度的纳米针入度来测量模量。实施例5的数据表明:通过将3,7,11,15-四甲基-3-羟基-十六烷基基团的摩尔百分数在24-10%的范围内变化,可使得由3,7,11,15-四甲基-3-羟基-十六烷基氢化硅氧烷树脂制得的薄膜的介电常数和模量分别在1.7-2.1和2.6-7.0之间变化。
表6
试样号 | 重量份(B) | 重量份(C) | 重量份(D) | 重量份(E) | B的摩尔百分数 | 介电常数 | 薄膜模量GPa |
5-1 | 0.31 | 4.47 | 0.04 | 0.40 | 10 | 2.12 | 7.0 |
5-2 | 0.38 | 4.98 | 0.04 | 0.41 | 12 | 2.07 | 6.8 |
5-3 | 0.46 | 5.52 | 0.04 | 0.42 | 14 | 2.04 | 5.9 |
5-4 | 0.53 | 6.09 | 0.04 | 0.43 | 16 | 1.95 | 4.7 |
5-5 | 0.62 | 6.68 | 0.04 | 0.44 | 18 | 1.90 | 3.4 |
5-6 | 0.70 | 7.31 | 0.04 | 0.45 | 20 | 1.85 | 3.1 |
5-7 | 0.89 | 8.65 | 0.04 | 0.48 | 24 | 1.73 | 2.6 |
实施例6
与试样5-4类似地制备试样6-1和6-2,并与试样5-7类似地制备试样6-3和6-4。向试样6-1和6-3中添加NaOH浓度为2%的NaOH/乙醇溶液,从而使溶液中的Na含量为1ppm。使个树脂溶液的试样过滤通过0.2微米的聚四氟乙烯针筒式滤器,旋涂至硅片上,并在氮气氛下于425℃固化1小时。选择旋转速度,以使固化薄膜的厚度在600-800纳米的范围内。测量薄膜的模量和介电常数,并将结果示于表7中。通过用10%渗透深度的纳米针入度来测量模量。实施例5的数据表明:通过添加碱性催化剂,可增加由3,7,11,15-四甲基-3-羟基-十六烷基氢化硅氧烷树脂制得的薄膜的模量。业已发现,树脂溶液过滤通过1.0微米的玻璃纤维过滤器也将NaOH带入树脂溶液中,这也将增加薄膜的模量(参见实施例5)。
表7
试样号 | 重量份(B) | 重量份(C) | 重量份(D) | 重量份(E) | B的摩尔百分数 | 添加NaOH | 介电常数 | 薄膜模量GPa |
6-1 | 0.53 | 6.09 | 0.04 | 0.43 | 16 | 是 | 1.93 | 4.8 |
6-2 | 0.53 | 6.09 | 0.04 | 0.43 | 16 | 否 | 1.96 | 2.0 |
6-3 | 0.89 | 8.65 | 0.04 | 0.48 | 24 | 是 | 1.75 | 2.5 |
6-4 | 0.89 | 8.65 | 0.04 | 0.48 | 24 | 否 | 1.73 | 1.5 |
Claims (12)
1.一种有机硅树脂,具有式(R1SiO3/2)x(HSiO3/2)y,其中R1为具有8-24个碳原子的烷基,x为0.05-0.7的值,y为0.3-0.95的值并且x+y=1。
2.权利要求1的有机硅树脂,其中R1为在烷基链上的侧链位置含吸电子基团的具有8-24个碳原子的支链烷基。
3.权利要求1的有机硅树脂,其中R1选自辛基,氯代辛基,三甲基甲硅烷氧基十六烷基,十八烷基,二十二烷基,3,7,11,15-四甲基-3-羟基-十六烷基,3,7,11,15-四甲基-3-甲氧基-十六烷基,4-庚基-4-乙氧基癸基,和3,7-二乙基-3-羟基-十二烷基及其混合物。
4.权利要求1的有机硅树脂,其中,x为0.1-0.3;y为0.7-0.9且x+y=1。
5.一种有机硅树脂的生产方法,包括:
(I)在(C)溶剂、(D)水和(E)水解催化剂的存在下,将(A)具有式R1SiX3的硅烷与(B)具有式HSiX3的硅烷混合,其中R1是具有8-24个碳原子的烷基,并且每个X选自可水解基团或羟基;
(II)在足以形成具有式(R1SiO3/2)x(HSiO3/2)y的有机硅树脂的温度和时间下,使该混合物(I)反应,其中R1为具有8-24个碳原子的烷基,x为0.05-0.7的值,y为0.3-0.95的值并且x+y=1。
6.权利要求5的方法,其中R1选自辛基,氯代辛基,三甲基甲硅烷氧基十六烷基,十八烷基,二十二烷基,3,7,11,15-四甲基-3-羟基-十六烷基,3,7,11,15-四甲基-3-甲氧基-十六烷基,4-庚基-4-乙氧基癸基,和3,7-二乙基-3-羟基十二烷基及其混合物。
7.权利要求5或6的方法,其中X为烷氧基。
8.权利要求5-7任一项的方法,其中(A)的用量以(A)和(B)的用量计在14-20%摩尔的范围内;(B)的用量以(A)和(B)的用量计在80-86%摩尔的范围内;(C)的用量以(A)和(B)的总重量计在70-90%摩尔的范围内;(D)的用量以(A)和(B)中每摩尔X计在0.8-1.5摩尔的范围内;和(E)的用量以每摩尔(A)和(B)计在0.1-0.3摩尔的范围内。
9.权利要求5-8任一项的方法,其中(C)选自至少一种饱和的脂族溶剂,脂环族溶剂,芳香族溶剂,环醚溶剂,酮溶剂,卤素取代的链烷溶剂,卤化的芳香族溶剂,酯溶剂,有机硅溶剂及其混合物。
10.一种多孔陶瓷的生产方法,包括:
(I)在足以使式(R1SiO3/2)x(HSiO3/2)y的有机硅树脂固化的温度下,对该有机硅树脂进行加热,其中R1为具有8-24个碳原子的烷基,x为0.05-0.7的值,y为0.3-0.95的值并且x+y=1;
(II)在足以从固化树脂中除去R1基团的温度下,对固化树脂进行进一步加热,从而形成多孔陶瓷。
11.一种在基片上生产多孔涂层的方法,包括:
(I)用具有式(R1SiO3/2)x(HSiO3/2)y的有机硅树脂涂布基材,其中R1为具有8-24个碳原子的烷基,x为0.05-0.7的值,y为0.3-0.95的值并且x+y=1;
(II)在足以使所述有机硅树脂固化的温度下,在惰性气氛下加热涂布的基片;
(III)在足以从固化的树脂涂层中除去R1基团的温度下,在惰性气氛下,进一步加热固化的树脂涂层,从而在基材上形成多孔涂层。
12.权利要求10或11的方法,其中R1选自辛基,氯代辛基,三甲基甲硅烷氧基十六烷基,十八烷基,二十二烷基,3,7,11,15-四甲基-3-羟基-十六烷基,3,7,11,15-四甲基-3-甲氧基-十六烷基,4-庚基-4-乙氧基癸基,和3,7-二乙基-3-羟基-十二烷基及其混合物。
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US6143855A (en) * | 1997-04-21 | 2000-11-07 | Alliedsignal Inc. | Organohydridosiloxane resins with high organic content |
US6177199B1 (en) | 1999-01-07 | 2001-01-23 | Alliedsignal Inc. | Dielectric films from organohydridosiloxane resins with low organic content |
US6281285B1 (en) * | 1999-06-09 | 2001-08-28 | Dow Corning Corporation | Silicone resins and process for synthesis |
US6197913B1 (en) | 1999-08-26 | 2001-03-06 | Dow Corning Corporation | Method for making microporous silicone resins with narrow pore-size distributions |
DE60025872T2 (de) * | 1999-10-25 | 2006-08-17 | Dow Corning Corp., Midland | Lösliche Siliconharzzusammensetzungen |
US6313045B1 (en) | 1999-12-13 | 2001-11-06 | Dow Corning Corporation | Nanoporous silicone resins having low dielectric constants and method for preparation |
US6232424B1 (en) | 1999-12-13 | 2001-05-15 | Dow Corning Corporation | Soluble silicone resin compositions having good solution stability |
US6359096B1 (en) * | 1999-10-25 | 2002-03-19 | Dow Corning Corporation | Silicone resin compositions having good solution solubility and stability |
US6143360A (en) * | 1999-12-13 | 2000-11-07 | Dow Corning Corporation | Method for making nanoporous silicone resins from alkylydridosiloxane resins |
US6399210B1 (en) | 2000-11-27 | 2002-06-04 | Dow Corning Corporation | Alkoxyhydridosiloxane resins |
-
2001
- 2001-09-12 US US09/951,819 patent/US6596834B2/en not_active Expired - Fee Related
-
2002
- 2002-08-29 CN CNA028161130A patent/CN1543664A/zh active Pending
- 2002-08-29 EP EP02766195A patent/EP1425781A1/en not_active Withdrawn
- 2002-08-29 JP JP2003527779A patent/JP2005502775A/ja active Pending
- 2002-08-29 KR KR10-2004-7003608A patent/KR20040044895A/ko not_active Application Discontinuation
- 2002-08-29 WO PCT/US2002/027755 patent/WO2003023831A1/en active Application Filing
- 2002-09-12 TW TW091120929A patent/TW593439B/zh not_active IP Right Cessation
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101072813B (zh) * | 2004-12-17 | 2011-06-08 | 陶氏康宁公司 | 硅氧烷树脂涂料 |
CN101681939B (zh) * | 2006-06-05 | 2014-02-26 | 陶氏康宁公司 | 包括有机硅树脂层的太阳能电池 |
CN101675097B (zh) * | 2007-05-01 | 2012-03-14 | 陶氏康宁公司 | 增强的有机硅树脂膜 |
CN104395327A (zh) * | 2012-07-05 | 2015-03-04 | 日本曹达株式会社 | 有机硅化合物、使用其的薄膜形成用组合物以及有机薄膜 |
CN104395327B (zh) * | 2012-07-05 | 2017-06-23 | 日本曹达株式会社 | 有机硅化合物、使用其的薄膜形成用组合物以及有机薄膜 |
Also Published As
Publication number | Publication date |
---|---|
WO2003023831A1 (en) | 2003-03-20 |
US6596834B2 (en) | 2003-07-22 |
EP1425781A1 (en) | 2004-06-09 |
JP2005502775A (ja) | 2005-01-27 |
KR20040044895A (ko) | 2004-05-31 |
TW593439B (en) | 2004-06-21 |
US20030088016A1 (en) | 2003-05-08 |
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