WO2003011945A2 - Siloxane resins - Google Patents
Siloxane resins Download PDFInfo
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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.
Abstract
Description
Claims
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EP02756227A EP1412435A2 (en) | 2001-07-26 | 2002-06-18 | Siloxane resins |
AU2002322250A AU2002322250A1 (en) | 2001-07-26 | 2002-06-18 | Siloxane resins |
KR10-2004-7000882A KR20040043160A (en) | 2001-07-26 | 2002-06-18 | Siloxane resins |
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US10/121,971 US6596404B1 (en) | 2001-07-26 | 2002-04-15 | Siloxane resins |
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
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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 |
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JP5107354B2 (en) * | 2006-08-04 | 2012-12-26 | ダウ・コーニング・コーポレイション | 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 |
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EP0997497A1 (en) * | 1997-07-15 | 2000-05-03 | Asahi Kasei Kogyo Kabushiki Kaisha | Alkoxysilane/organic polymer composition for thin insulating film production and use thereof |
EP1095958A1 (en) * | 1999-10-25 | 2001-05-02 | Dow Corning Corporation | Soluble silicone resin compositions |
US6231989B1 (en) * | 1998-11-20 | 2001-05-15 | Dow Corning Corporation | Method of forming coatings |
-
2002
- 2002-06-18 EP EP02756227A patent/EP1412435A2/en not_active Withdrawn
- 2002-06-18 WO PCT/US2002/019283 patent/WO2003011945A2/en not_active Application Discontinuation
- 2002-06-18 CN CNA028147286A patent/CN1535301A/en active Pending
- 2002-06-26 TW TW091114016A patent/TW591057B/en active
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EP0997497A1 (en) * | 1997-07-15 | 2000-05-03 | Asahi Kasei Kogyo Kabushiki Kaisha | Alkoxysilane/organic polymer composition for thin insulating film production and use thereof |
US6231989B1 (en) * | 1998-11-20 | 2001-05-15 | Dow Corning Corporation | Method of forming coatings |
EP1095958A1 (en) * | 1999-10-25 | 2001-05-02 | Dow Corning Corporation | Soluble silicone resin compositions |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
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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 |
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