# US 5,702,767 A · Non-Aminic photoresist adhesion promoters for microelectronic applications > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 5,702,767 A - Document ID: US5702767A - Status: Granted - Kind: A - Application number: 08/562,725 - Filed: 1995-11-27 - Granted: 1997-12-30 - Earliest claimed: 1994-11-22 - Assignees: Complex Fluid Systems, Inc. - Inventors: William R. Peterson; Craig M. Stauffer - Web page: https://patentgrep.com/patent/US5702767A ## CPC - G03F 7/0751: {used as adhesion-promoting additives or as means to improve adhesion} - H10P 14/683: {carbon-based polymeric organic materials, e.g. polyimides, poly cyclobutene or PVC} - G03F: PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR; (phototypographic composing devices B41B; photosensitive materials or processes for photographic purposes G03C; electrophotography, sensitive layers or processes therefor G03G) - H10P: GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10 ## Abstract A method for providing an inorganic substrate having improved adherence for polymeric films is disclosed. The method entails reacting at least one organosilane compound having at least one alkylsilyl moiety therein and at least one hydrolyzable group capable of reacting with the substrate to silylate the substrate. Hydrolyzable by-products from the reaction, if any, have a pH less than or equal to about 7. ## Claims ### Claim 1 A method for improving the adherence of a polymeric material to an inorganic, unprimed substrate comprising, priming said substrate with at least one organosilane compound having at least one alkylsilyl moiety and at least one hydrolyzable leaving group bound to silicon; reacting said at least one organosilane compound during priming with said substrate under conditions sufficient to silylate said substrate with a surface layer comprising the alkylsilyl moiety, wherein said hydrolyzable leaving group reacts with said substrate to form by-products having a pH less than or equal to about 7; and applying said polymeric material to said silylated substrate. ### Claim 2 (depends on 1) The method of claim 1 wherein the substrate is selected from the group consisting of at least one of single crystal silicon, polysilicon, silicon dioxide, silicon nitride, aluminum, aluminum oxide, copper, copper oxide, titanium, titanium nitride, titanium tungsten, boron phosphorus silicon glass, spin-on-glass, and silicides. ### Claim 3 (depends on 1) The method of claim 1 wherein said polymeric material is a photoresist which comprises a polymer selected from the group consisting of polyvinylphenol, polyhydroxystyrene, poly(t-butyl-carboxy) styrene, polyfumerates, poly(t-butoxystyrene), polyisoprenes, formaldehyde novolacs, and polyacrylic esters. ### Claim 4 (depends on 3) The method of claim 3 wherein the photoresist further comprises a cyanurate and a photoinitiator selected from the group consisting of onium salts, diazonaphthenates, and azides. ### Claim 5 (depends on 1) The method of claim 1, wherein the organosilane compound is a trialkylsilane compound. ### Claim 6 (depends on 5) The method according to claim 5, wherein the trialkylsilane compound has the formula: ##STR8## wherein X is O or NR; Y is O, CH.sub.2, CHR, CHOR, CRR, or NR and R is hydrogen, saturated C.sub.1 -C.sub.8 alkyl, saturated C.sub.4 -C.sub.6 cyclic alkyl, unsaturated C.sub.1 -C.sub.8 alkyl, unsaturated C.sub.4 -C.sub.6 cylic alkyl, fluorinated C.sub.2 -C.sub.10 alkyl, fluorinated C.sub.5 -C.sub.8 cyclic alkyl, trialkylsiloxy, trialkylsilyl, C.sub.1 -C.sub.12 alkoxy, phenyl, fluorophenyl, phenethyl, or C.sub.3 -C.sub.6 alkyl ketones. ### Claim 7 (depends on 1) The method according to claim 1 wherein the organosilane compound has the formula: ##STR9## where R.sup.2 is saturated C.sub.1 -C.sub.6 alkyl, saturated C.sub.3 -C.sub.8 cyclic alkyl, unsaturated C.sub.2 -C.sub.8 alkyl, unsaturated C.sub.4 -C.sub.8 cyclic alkyl, fluorinated C.sub.1 -C.sub.8 alkyl, fluorinated C.sub.5 -C.sub.8 cyclic alkyl, phenyl, fluorinated phenyl, C.sub.3 -C.sub.6 alkyl ketones, C.sub.2 -C.sub.9 alkyl ether, C.sub.3 -C.sub.6 unsaturated alkyl ketone or, fluorinated alkyl ether. ### Claim 8 (depends on 7) The method of claim 7 wherein R.sup.2 is selected from the group consistinq of said fluorinated phenyl and said fluorinated alkyl ether. ### Claim 9 (depends on 7) The method according to claim 7 wherein R.sup.2 is trifluoromethyl. ### Claim 10 (depends on 1) The method according to claim 1 wherein the organosilane compound has the formula: ##STR10## wherein R.sup.3 is straight or branched chain saturated alkyl. ### Claim 11 (depends on 1) The method of claim 1 wherein the hydrolyzable group is selected from the group consisting of acetates, carboxylates, enols, alkoxides, sulfates and amides. ### Claim 12 (depends on 5) The method according to claim 5 wherein the trialkylsilane compound is selected from the group consisting of O-trimethylsilylacetate, isopropenoxytrimethylsilane, N-methyltrimethylsilyltrifluoroacetamide, trimethylmethoxysilane and trimethylethoxysilane. ### Claim 13 (depends on 1) The method of claim 1 wherein the organosilane compound is reacted as a vapor with said substrate at temperatures from about ambient to about 250.degree. F. and at pressures from about atmospheric pressure to less than about 1 torr. ### Claim 14 (depends on 1) The method of claim 1 wherein said organosilane is a dialkylsilane having two reactive hydrolyzable groups bound to silicon. ### Claim 15 (depends on 14) The method of claim 14 wherein said dialkylsilane is selected from the group consisting of dimethyldimethoxysilane and dimethyldiacetoxysilane. ### Claim 16 A method for improving the adherence of a polymeric material to an inorganic, unprimed substrate comprising, priming said substrate with at least one organosilane compound having at least one hydrolyzable leaving group bound to silicon and selected from the group consisting of O-trimethylsilylacetate, O-trimethylsilylproprionate, O-trimethylsilylbutyrate, trimethylsilyltrifluoroacetate, trimethylmethyoxysilane, N-methyltrimethylsilyltrifluoroacetamide, O-trimethylsilylacetylacetone, isopropenoxytrimethylsilane, bis(trimethylsilyl)trifluoroacetamide, methyltrimethylsilyldimethylketone acetate, and trimethylethoxysilane, reacting said at least one organosilane compound during priming with said substrate under conditions sufficient to silylate said substrate, wherein said hydrolyzable leaving group reacts with said substrate to form by-products having a pH less than or equal to about 7; and applying said polymeric material to said silylated substrate. ### Claim 17 (depends on 16) The method of claim 16 wherein said substrate is selected from the group consisting of single crystal silicon, polysilicon, silicon dioxide, silicon nitride, aluminum, aluminum oxide, copper, copper oxide, titanium, titanium nitride, titanium tungsten, boron phosphorus silicon glass, spin-on-glass, metal oxides, and silicides. ### Claim 18 (depends on 1) The method according to claim 1, further comprising priming said substrate with said organosilane compound in a liquid form. ### Claim 19 (depends on 1) The method according to claim 1, further comprising providing said organosilane compound in a solvent solution and priming said substrate with said solution in vapor form. ### Claim 20 (depends on 1) The method according to claim 1 further comprising providing said organosilane compound in a solvent solution and priming said substrate with said solution in liquid form.