# US 5,700,581 A · Solvent-free epoxy based adhesives for semiconductor chip attachment and process > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 5,700,581 A - Document ID: US5700581A - Status: Granted - Kind: A - Application number: 08/670,463 - Filed: 1996-06-26 - Granted: 1997-12-23 - Earliest claimed: 1996-06-26 - Assignees: International Business Machines Corporation - Inventors: Krishna G. Sachdev; Michael Berger; Mark S. Chace - Web page: https://patentgrep.com/patent/US5700581A ## CPC - C09J 163/00: Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins - C08G 59/306: {containing silicon} - H10W 72/073: {of die-attach connectors} - H10W 72/07337: {using a polymer adhesive, e.g. an adhesive based on silicone or epoxy} - H10W 72/30: Die-attach connectors - H10W 72/325: {Die-attach connectors having a filler embedded in a matrix} - H10W 72/352: {comprising metals or metalloids, e.g. solders} - H10W 72/353: {not comprising solid metals or solid metalloids, e.g. ceramics} - H10W 72/354: {comprising polymers} - Y10T 428/31663: As siloxane, silicone or silane - C09J: ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES (preparation of glue or gelatine C09H) - C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS - H10W: GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10 - Y10T: TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION ## Abstract The present invention discloses chip (die) bond adhesive formulations preferably comprising a siloxane containing epoxide preferably a diglycidyl ether derivative, an anhydride curing additive which is soluble in the epoxide without the use of a solvent, and, optionally comprising, and oligomeric/polymeric co-additive of the type poly(alkylacrylate or -methacrylate), in conjunction with thermal and electrically conductive fillers and conventional co-catalysts used for curing epoxy systems to provide reworkable epoxy adhesives. Also disclosed are adhesive formulations comprising a siloxane containing epoxide and a hydroxybenzophenone curing additive which is soluble in the epoxide without the use of a solvent. The chips can be bonded to the substrate by conventional heating and curing techniques. With epoxy adhesive compositions comprising polyacrylate additives, the die bonded assembly can be reworked by heating the assembly to about 180.degree. C. to 250.degree. C. removing the chip, and rebonding a new chip on the same surface without any effect on the shear strength for die bonded on to gold, copper, silver or a ceramic die pad. Die shear strength using the adhesives remains unchanged when exposed to thermal shock involving -65.degree. C. to +150.degree. C. excursions, and HAST test at 130.degree. C. /85 percent RH (Relative Humidity) or 85.degree. C./85% RH. A method is also provided for using the adhesives to make electronic component assemblies. ## Claims ### Claim 1 A solvent-free curable epoxy base adhesive resin composition which is made without solvents and which when applied as an adhesive and cured to bond electronic components maintains adhesion during product stress testing, the composition comprising a solution of: a siloxane containing polyepoxide; a curing additive for the polyepoxide; and a curing catalyst for the polyepoxide; the siloxane containing polyepoxide, the curing additive and curing catalyst being mutually soluble without a solvent at the temperature of application. ### Claim 2 (depends on 1) The composition of claim 1 wherein the polyepoxide is represented by the formula: ##STR3## wherein x is 2 to 8 and n is 1 to 10. ### Claim 3 (depends on 2) The composition of claim 2 wherein the curing additive is selected from the group consisting of anhydrides, amines and hydroxybenzophenones. ### Claim 4 (depends on 1) The composition of claim 1 further comprising a conductive filler. ### Claim 5 (depends on 1) The composition of claim 1 further comprising an additive to the composition wherein the additive enables the bonded components to be reworked without the need for solvents which additive is selected from the group consisting of polyacrylate, poly(meth)acrylate, polyalkylacrylate and polyalkylmethacrylate, polyfluoro alkyl acrylate and polyfluoroalkyl methacrylate wherein the alkyl group is C1-C8. ### Claim 6 (depends on 5) The composition of claim 5 further comprising a conductive filler. ### Claim 7 (depends on 6) The composition of claim 6 wherein the polyepoxide is a siloxane containing diglycidyl ether epoxide and the curing additive is an anhydride. ### Claim 8 (depends on 3) The composition of claim 3 wherein the polyepoxide is selected from the group consisting of bis(1,3-glycidoxy propyl) tetramethyl disiloxane, bis(1,5-glycidoxy propyl) hexamethyl trisiloxane and mixtures thereof. ### Claim 9 (depends on 8) The composition of claim 8 wherein the curing additive is selected from the group consisting of hexahydrophthalic anhydride, methyl-hexa hydrophthal anhydride, maleic anhydride, succinic anhydride, alicyclic anhydrides, alicyclic dianhydrides and mixtures thereof. ### Claim 10 (depends on 9) The composition of claim 9 further comprising an additive to the composition wherein the additive enables the bonded components to be reworked without the need for solvents which additive is selected from the group consisting of polyacrylate, poly(meth)acrylate, polyalkylacrylate, and polyalkymethacrylate, polyfluoroalkyl acrylate and polyfluoroalkyl methacrylate wherein the alkyl group is C1-C8. ### Claim 11 (depends on 2) The composition of claim 2 wherein the epoxide is selected from the group consisting of bis(1,3-glycidoxy propyl)tetramethyl disiloxane, bis(1,5-glycidoxy propyl) hexamethyl trisiloxane and mixtures thereof. ### Claim 12 (depends on 11) The composition of claim 11 wherein the curing additive is a hydroxybenzophenone selected from the group consisting of 2,2',4,4'-tetrahydroxybenzophenone; 2,3,4 trihydroxy benzophenone; 2,4'dihydroxybenzophenone and mixtures thereof. ### Claim 13 (depends on 1) An article of manufacture comprising a substrate having disposed thereon a polymeric composition comprising the reaction product of the solvent-free curable epoxy based adhesive resin composition of claim 1. ### Claim 14 (depends on 13) The article of claim 13 which is an electronic component. ### Claim 15 (depends on 13) The article of claim 13 wherein the electronic component comprises a chip attached to a substrate by the adhesive composition. ### Claim 16 (depends on 5) An article of manufacture comprising an electronic component having a chip bonded to a substrate by the adhesive composition of claim 5. ### Claim 17 (depends on 6) An article of manufacture comprising an electronic component having a chip bonded to a substrate by the adhesive composition of claim 6. ### Claim 18 (depends on 7) An article of manufacture comprising an electronic component having a chip bonded to a substrate by the adhesive composition of claim 7. ### Claim 19 (depends on 1) A method for making an electronic component assembly which requires attachment of separate components comprises: applying the adhesive of claim 1 onto one of the components to be bonded; placing the other component to be bonded on the adhesive of the adhesive coated component; heating the assembly to cure the adhesive to attach the components. ### Claim 20 (depends on 19) The method of claim 19 wherein the adhesive further comprises a conductive filler. ### Claim 21 (depends on 19) The method of claim 19 wherein the adhesive further comprises an additive to the composition wherein the additive enables the bonded components to be reworked without the need for solvents which additive is selected from the group consisting of polyacrylate, poly(meth)acrylate, polyalkylacrylate and polyalkylmethacrylate, polyfluoro alkyl acrylate and polyfluoroalkyl methacrylate wherein the alkyl group is C1-C8. ### Claim 22 (depends on 19) The method of claim 19 wherein the adhesive further comprises a conductive filler and an additive to the composition wherein the additive enables the bonded components to be reworked without the need for solvents which additive is selected from the group consisting of polyacrylate, poly(meth)acrylate, polyalkylacrylate and polyalkylmethacrylate, polyfluoro alkyl acrylate and polyfluoroalkyl methacrylate wherein the alkyl group is C1-C8.