Thermal conductive silicone composition, semiconductor device, and method for manufacturing semiconductor device
Provided is a thermal conductive silicone composition containing: (A) an organopolysiloxane having a kinetic viscosity of 10 to 100,000 mm 2 /s at 25° C., and represented by the following average composition formula (1) R 1 a SiO (4-a)/2 (1) wherein R 1 represents a hydrogen atom or a monovalent hydrocarbon group, and a represents a number satisfying 1.8≤a≤2.2; (B) silver nanoparticles having an average particle size of 3 to 600 nm; (C) a thermal conductive filler other than the component (B), having an average particle size of 0.7 to 100 μm and a thermal conductivity of 10 W/m° C. or higher; and (D) a catalyst selected from the group consisting of a platinum based catalyst, an organic peroxide and a catalyst for condensation reaction.
1. A thermal conductive silicone composition comprising:
(A) an organopolysiloxane having a kinetic viscosity of 10 to 100,000 mm 2 /s at 25° C., and represented by the following average composition formula (1)
R 1 a SiO (4-a)/ 2 (1)
wherein R 1 represents a hydrogen atom, a hydroxy group or a saturated or unsaturated monovalent hydrocarbon group having 1 to 18 carbon atoms, and a represents a number satisfying 1.8≤a≤2.2;
(B) silver nanoparticles having an average particle size of 3 to 600 nm, the silver nanoparticles being in an amount of 50 to 1,700 parts by mass per 100 parts by mass of the component (A);
(C) a thermal conductive filler other than the component (B), having an average particle size of 0.7 to 100 μm and a thermal conductivity of 10 W/m° C. or higher, the thermal conductive filler being in an amount of 50 to 3,000 parts by mass per 100 parts by mass of the component (A); and
(D) a catalyst selected from the group consisting of a platinum based catalyst, an organic peroxide and a catalyst for condensation reaction, the catalyst (D) being in a catalytic amount,
wherein the thermal conductive filler as the component (C) has a tap density of 3.0 to 7.0 g/cm 3 and a specific surface area of 0.08 to 2.0 m 2 /g.
2. The thermal conductive silicone composition according to claim 1 , wherein a ratio of a thermal resistance of the composition after heating at 150° C. for 90 min with respect to a thermal resistance of the composition before the heating (thermal resistance after the heating/thermal resistance before the heating) is not higher than 0.5; and a value of (adhesion strength after the heating at 150° C. for 90 min)/(adhesion strength after heating at 60° C. for 90 min) is not smaller than 2.0.
3. The thermal conductive silicone composition according to claim 2 , wherein a part of or the whole component (A) is a component (E) which is an organopolysiloxane containing in one molecule at least two silicon atom-bonded alkenyl groups; and/or a component (F) which is an organohydrogenpolysiloxane containing in one molecule at least two silicon atom-bonded hydrogen atoms.
4. The thermal conductive silicone composition according to claim 2 , further comprising:
(G) an organosilane being in an amount of 0.1 to 20 parts by mass per 100 parts by mass of the component (A), and represented by the following average composition formula (2)
R 2 b Si(OR 3 ) 4-b (2)
wherein R 2 represents at least one group selected from: a saturated or unsaturated monovalent hydrocarbon group that may have a substituent group(s) and has 1 to 18 carbon atoms; an epoxy group; an acryl group; and a methacryl group, R 3 represents a monovalent hydrocarbon group having 1 to 18 carbon atoms, and b represents a number satisfying 1≤b≤3.
5. The thermal conductive silicone composition according to claim 1 , wherein the thermal conductive filler as the component (C) is a silver powder having an average particle size of 0.7 to 20 μm.
6. The thermal conductive silicone composition according to claim 5 , wherein a part of or the whole component (A) is a component (E) which is an organopolysiloxane containing in one molecule at least two silicon atom-bonded alkenyl groups; and/or a component (F) which is an organohydrogenpolysiloxane containing in one molecule at least two silicon atom-bonded hydrogen atoms.
7. The thermal conductive silicone composition according to claim 5 , further comprising:
(G) an organosilane being in an amount of 0.1 to 20 parts by mass per 100 parts by mass of the component (A), and represented by the following average composition formula (2)
R 2 b Si(OR 3 ) 4-b (2)
wherein R 2 represents at least one group selected from: a saturated or unsaturated monovalent hydrocarbon group that may have a substituent group(s) and has 1 to 18 carbon atoms; an epoxy group; an acryl group; and a methacryl group, R 3 represents a monovalent hydrocarbon group having 1 to 18 carbon atoms, and b represents a number satisfying 1≤b≤3.
8. The thermal conductive silicone composition according to claim 1 , wherein a mass ratio α/β which is a ratio of a mass α of the silver nanoparticles as the component (B) to a mass β of the thermal conductive filler as the component (C) is 0.03 to 40.
9. The thermal conductive silicone composition according to claim 8 , wherein a part of or the whole component (A) is a component (E) which is an organopolysiloxane containing in one molecule at least two silicon atom-bonded alkenyl groups; and/or a component (F) which is an organohydrogenpolysiloxane containing in one molecule at least two silicon atom-bonded hydrogen atoms.
10. The thermal conductive silicone composition according to claim 8 , further comprising:
(G) an organosilane being in an amount of 0.1 to 20 parts by mass per 100 parts by mass of the component (A), and represented by the following average composition formula (2)
R 2 b Si(OR 3 ) 4-b (2)
wherein R 2 represents at least one group selected from: a saturated or unsaturated monovalent hydrocarbon group that may have a substituent group(s) and has 1 to 18 carbon atoms; an epoxy group; an acryl group; and a methacryl group, R 3 represents a monovalent hydrocarbon group having 1 to 18 carbon atoms, and b represents a number satisfying 1≤b≤3.
11. The thermal conductive silicone composition according to claim 1 , wherein a part of or the whole component (A) is a component (E) which is an organopolysiloxane containing in one molecule at least two silicon atom-bonded alkenyl groups; and/or a component (F) which is an organohydrogenpolysiloxane containing in one molecule at least two silicon atom-bonded hydrogen atoms.
12. The thermal conductive silicone composition according to claim 11 , further comprising:
(G) an organosilane being in an amount of 0.1 to 20 parts by mass per 100 parts by mass of the component (A), and represented by the following average composition formula (2)
R 2 b Si(OR 3 ) 4-b (2)
wherein R 2 represents at least one group selected from: a saturated or unsaturated monovalent hydrocarbon group that may have a substituent group(s) and has 1 to 18 carbon atoms; an epoxy group; an acryl group; and a methacryl group, R 3 represents a monovalent hydrocarbon group having 1 to 18 carbon atoms, and b represents a number satisfying 1≤b≤3.
13. The thermal conductive silicone composition according to claim 1 , further comprising:
(G) an organosilane being in an amount of 0.1 to 20 parts by mass per 100 parts by mass of the component (A), and represented by the following average composition formula (2)
R 2 b Si(OR 3 ) 4-b (2)
wherein R 2 represents at least one group selected from: a saturated or unsaturated monovalent hydrocarbon group that may have a substituent group(s) and has 1 to 18 carbon atoms; an epoxy group; an acryl group; and a methacryl group, R 3 represents a monovalent hydrocarbon group having 1 to 18 carbon atoms, and b represents a number satisfying 1≤b≤3.
14. A semiconductor device comprising a heat-generating electronic part and a heat dissipator wherein the thermal conductive silicone composition as set forth in claim 1 is interposed between the heat-generating electronic part and the heat dissipator.
15. A method for manufacturing a semiconductor device, comprising a step of heating the thermal conductive silicone composition as set forth in claim 1 to 80° C. or higher with the thermal conductive silicone composition being sandwiched between a heat-generating electronic part and a heat dissipator, and with a pressure of 0.01 MPa or higher being applied thereto.
16. A thermal conductive silicone composition comprising:
(A) an organopolysiloxane having a kinetic viscosity of 10 to 100,000 mm 2 /s at 25° C., and represented by the following average composition formula (1)
R 1 a SiO (4-a)/ 2 (1)
wherein R 1 represents a hydrogen atom, a hydroxy group or a saturated or unsaturated monovalent hydrocarbon group having 1 to 18 carbon atoms, and a represents a number satisfying 1.8≤a≤2.2;
(B) silver nanoparticles having an average particle size of 3 to 600 nm, the silver nanoparticles being in an amount of 50 to 1,700 parts by mass per 100 parts by mass of the component (A);
(C) a thermal conductive filler other than the component (B), having an average particle size of 0.7 to 100 μm and a thermal conductivity of 10 W/m° C. or higher, the thermal conductive filler being in an amount of 50 to 3,000 parts by mass per 100 parts by mass of the component (A);
(D) a catalyst selected from the group consisting of a platinum based catalyst, an organic peroxide and a catalyst for condensation reaction, the catalyst (D) being in a catalytic amount; and
(G) an organosilane being in an amount of 0.1 to 20 parts by mass per 100 parts by mass of the component (A), and represented by the following average composition formula (2)
R 2 b Si(OR 3 ) 4-b (2)
wherein R 2 represents at least one group selected from: a saturated or unsaturated monovalent hydrocarbon group that may have a substituent group(s) and has 1 to 18 carbon atoms; an epoxy group; an acryl group; and a methacryl group, R 3 represents a monovalent hydrocarbon group having 1 to 18 carbon atoms, and b represents a number satisfying 1≤b≤3.
17. The thermal conductive silicone composition according to claim 16 , wherein a ratio of a thermal resistance of the composition after heating at 150° C. for 90 min with respect to a thermal resistance of the composition before the heating (thermal resistance after the heating/thermal resistance before the heating) is not higher than 0.5; and a value of (adhesion strength after the heating at 150° C. for 90 min)/(adhesion strength after heating at 60° C. for 90 min) is not smaller than 2.0.
18. The thermal conductive silicone composition according to claim 17 , wherein a part of or the whole component (A) is a component (E) which is an organopolysiloxane containing in one molecule at least two silicon atom-bonded alkenyl groups; and/or a component (F) which is an organohydrogenpolysiloxane containing in one molecule at least two silicon atom-bonded hydrogen atoms.
19. The thermal conductive silicone composition according to claim 16 , wherein the thermal conductive filler as the component (C) is a silver powder having an average particle size of 0.7 to 20 μm.
20. The thermal conductive silicone composition according to claim 19 , wherein a part of or the whole component (A) is a component (E) which is an organopolysiloxane containing in one molecule at least two silicon atom-bonded alkenyl groups; and/or a component (F) which is an organohydrogenpolysiloxane containing in one molecule at least two silicon atom-bonded hydrogen atoms.
21. The thermal conductive silicone composition according to claim 16 , wherein a mass ratio α/β which is a ratio of a mass α of the silver nanoparticles as the component (B) to a mass β of the thermal conductive filler as the component (C) is 0.03 to 40.
22. The thermal conductive silicone composition according to claim 21 , wherein a part of or the whole component (A) is a component (E) which is an organopolysiloxane containing in one molecule at least two silicon atom-bonded alkenyl groups; and/or a component (F) which is an organohydrogenpolysiloxane containing in one molecule at least two silicon atom-bonded hydrogen atoms.
23. The thermal conductive silicone composition according to claim 16 , wherein a part of or the whole component (A) is a component (E) which is an organopolysiloxane containing in one molecule at least two silicon atom-bonded alkenyl groups; and/or a component (F) which is an organohydrogenpolysiloxane containing in one molecule at least two silicon atom-bonded hydrogen atoms.
24. A semiconductor device comprising a heat-generating electronic part and a heat dissipator wherein the thermal conductive silicone composition as set forth in claim 16 is interposed between the heat-generating electronic part and the heat dissipator.
25. A method for manufacturing a semiconductor device, comprising a step of heating the thermal conductive silicone composition as set forth in claim 16 to 80° C. or higher with the thermal conductive silicone composition being sandwiched between a heat-generating electronic part and a heat dissipator, and with a pressure of 0.01 MPa or higher being applied thereto.