Silicone-based resin composition and semiconductor device including the same

Abstract

Disclosed is a silicone-based resin composition comprising an organopolysiloxane and a conductive filler; a silicone-based resin composition and a semiconductor device comprising the same, wherein the relative ratio of the change in thermal conductivity to the change in Shore A hardness of the silicone-based resin composition measured by the following measurement method is 40% or less: [measurement method] (see the specification of the present invention)

Description

Technical Field

[0001] The present invention relates to a silicone-based resin composition and a semiconductor device including the same. Background Art

[0002] Since most electronic components generate heat during use, it is necessary to remove this heat from the components to ensure their proper operation. In particular, in integrated circuit components such as CPUs used in personal computers, the amount of heat dissipated is increasing due to increases in operating frequency, and thus countermeasures against this heat have become a significant issue.

[0003] Therefore, many methods for dissipating this heat have been proposed. In electronic components that dissipate a large amount of heat, a method has been proposed for dissipating heat by inserting a thermally conductive material, such as thermal grease or a thermally conductive sheet, between the electronic component and a member, such as a heat sink. Korean Patent Application Publication No. 10-2020-0086307 discloses a semiconductor device that includes a thermally conductive material.

[0004] However, the thermal conductive material has hardness variations depending on process conditions, which leads to a problem in that the reliability of product performance is reduced due to differently expressed thermal conductivity characteristics.

[0005] Related technical literature

[0006] Patent Literature

[0007] (Patent Document 1) Korean Patent Application Publication No. 10-2020-0086307 Summary of the Invention

[0008] Technical issues

[0009] According to one aspect of the present invention, the above and other objects can be achieved by providing a silicone-based resin composition having minimized thermal conductivity variation and excellent mechanical properties, and a semiconductor device including the same.

[0010] Technical Solution

[0011] According to one aspect of the present invention, the above and other objects can be achieved by providing a silicone-based resin composition comprising: an organopolysiloxane; and a conductive filler, wherein a relative ratio of a change in thermal conductivity to a change in Shore A hardness of the silicone-based resin composition measured by the following measurement method is 40% or less:

[0012] [Measurement method]

[0013] 1) By 165℃ and 26kgf / cm 2The silicone-based resin composition was molded by hot pressing under a pressure of 1000 Å for 15 minutes to produce a sheet.

[0014] 2) The sheet was cured at 150° C. for 5 minutes to produce a first cured product. The first cured product was measured for Shore A hardness according to ASTM D-2240 and for thermal conductivity at 25° C. according to ISO 22007-2.

[0015] 3) The first cured product was cured at 150° C. for 120 minutes to produce a second cured product. The second cured product was measured for Shore A hardness according to ASTM D-2240 and for thermal conductivity at 25° C. according to ISO 22007-2.

[0016] 4) The relative ratio of the change in thermal conductivity to the change in Shore A hardness was calculated according to the following equation 1:

[0017] [Equation 1]

[0018] [(│TC H2 –TC H1 │) / (H2-H1)]×100

[0019] (where H1 represents the Shore A hardness of the first cured product, H2 represents the Shore A hardness of the second cured product, TC H1 Indicates the thermal conductivity in H1 W / mK, TC H2 represents the thermal conductivity in H2 (W / mK).

[0020] In one embodiment of the present invention, the silicone-based resin composition may have a thermal conductivity variation rate of 30% or less calculated according to the following Equation 2:

[0021] [Equation 2]

[0022] (│TC H2 –TC H1 │ / TC H2 )×100

[0023] (TC H1 and TC H2 As defined in Equation 1 above. ).

[0024] In one embodiment of the present invention, the cured product of the silicone-based resin composition may have a Shore A hardness according to ASTM D-2240 of 95 or less.

[0025] In one embodiment of the present invention, the silicone-based resin composition may satisfy the following Equation 3:

[0026] [Equation 3]

[0027] Y=0.0169X+6.5193

[0028] (wherein X represents the Shore A hardness of the cured product of the silicone-based resin composition according to ASTM D-2240, Y represents the thermal conductivity of the cured product of the silicone-based resin composition at 25° C. according to ISO 22007-2, and Y is 6 W / mK to 8 W / mK.).

[0029] In one embodiment of the present invention, X may be in the range of 3 to 57, and the coefficient of determination (R 2 ) is 0.95 or greater.

[0030] In one embodiment of the present invention, the conductive filler may include conductive powder including flake-shaped particles having a thickness of 0.01 μm to 5 μm.

[0031] In one embodiment of the present invention, the conductive powder may have a 0.1 m 2 / g to 1.5m 2 / g specific surface area.

[0032] In one embodiment of the present invention, the conductive powder may have an average particle size (D 50 ).

[0033] In one embodiment of the present invention, the loss on ignition of the conductive powder may be 0.4 wt % or less.

[0034] According to another aspect of the present invention, there is provided a semiconductor device comprising: a semiconductor package; a heat dissipation component provided on the semiconductor package; and a heat conduction layer interposed between the semiconductor package and the heat dissipation component, wherein the heat conduction layer comprises a silicone-based resin composition comprising an organopolysiloxane and a conductive filler, and a relative ratio of a change in thermal conductivity to a change in Shore A hardness of the silicone-based resin composition measured by the following measurement method is 40% or less:

[0035] [Measurement method]

[0036] 1) By 165℃ and 26kgf / cm 2 The silicone-based resin composition was molded by hot pressing under a pressure of 1000 nm for 15 minutes to produce a sheet.

[0037] 2) The sheet was cured at 150° C. for 5 minutes to produce a first cured product. The first cured product was measured for Shore A hardness according to ASTM D-2240 and for thermal conductivity at 25° C. according to ISO 22007-2.

[0038] 3) The first cured product was cured at 150° C. for 120 minutes to produce a second cured product. The second cured product was measured for Shore A hardness according to ASTM D-2240 and for thermal conductivity at 25° C. according to ISO 22007-2.

[0039] 4) The relative ratio of the change in thermal conductivity to the change in Shore A hardness was calculated according to the following equation 1:

[0040] [Equation 1]

[0041] [(│TC H2 –TC H1 │) / (H2-H1)]×100

[0042] (where H1 represents the Shore A hardness of the first cured product, H2 represents the Shore A hardness of the second cured product, TC H1 Indicates the thermal conductivity in H1 W / mK, TC H2 represents the thermal conductivity in H2 (W / mK).

[0043] Beneficial effects

[0044] The silicone-based resin composition according to the present invention exhibits a thermal conductivity value capable of performing an appropriate heat dissipation function even when hardness varies, and can improve reliability of product performance due to small variations in thermal conductivity.

[0045] Furthermore, the silicone-based resin composition according to the present invention includes conductive particles having a relatively thin flake shape, thereby reducing the empty space between the conductive filler particles, and thus, can alleviate the arrangement deformation of the conductive filler during the curing process, thereby reducing the change in thermal conductivity caused by the change in hardness.

[0046] Furthermore, the silicone-based resin composition according to the present invention can exhibit relatively high thermal conductivity with only a low content of the conductive filler, compared to a silicone-based resin composition containing a high content of the conductive filler, thereby being able to improve adhesion reliability and moldability. BRIEF DESCRIPTION OF THE DRAWINGS

[0047] Figure 1 Methods of measuring the Shore A hardness and thermal conductivity of the silicone-based resin composition according to the present invention are sequentially shown.

[0048] Figure 2 A semiconductor device according to the present invention is schematically shown.

[0049] Best Way

[0050] The structural or functional descriptions of the embodiments disclosed in this specification or application are merely illustrative for explaining the embodiments according to the technical ideas of the present invention. The embodiments according to the technical ideas of the present invention may be implemented in various forms different from the embodiments disclosed in this specification or application, and it should not be understood that the technical ideas of the present invention are limited to the embodiments described in this specification or application.

[0051] In addition, when a component (component) is “included” or “comprising” in this specification or application, other components (components) may be further included or comprised, rather than excluding other components (components), unless otherwise specified. In addition, it should be understood that, unless otherwise specified, all numerical ranges representing physical property values, dimensions, etc. of components (components) described in this specification or application are modified by the term “about” in all cases.

[0052] Hereinafter, a silicone-based resin composition and a semiconductor device including the same according to the present invention are described.

[0053] <Silicone-based resin composition>

[0054] The silicone-based resin composition according to the present invention includes an organopolysiloxane and a conductive filler, and a relative ratio of a change in thermal conductivity to a change in Shore A hardness of the silicone-based resin composition measured by the following measurement method is 40% or less:

[0055] [Measurement method]

[0056] 1) By 165℃ and 26kgf / cm 2 The silicone-based resin composition was molded by hot pressing under a pressure of 1000 nm for 15 minutes to produce a sheet.

[0057] 2) The sheet was cured at 150° C. for 5 minutes to produce a first cured product. The first cured product was measured for Shore A hardness according to ASTM D-2240 and for thermal conductivity at 25° C. according to ISO 22007-2.

[0058] 3) The first cured product was cured at 150° C. for 120 minutes to produce a second cured product. The second cured product was measured for Shore A hardness according to ASTM D-2240 and for thermal conductivity at 25° C. according to ISO 22007-2.

[0059] 4) The relative ratio of the change in thermal conductivity to the change in Shore A hardness was calculated according to the following equation 1:

[0060] [Equation 1]

[0061] [(│TC H2 –TCH1 │) / (H2-H1)]×100

[0062] (where H1 represents the Shore A hardness of the first cured product, H2 represents the Shore A hardness of the second cured product, TC H1 Indicates the thermal conductivity in H1 (W / mK), TC H2 represents the thermal conductivity in H2 (W / mK).

[0063] The silicone-based resin composition includes an organopolysiloxane.

[0064] The organopolysiloxane can be represented by the following formula 1:

[0065] [Formula 1]

[0066] R 1 a SiO b

[0067] where R 1 represents one or two or more groups selected from hydrogen atoms, hydroxyl groups, and saturated or unsaturated monovalent hydrocarbon groups having 1 to 18 carbon atoms, a may be from about 1.8 to about 2.2, and a+b may be from about 3.5 to about 8.

[0068] a+b can be 4.

[0069] In formula 1, R 1 The saturated or unsaturated monovalent hydrocarbon radical having 1 to 18 carbon atoms represented may be, for example, an alkyl radical such as methyl, ethyl, propyl, hexyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl or octadecyl; a cycloalkyl radical such as cyclopentyl or cyclohexyl; an alkenyl radical such as vinyl or allyl; an aryl radical such as phenyl or tolyl; an aralkyl radical such as 2-phenylethyl or 2-methyl-2-phenylethyl; a halogenated hydrocarbon radical such as 3,3,3-trifluoropropyl, 2-(perfluorobutyl)ethyl, 2-(perfluorooctyl)ethyl or p-chlorophenyl.

[0070] The organopolysiloxane may have a weight average molecular weight of about 40,000 g / mol to about 80,000 g / mol, about 30,000 g / mol to about 100,000 g / mol, about 500 g / mol to about 10,000 g / mol, about 700 g / mol to about 7,000 g / mol, about 1,000 g / mol to about 5,000 g / mol, or about 1,500 g / mol to about 3,000 g / mol. The weight average molecular weight may be measured based on polystyrene.

[0071] In organopolysiloxane, the kinematic viscosity at 25°C can be 10 mm 2 / s to 100,000mm2 / s、20,000mm 2 / s to 100,000mm 2 / s, or about 30mm 2 / s to about 10,000mm 2 The kinematic viscosity of the organopolysiloxane may be a value measured at 25° C. using an Ostwald viscometer.

[0072] When the organopolysiloxane has a weight average molecular weight and a kinematic viscosity within the above ranges, since voids and cracks due to thermal shock do not occur, appropriate bonding strength with an adherend can be maintained and durability can be improved.

[0073] The organopolysiloxane may include a first organopolysiloxane.

[0074] The first organopolysiloxane includes alkenyl groups bonded to silicon atoms, and the number of the alkenyl groups present in one molecule of the first organopolysiloxane may be at least two, two to ten, two to five, or two.

[0075] The first organopolysiloxane may be represented by the following Formula 2:

[0076] [Formula 2]

[0077] R 1 a R 2 c SiO b

[0078] where R 1 may be a hydrogen atom, a hydroxyl group, or a saturated or unsaturated monovalent hydrocarbon group having 1 to 18 carbon atoms, and R 2 It may be an alkenyl group. In Formula 2, a+c may be about 1.8 to about 2.2, and a+b+c may be about 3.5 to about 8. In Formula 2, a+b+c may be about 4. In Formula 2, a may be about 1.8 to about 2.2. In addition, c may be 0.0001 to 0.1.

[0079] The first organopolysiloxane may be represented by the following Formula 3:

[0080] [Formula 3]

[0081]

[0082] where R 1 It can be a hydrogen atom, a hydroxyl group or a saturated or unsaturated monovalent hydrocarbon group having 1 to 18 carbon atoms, R 2It may be an alkenyl group. In addition, in Formula 3, n may be 1 to 1500, and m may be 0 to 20. In Formula 3, n may be 10 to 1000, and m may be 0 to 20.

[0083] The first organopolysiloxane may be represented by the following Formula 4:

[0084] [Formula 4]

[0085]

[0086] wherein n may be from 1 to 1,500. wherein n may be from 10 to 1,000.

[0087] The first organopolysiloxane may have a weight average molecular weight (Mw) of about 500 g / mol to about 10,000 g / mol, about 700 g / mol to about 7,000 g / mol, about 1,000 g / mol to about 5,000 g / mol, or about 1,500 g / mol to about 3,000 g / mol. The weight average molecular weight may be measured based on polystyrene.

[0088] The first organopolysiloxane may have a kinematic viscosity of 10 to 100,000 cPs, 30 to 50,000 cPs, or 10,000 to 40,000 cPs at 23° C. The kinematic viscosity of the first organopolysiloxane may be a value measured at 25° C. using an Ostwald viscometer.

[0089] The organopolysiloxane may include a second organopolysiloxane.

[0090] The second organopolysiloxane may include hydrogen groups bonded to silicon atoms. The number of hydrogen groups per molecule of the second organopolysiloxane may be 1-10, 2-10, 2-5, or 2.

[0091] The second organopolysiloxane may be represented by the following Formula 5:

[0092] [Formula 5]

[0093]

[0094] where R 1 may be a hydrogen atom, a hydroxyl group, or a saturated or unsaturated monovalent hydrocarbon group having 1 to 18 carbon atoms, and R 3 It may be a hydrogen atom. In addition, in Formula 5, n may be 1 to 1,500, and m may be 0 to 20. In Formula 5, n may be 10 to 1,000, and m may be 0 to 20. In Formula 5, n may be 1 to 1,500, and m may be 0.

[0095] The second organopolysiloxane may be represented by the following Formula 6:

[0096] [Formula 6]

[0097]

[0098] The second organopolysiloxane may have a viscosity of about 500 cPs to about 5,000 cPs, about 500 cPs to about 3,000 cPs, or about 500 cPs to about 2,000 cPs at about 23°C.

[0099] The organopolysiloxane may further include a third organopolysiloxane. The third organopolysiloxane may be represented by the following formula 7:

[0100] [Formula 7]

[0101]

[0102] where R 1 It can be a hydrogen atom, a hydroxyl group or a saturated or unsaturated monovalent hydrocarbon group having 1 to 18 carbon atoms, R 3 It may be a hydrogen atom. In addition, in Formula 7, n may be 1 to 1,500, and m may be 1 to 500. In Formula 7, n may be 10 to 1,000, and m may be 1 to 100.

[0103] The third organopolysiloxane may be represented by the following Formula 8:

[0104] [Formula 8]

[0105]

[0106] wherein n may be 1 to 1,500, and m may be 1 to 500. In Formula 8, n may be 10 to 1,000, and m may be 1 to 100.

[0107] The third organopolysiloxane may have a viscosity of about 50 cPs to about 1,000 cPs, about 100 cps to about 500 cPs, or about 100 cPs to about 500 cPs at about 23°C.

[0108] The ratio of the viscosity of the first organopolysiloxane to the viscosity of the second organopolysiloxane may be 10:1 to 40:1.

[0109] In addition, the ratio of the viscosity of the second organopolysiloxane to the viscosity of the third organopolysiloxane may be 2:1 to 10:1.

[0110] The first organopolysiloxane may be included in an amount of about 60 parts by weight to about 90 parts by weight, about 70 parts by weight to about 85 parts by weight, or about 75 parts by weight to about 85 parts by weight, based on 100 parts by weight of the total organopolysiloxane.

[0111] The second organopolysiloxane may be included in an amount of about 10 parts by weight to about 40 parts by weight, about 10 parts by weight to about 30 parts by weight, or about 12 parts by weight to about 23 parts by weight, based on 100 parts by weight of the first organopolysiloxane.

[0112] The third organopolysiloxane may be included in an amount of about 3 parts by weight to about 20 parts by weight, about 3 parts by weight to about 15 parts by weight, or about 4 parts by weight to about 10 parts by weight, based on 100 parts by weight of the first organopolysiloxane.

[0113] When the silicone-based resin composition includes the first, second, and third organopolysiloxanes within the above ranges, proper adhesion to an adherend may be maintained, and the silicone-based resin composition may be uniformly spread during a coating process.

[0114] The silicone-based resin composition contains a conductive filler.

[0115] The conductive filler may include conductive powder including flaky particles. The conductive powder may include flaky silver particles.

[0116] The conductive filler may include conductive powder comprising flaky particles having a thickness of 0.01 μm to 5 μm, 0.01 μm to 4 μm, 0.01 μm to 3 μm, or 0.01 μm to 2 μm. The inclusion of flaky particles within this thickness range reduces the empty space between the conductive filler particles, thereby alleviating deformation of the conductive filler arrangement during the curing process, thereby reducing changes in thermal conductivity caused by changes in hardness.

[0117] The conductive powder can have a 0.1 g / cm 3 Up to 10.0g / cm 3 , 1.0g / cm 3 Up to 8.0g / cm 3 , 2.0g / cm 3 Up to 8.0g / cm 3 , 3.0g / cm 3 Up to 8.0g / cm 3 , 4.0g / cm 3 Up to 8.0g / cm 3 , or 4.0g / cm 3 Up to 7.0g / cm 3 The tap density.

[0118] The tap density is calculated based on the volume of silver powder, which is obtained by weighing 100 g of silver powder and gently dropping it into a 100 ml graduated cylinder with a funnel, then placing the graduated cylinder on a tap density meter and dropping it 600 times at a speed of 60 times / min with a dropping distance of 20 mm to compact it.

[0119] The conductive powder may have an average particle size (D) of about 0.5 μm to about 20 μm, about 1 μm to about 20 μm, about 1 μm to about 15 μm, about 1 μm to about 10 μm, about 1 μm to about 5 μm, or about 1.5 μm to about 2.5 μm. 50 ).

[0120] Average particle size (D 50 ) is defined as the particle size corresponding to 50% cumulative volume in the particle size distribution curve of silver powder derived using a laser diffraction method.

[0121] Conductive powder can have 0.1m 2 / g to 3.0m 2 / g, 0.1m 2 / g to 2.0m 2 / g, 0.1m 2 / g to 1.8m 2 / g, 0.1m 2 / g to 1.5m 2 / g, 0.1m 2 / g to 1.0m 2 / g, 0.1m 2 / g to 0.9m 2 / g, 0.1m 2 / g to 0.8m 2 / g, or 0.1m 2 / g to 0.7m 2 / g specific surface area.

[0122] The specific surface area is determined by taking about 2 g of silver powder as a sample and degassing it at 60±5° C. for 10 minutes, then measuring the total surface area with an automatic specific surface area measuring device (BET method), weighing the sample, and calculating according to the following equation.

[0123] Specific surface area (m 2 / g) = total surface area (m 2 ) / sample amount (g)

[0124] The flake-shaped particles included in the conductive powder may have an aspect ratio of about 2 to 30, about 2 to 25, about 2 to 20, or about 2 to 18.

[0125] The conductive powder may be surface treated with a surface treatment agent. The surface treatment agent may include C10 to C20 fatty acids. Examples of fatty acids include capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, myristoleic acid, palmitoleic acid, hexadecenoic acid, oleic acid, elaidic acid, vaccinic acid, linoleic acid, lionelidic acid, arachidonic acid, eicosapentaenoic acid, α-linolenic acid, and the like.

[0126] The conductive powder may have a loss on ignition (Ig loss) of less than about 0.8 wt%, less than about 0.7 wt%, less than about 0.6 wt%, less than about 0.5 wt%, less than about 0.4 wt%, less than about 0.3 wt%, less than about 0.2 wt%, or about 0.01 wt% or more to less than about 0.4 wt%. The loss on ignition may be measured at about 538° C. for about 1 hour.

[0127] Even with a small amount of surface treatment agent, the conductive powder can be effectively surface-treated. That is, conductive powder has a relatively low tap density and a large specific surface area, and can be surface-treated even with a small amount of surface treatment agent. Therefore, the conductive powder can improve the thermal connection of the conductive filler while being uniformly dispersed in the organopolysiloxane. In other words, because the conductive powder has improved dispersibility, it can be added to the organopolysiloxane in high concentrations. Furthermore, because the conductive powder has a thin flaky surface area and the coating formed by the surface treatment agent is thin, the contact characteristics between the conductive fillers can be improved. Therefore, the conductive powder can increase the thermal conductivity of the silicone-based resin composition.

[0128] The silicone-based resin composition may include the first silver powder in an amount of about 300 to about 1,000 parts by weight, about 400 to 900 parts by weight, or about 500 to 800 parts by weight, based on 100 parts by weight of the organopolysiloxane.

[0129] The conductive powder may further include dendritic silver particles or spherical silver particles.

[0130] Since the conductive filler includes flaky silver particles and dendritic silver particles or spherical silver particles having a shape different from that of the flaky silver particles, formation of an electrical network between particles may be improved, thereby improving thermal conductivity.

[0131] The silicone-based resin composition may include the organopolysiloxane and the conductive filler in a weight ratio of 20:80 to 5:95, 20:80 to 6:94, or 20:80 to 10:90. When this range is met, since voids and cracks due to thermal shock do not occur, proper adhesion to the adherend can be maintained and durability can be improved.

[0132] In the silicone-based resin composition according to the present invention, a relative ratio of a change in thermal conductivity to a change in Shore A hardness measured by the following measurement method is 40% or less:

[0133] [Measurement method]

[0134] 1) By 165℃ and 26kgf / cm 2 The silicone-based resin composition was molded by hot pressing under a pressure of 1000 nm for 15 minutes to produce a sheet.

[0135] 2) The sheet was cured at 150° C. for 5 minutes to produce a first cured product. The first cured product was measured for Shore A hardness according to ASTM D-2240 and for thermal conductivity at 25° C. according to ISO 22007-2.

[0136] 3) The first cured product was cured at 150° C. for 120 minutes to produce a second cured product. The second cured product was measured for Shore A hardness according to ASTM D-2240 and for thermal conductivity at 25° C. according to ISO 22007-2.

[0137] 4) The relative ratio of the change in thermal conductivity to the change in Shore A hardness was calculated according to the following equation 1:

[0138] [Equation 1]

[0139] [(│TC H2 –TC H1 │) / (H2-H1)]×100

[0140] (where H1 represents the Shore A hardness of the first cured product, H2 represents the Shore A hardness of the second cured product, TC H1 Indicates the thermal conductivity in H1 (W / mK), TC H2 represents the thermal conductivity in H2 (W / mK). ).

[0141] Figure 1 Methods of measuring the Shore A hardness and thermal conductivity of the silicone-based resin composition according to the present invention are sequentially shown.

[0142] Reference Figure 1 , (a) feeding the silicone-based resin composition 10 into the mold 20, and then heating the mold 20 by heating the mold 20 at 165°C and 26 kgf / cm 2 The silicone-based resin composition 10 was molded by hot pressing under a pressure of 1000 Å for 15 minutes to produce a sheet 11 .

[0143] Next, (b) the sheet 11 was cured at 150° C. for 5 minutes to produce a first cured product 11 - 1 .

[0144] Next, (c) the first cured product 11-1 was subjected to Shore A hardness measurement according to ASTM D-2240, and thermal conductivity measurement at 25°C according to ISO 22007-2.

[0145] Next, (d) the first cured product 11 - 1 was cured at 150° C. for 120 minutes to produce a second cured product 11 - 2 .

[0146] Next, (e) the second cured product 11-2 was subjected to Shore A hardness measurement according to ASTM D-2240, and thermal conductivity measurement at 25° C. according to ISO 22007-2.

[0147] The sheet 11 and the first cured product 11 - 1 may be fed into the oven 30 and cured therein.

[0148] Next, the hardness and thermal conductivity measurement values of the first cured product 11-1 and the hardness and thermal conductivity measurement values of the second cured product 11-2 are substituted into Equation 1 to calculate the relative ratio of the change in thermal conductivity of the first cured product 11-1 and the second cured product 11-2 to the change in Shore A hardness of the first cured product 11-1 and the second cured product 11-2.

[0149] In the silicone-based resin composition, a relative ratio of a change in thermal conductivity to a change in Shore A hardness measured by the measurement method may be 35% or less, 30% or less, 25% or less, 20% or less, 10% or less, 5% or less, or 1% or less.

[0150] The silicone-based resin composition may have a thermal conductivity variation rate of 30% or less calculated according to the following Equation 2:

[0151] [Equation 2]

[0152] (│TC H2 –TC H1 │ / TC H2 )×100

[0153] (TC H1 and TC H2 As defined in Equation 1 above. ).

[0154] The silicone-based resin composition may have a thermal conductivity variation rate of 25% or less, 20% or less, 15% or less, 13% or less, 10% or less, 5% or less, 3% or less, or 1.5% or less.

[0155] Typically, silicone-based resin compositions can cause changes in the hardness of products manufactured from the composition, depending on the curing temperature, curing time, or composition of the composition. Furthermore, since changes in thermal conductivity occur due to changes in product hardness, this can be problematic when used in products that require heat dissipation.

[0156] Therefore, since the relative ratio of the change in thermal conductivity to the change in Shore A hardness of the silicone-based resin composition according to the present invention measured by the measurement method is 40% or less, the change in thermal conductivity is significantly reduced compared to the change in hardness, indicating a thermal conductivity value capable of performing an appropriate heat dissipation function, and even if the hardness of a product manufactured from the silicone-based resin composition changes, reliability can be improved when applying a product that needs to perform a heat dissipation function due to a small change in thermal conductivity.

[0157] Furthermore, since the silicone-based resin composition according to the present invention can exhibit relatively high thermal conductivity with only a low content of the conductive filler, adhesion reliability and moldability can be improved compared to a silicone-based resin composition including a high content of the conductive filler.

[0158] The cured product of the silicone-based resin composition may have a Shore A hardness according to ASTM D-2240 of 95 or less, 85 or less, 75 or less, 65 or less, 60 or less, 10 to 60 or less, 20 to 60 or less, or 30 to 60 or less. When the hardness is within this range, the occurrence of wear or cracking during product manufacturing can be minimized.

[0159] The silicone-based resin composition may satisfy the following Equation 3:

[0160] [Equation 3]

[0161] Y=0.0169X+6.5193

[0162] (wherein X represents the Shore A hardness of the cured product of the silicone-based resin composition according to ASTM D-2240, Y represents the thermal conductivity of the cured product of the silicone-based resin composition at 25° C. according to ISO 22007-2, and Y is 6 to 8 W / mK.)

[0163] The coefficient of determination (R 2 ) can be 0.95 or greater.

[0164] Equation 3 represents a linear trend line with Shore A hardness as the X variable and thermal conductivity (which is the dependent variable according to the X variable) as the Y variable. The linear trend line can be exported using Microsoft Excel, and the coefficient of determination (R2 ). The coefficient of determination as a statistical term is a measure of the goodness of fit of a known regression equation and represents the relationship between the data Y and the dependent variable Y. i The sum of fluctuations of Y i The coefficient of determination is usually represented by R 2 It is indicated that the goodness of fit of the regression equation increases as the coefficient of determination approaches 1.

[0165] For example, in Equation 3, when X is in the range of 3 to 57, Y is 6.6 to 7.4, which means that when the Shore A hardness is in the range of 3 to 57, the thermal conductivity is 6.6 W / mK to 7.4 W / mK. Here, the coefficient of determination (R 2 ) indicates 0.95 or greater. Therefore, even if the change in hardness is large, the change in thermal conductivity is not relatively large, which may indicate that the goodness of fit of the regression equation is high. Therefore, even if there is a change in hardness, the silicone-based resin composition that satisfies Equation 3 can also meet the reliability of product performance due to the small change in thermal conductivity.

[0166] The silicone-based resin composition may further include a tackifier.

[0167] The tackifier may include an alkoxysilane. In addition, the tackifier may include an epoxy group. The tackifier may be at least one selected from the group consisting of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltriethoxysilane.

[0168] The silicone-based resin composition may include an amount of a tackifier in an amount of about 1 to about 20 parts by weight, about 1 to about 10 parts by weight, or about 2 to about 8 parts by weight, based on 100 parts by weight of the organopolysiloxane. The tackifier may improve the bonding strength between the organopolysiloxane and the conductive filler.

[0169] The silicone-based resin composition may further include a curing catalyst. The curing catalyst may accelerate the curing of the silicone-based resin composition.

[0170] The curing catalyst may include a platinum-based catalyst.

[0171] Examples of curing catalysts include organic titanates such as platinum-divinyltetramethyldisiloxane complex, tetrabutyl titanate and tetraisopropyl titanate; organic titanium chelate compounds such as diisopropoxybis(acetoacetate)titanium and diisopropoxybis(ethylacetoacetate)titanium; organic aluminum compounds such as tris(acetylacetonate)aluminum and tris(ethylacetoacetate)aluminum; organic zirconium compounds such as tetra(acetylacetonate)zirconium and zirconium tetrabutyrate; organic tin compounds such as dibutyltin dioctoate, dibutyltin dilaurate and butyltin 2-ethylhexanoate; metal salts of organic carboxylic acids such as tin naphthenate, tin oleate, tin butyrate, cobalt naphthenate and zinc stearate; amine compounds such as hexylamine and dodecylamine phosphate and salts thereof; quaternary ammonium salts such as benzyltriethylammonium acetate; lower fatty acid salts of alkali metals such as potassium acetate; dialkylhydroxylamines such as dimethylhydroxylamine and diethylhydroxylamine; and guanidine-containing organic silicon compounds.

[0172] The silicone-based resin composition may include the curing catalyst in an amount of about 0.01 to about 5 parts by weight, about 0.03 to about 3 parts by weight, or about 0.1 to about 2 parts by weight, based on 100 parts by weight of the organopolysiloxane.

[0173] The silicone-based resin composition may further include a reaction inhibitor. The reaction inhibitor may be at least one selected from the following: an acetylenic compound such as 2-methyl-3-butyn-2-ol, 2-phenyl-3-butyn-2-ol, and 1-ethynyl-1-cyclohexanol; an ene-yne compound such as 3-methyl-3-pentene-1-yne and 3,5-dimethyl-3-hexene-1-yne; a curing reaction inhibitor such as a hydrazine compound, a phosphine compound, and a thiol compound; and the like.

[0174] The silicone-based resin composition may include the reaction inhibitor in an amount of about 0.0001 parts by weight to about 10 parts by weight based on 100 parts by weight of the organopolysiloxane.

[0175] <Method for preparing silicone-based resin composition>

[0176] The method of preparing the silicone-based resin composition may be a known preparation method without being particularly limited.

[0177] For example, a silicone-based resin composition can be prepared by mixing an organopolysiloxane, a conductive filler, a tackifier, a curing catalyst, a curing reaction inhibitor, and the like using a mixer such as Trimix, Twinmix, and a planetary mixer (all manufactured by Inoue Seisakusho Co., Ltd., registered trademarks); Ultramixer (manufactured by Mizuho Kogyo Co., Ltd., registered trademarks); or Hibis Disper Mix (manufactured by Primix Co., Ltd., registered trademarks) for 30 minutes to 4 hours. During the mixing process, the process temperature may be about 0° C. to about 25° C.

[0178] Semiconductor devices

[0179] Figure 2 A semiconductor device according to the present invention is schematically shown.

[0180] See also Figure 2 , the semiconductor device may include a circuit board 100 , a semiconductor package 200 , conductive bumps 300 , a heat dissipation member 400 , and a heat conduction layer 500 .

[0181] A semiconductor device according to the present invention includes a semiconductor package 200, a heat dissipation member 400 provided on the semiconductor package 200, and a heat conduction layer 500 interposed between the semiconductor package 200 and the heat dissipation member 400, the heat conduction layer 500 comprising a silicone-based resin composition comprising an organopolysiloxane and a conductive filler, and wherein a relative ratio of a change in thermal conductivity to a change in Shore A hardness of the silicone-based resin composition measured by the following measurement method is 40% or less:

[0182] [Measurement method]

[0183] 1) By 165℃ and 26kgf / cm 2 The silicone-based resin composition was molded by hot pressing under a pressure of 1000 nm for 15 minutes to produce a sheet.

[0184] 2) The sheet was cured at 150° C. for 5 minutes to produce a first cured product. The first cured product was measured for Shore A hardness according to ASTM D-2240 and for thermal conductivity at 25° C. according to ISO 22007-2.

[0185] 3) The first cured product was cured at 150° C. for 120 minutes to produce a second cured product. The second cured product was measured for Shore A hardness according to ASTM D-2240 and for thermal conductivity at 25° C. according to ISO 22007-2.

[0186] 4) The relative ratio of the change in thermal conductivity to the change in Shore A hardness was calculated according to the following equation 1:

[0187] [Equation 1]

[0188] [(│TC H2 –TC H1 │) / (H2-H1)]×100

[0189] (where H1 represents the Shore A hardness of the first cured product, H2 represents the Shore A hardness of the second cured product, TC H1 Indicates the thermal conductivity in H1 (W / mK), TC H2 represents the thermal conductivity in H2 (W / mK). ).

[0190] Specific methods for measuring hardness and thermal conductivity of silicone-based resin compositions Figure 1 Same as shown in .

[0191] Since the relative ratio of the change in thermal conductivity of the silicone-based resin composition to the change in Shore A hardness is 40% or less, the heat-conducting layer 500 including the silicone-based resin composition has a small change in thermal conductivity, thereby ensuring the reliability of product performance. In addition, the heat-conducting layer 500 can maintain proper adhesion to the semiconductor package 200 and the heat dissipation member 400.

[0192] The circuit board 100 may support the semiconductor package 200 , the conductive bumps 300 , the heat dissipation member 400 , and the heat conduction layer 500 .

[0193] The circuit board 100 may include a circuit pattern. The circuit board 100 may include a plurality of circuit patterns disposed within a flat body comprising insulating and heat-resistant materials and having a predetermined strength. In addition, the circuit board 100 may include connection pads electrically connected to the circuit patterns and disposed on the body.

[0194] For example, the main body of the circuit board 100 may include a thermosetting resin-based substrate (such as an epoxy resin substrate or a polyimide substrate), a flat plate, or a flat plate with a heat-resistant organic film attached thereto, such as a liquid crystal polyester film or a polyamide film. The circuit pattern may be arranged in a pattern shape inside the main body and may include power wiring for power supply, ground wiring, and signal wiring for signal transmission. Each wiring may be arranged to be separated from each other by a plurality of interlayer insulating films formed on the upper and lower surfaces of the main body.

[0195] The connection pads may be exposed to the outside from the upper surface of the body and may be connected to the circuit pattern. Therefore, the external connector connected to the circuit board 100 may be electrically connected to the internal circuit pattern through the connection pads.

[0196] Various electronic components may be mounted on the connection pads included in the circuit board 100. That is, the circuit board 100 may be a system board on which electronic components including the semiconductor package 200 are mounted.

[0197] The semiconductor package 200 may be mounted on the circuit board 100. The semiconductor package 200 may be provided on the circuit board 100. The semiconductor package 200 may be connected to the circuit board 100 through the conductive bumps 300.

[0198] The semiconductor package 200 may include a semiconductor chip including an integrated circuit, a semiconductor package substrate connected to the semiconductor chip, a conductive solder for connecting the semiconductor chip and the semiconductor package substrate, and a sealing portion for sealing the semiconductor chip and the conductive solder. The sealing portion may include a resin composition such as epoxy resin molding.

[0199] The semiconductor package 200 may be a memory device, a central processing unit, or the like.

[0200] The conductive bump 300 may be disposed between the semiconductor package 200 and the circuit board 100. The conductive bump 300 may electrically connect the semiconductor package 200 and the circuit board 100 to each other. The conductive bump 300 may be electrically connected to the semiconductor package 200 and the connection pad.

[0201] The heat dissipation member 400 may be provided on the semiconductor package 200. The heat dissipation member 400 may cover the semiconductor package 200. The heat dissipation member 400 may be coupled to the circuit board 100. The heat dissipation member 400 may cover the side surface of the semiconductor package 200.

[0202] The heat dissipation member 400 may include a conductor, may include metal, or may be thermally connected to an external heat sink.

[0203] In addition, the heat dissipation member 400 can protect the semiconductor package 200 from external physical impact. The heat dissipation member 400 can protect the semiconductor package 200 from external electromagnetic waves. In other words, the heat dissipation member 400 can block external electromagnetic waves.

[0204] The heat conduction layer 500 may be disposed between the semiconductor package 200 and the heat dissipation member 400. The heat conduction layer 500 may directly contact the semiconductor package 200 and the heat dissipation member 400. The heat conduction layer 500 may be in close contact between the semiconductor package 200 and the heat dissipation member 400.

[0205] The heat conduction layer 500 may be thermally connected to the semiconductor package 200 and the heat dissipation member 400. That is, the heat conduction layer 500 may transfer heat generated from the semiconductor package 200 to the heat dissipation member 400.

[0206] The thickness of the heat conducting layer 500 may be about 1 μm to about 100 μm, about 2 μm to about 70 μm, about 5 μm to about 60 μm, or about 10 μm to about 40 μm.

[0207] <Method for manufacturing a semiconductor device>

[0208] The method of manufacturing the semiconductor device may be a known manufacturing method without particular limitation.

[0209] First, the semiconductor package 200 may be mounted on the circuit board 100 through the conductive bumps 300. Next, the silicone-based resin composition may be coated on the semiconductor package 200. Alternatively, the silicone-based resin composition may be coated on the lower surface of the heat dissipation member 400.

[0210] Next, the heat dissipation member 400 may cover the semiconductor package 200. Thus, the applied silicone-based resin composition may be in direct contact with the lower surface of the heat dissipation member 400 and the upper surface of the semiconductor package 200, and the curable silicone resin composition may be cured at a temperature of about 80° C. or higher while applying a pressure of about 0.01 MPa or more.

[0211] The pressure during the curing process can be about 0.01 MPa or greater. The pressure during the curing process can be about 0.05 MPa to about 100 MPa. The pressure during the curing process can be about 0.1 MPa to about 100 MPa.

[0212] The temperature during the curing process may be about 110° C. to about 300° C. The temperature during the curing process may be about 120° C. to about 300° C. The temperature during the curing process may be about 140° C. to about 300° C. The curing time during the curing process may be about 30 minutes to about 5 hours. The heat conductive layer 500 may be formed by this method.

[0213] Hereinafter, the present invention will be described in more detail based on Examples and Comparative Examples. However, the following Examples and Comparative Examples are merely examples for explaining the present invention in more detail, and the present invention is not limited to the following Examples or Comparative Examples. Example

[0214] - Organopolysiloxane #1: a compound represented by Formula 4 above, having a viscosity of 20,000 cPs at 23° C. and containing silicon-bonded alkenyl groups

[0215] -Organopolysiloxane #2: a compound represented by the above formula 6, having a viscosity of 1,000 cPs at 23° C. and including a structure in which hydrogen groups are bonded to both ends thereof

[0216] -Organopolysiloxane #3: a compound represented by the above formula 8, having a viscosity of 1,000 cPs at 23° C. and including a structure in which a hydrogen group is bonded to a side chain thereof

[0217] - Conductive filler #1: flake silver powder with a density of approximately 5.0 g / cm 3 The tap density is about 0.42m 2 / g specific surface area, an average particle size (D50) of about 6.6 μm, a thickness of about 2 μm, and an Ig loss of 0.28 wt% at about 538°C.

[0218] - Conductive filler #2: flake silver powder with a density of approximately 4.9 g / cm 3 The tap density is about 0.40m 2 / g specific surface area, an average particle size (D50) of about 6.5 μm, a thickness of about 2 μm, a 1 g loss of 0.27 wt% at about 538°C, and a surface treatment with a fatty acid

[0219] - Conductive filler #3: flake silver powder with a density of approximately 5.3 g / cm 3 The tap density is about 0.79m 2 / g specific surface area, an average particle size (D50) of about 2.7 μm, a thickness of about 6 μm, and an Ig loss of 0.43 wt% at about 538°C.

[0220] -Adhesion promoter: 3-glycidoxypropyltrimethoxysilane

[0221] -Curing catalyst: platinum-divinyltetramethyldisiloxane complex

[0222] -Reaction inhibitor: 1-ethynyl-1-cyclohexanol

[0223] Examples 1 to 6 and Comparative Examples 1 and 2

[0224] A silicone-based resin composition was prepared by adding each composition shown in Table 1 below to a planetary mixer and uniformly mixing it at a speed of about 40 rpm at room temperature for 1 hour.

[0225] [Table 1]

[0226]

[0227] Experimental example

[0228] <Sheet production>

[0229] By 165℃ and 26kgf / cm 2The silicone-based resin composition of each of Examples 1 to 6 and Comparative Examples 1 and 2 was molded by hot pressing under a pressure of 100 Å for 15 minutes to produce a sheet.

[0230] Experimental Example 1 - Measurement of Hardness and Thermal Conductivity of the First Cured Product

[0231] Each of the manufactured sheets was cured at 150°C for 5 minutes to produce a first cured product. Next, the first cured product was subjected to Shore A hardness measurement according to ASTM D-2240, and the unit was expressed as Shore A scale. Furthermore, the thermal conductivity of the first cured product was measured at 25°C using a thermal conductivity analyzer (model name: TPS-2500S, manufacturer: Hot Disk AB) according to ISO 22007-2. The results are shown in Table 2 below.

[0232] Experimental Example 2-Measurement of Hardness and Thermal Conductivity of the Second Cured Product

[0233] The first cured product was cured at 150° C. for 120 minutes to produce a second cured product. Next, the hardness and thermal conductivity of the second cured product were measured in the same manner as in Experimental Example 1. The results are shown in Table 2 below.

[0234] Experimental Example 3-Adhesion Evaluation

[0235] The lap shear strength of each of the second cured products of Examples 1 to 6 and Comparative Examples 1 and 2 was measured using a tensile strength analyzer (manufacturer: ZwickRoell Gmbh) in accordance with DIN EN 1465. The results are shown in Table 2 below.

[0236] Experimental Example 4-Plasticity Assessment

[0237] In the process of preparing the sheet-shaped silicone-based resin compositions of Examples 1 to 6 and Comparative Examples 1 to 2, the case where the operation of pouring into the mold could be easily completed was classified as "0", and the case where it was difficult to handle and pour into the mold due to excessively high viscosity was classified as "X". The results are shown in Table 2 below.

[0238] [Table 2]

[0239]

[0240]

[0241] Referring to Tables 1 and 2, it is confirmed that in Examples 1 to 6, the variation in thermal conductivity, the variation in thermal conductivity: variation in hardness, and the thermal conductivity variation ratio are significantly reduced compared to Comparative Examples 1 and 2. Therefore, Examples 1 to 6 exhibit minimal variation in thermal conductivity even when the products exhibit different hardnesses due to process differences, thereby improving the reliability of heat dissipation performance.

[0242] In Comparative Examples 1 and 2, the relative ratio of the change in thermal conductivity to the change in hardness exceeded 40%, significantly increasing the change in thermal conductivity even when the same silicone-based resin composition was used, leading to significant deviations in the product's heat dissipation performance. Furthermore, in Comparative Example 2, even when the conductive filler content was increased to improve thermal conductivity, adhesion reliability decreased, and formability was reduced due to the increased viscosity.

[0243] Description of Reference Numerals

[0244] 10: Silicone-based resin composition

[0245] 11: Sheet

[0246] 11-1: First cured product

[0247] 11-2: Second cured product

[0248] 20: Mold

[0249] 30: Oven

[0250] 100: Circuit board

[0251] 200: Semiconductor packages

[0252] 300: Conductive bump

[0253] 400: Heat dissipation components

[0254] 500: Heat conduction layer

Claims

1. A silicone-based resin composition comprising: organopolysiloxane; and Conductive fillers, wherein a relative ratio of a change in thermal conductivity to a change in Shore A hardness of the silicone-based resin composition measured by the following measurement method is 40% or less: [Measurement method] 1) By 165℃ and 26kgf / cm 2 Molding the silicone-based resin composition by hot pressing under a pressure of 1000 nm for 15 minutes to produce a sheet, 2) curing the sheet at 150° C. for 5 minutes to produce a first cured product, and measuring the Shore A hardness of the first cured product according to ASTM D-2240 and measuring the thermal conductivity at 25° C. according to ISO 22007-2, 3) curing the first cured product at 150° C. for 120 minutes to produce a second cured product, measuring the Shore A hardness of the second cured product according to ASTM D-2240 and measuring the thermal conductivity at 25° C. according to ISO 22007-2, 4) The relative ratio of the change in thermal conductivity to the change in Shore A hardness was calculated according to the following equation 1: [Equation 1] [(│TC H2 –TC H1 │) / (H2-H1)]×100 (wherein H1 represents the Shore A hardness of the first cured product, H2 represents the Shore A hardness of the second cured product, TC H1 Indicates the thermal conductivity in H1 (W / mK), TC H2 represents the thermal conductivity in H2 (W / mK).

2. The silicone-based resin composition according to claim 1, wherein the silicone-based resin composition has a thermal conductivity variation rate of 30% or less calculated according to the following Equation 2: [Equation 2] (│TC H2 –TC H1 │ / TC H2 )×100 (TC H1 and TC H2 as defined in Equation 1 above). 3 . The silicone-based resin composition according to claim 1 , wherein a cured product of the silicone-based resin composition has a Shore A hardness of 95 or less according to ASTM D-2240.

4. The silicone-based resin composition according to claim 1, wherein the silicone-based resin composition satisfies the following Equation 3: [Equation 3] Y=0.0169X+6.5193 (wherein X represents the Shore A hardness of the cured product of the silicone-based resin composition according to ASTM D-2240, Y represents the thermal conductivity of the cured product of the silicone-based resin composition at 25° C. according to ISO 22007-2, and Y is 6 W / mK to 8 W / mK).

5. The silicone-based resin composition according to claim 4, wherein when X is in the range of 3 to 57, the coefficient of determination (R 2 ) is 0.95 or greater. 6 . The silicone-based resin composition according to claim 1 , wherein the conductive filler comprises a conductive powder comprising flaky particles having a thickness of 0.01 μm to 5 μm.

7. The silicone-based resin composition according to claim 6, wherein the conductive powder has a 2 / g to 1.5m 2 / g specific surface area.

8. The silicone-based resin composition according to claim 6, wherein the conductive powder has an average particle size (D 50 ). 9 . The silicone-based resin composition according to claim 6 , wherein the conductive powder has a loss on ignition of 0.4 wt % or less.

10. A semiconductor device comprising: semiconductor packages; a heat dissipation component provided on the semiconductor package; and a heat conducting layer interposed between the semiconductor package and the heat dissipation component, wherein the heat conducting layer comprises a silicone-based resin composition, The silicone-based resin composition comprises an organopolysiloxane and a conductive filler, and A relative ratio of a change in thermal conductivity to a change in Shore A hardness of the silicone-based resin composition measured by the following measurement method is 40% or less: [Measurement method] 1) By 165℃ and 26kgf / cm 2 Molding the silicone-based resin composition by hot pressing under a pressure of 1000 nm for 15 minutes to produce a sheet, 2) curing the sheet at 150° C. for 5 minutes to produce a first cured product, and measuring the Shore A hardness of the first cured product according to ASTM D-2240 and measuring the thermal conductivity at 25° C. according to ISO 22007-2, 3) curing the first cured product at 150° C. for 120 minutes to produce a second cured product, measuring the Shore A hardness of the second cured product according to ASTM D-2240 and measuring the thermal conductivity at 25° C. according to ISO 22007-2, 4) The relative ratio of the change in thermal conductivity to the change in Shore A hardness was calculated according to the following equation 1: [Equation 1] [(│TC H2 –TC H1 │) / (H2-H1)]×100 (wherein H1 represents the Shore A hardness of the first cured product, H2 represents the Shore A hardness of the second cured product, TC H1 Indicates the thermal conductivity in H1 (W / mK), TC H2 represents the thermal conductivity in H2 (W / mK).

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