Silicone resin composition and semiconductor device containing same

Abstract

Disclosed is a silicone-based resin composition containing an organic polysiloxane and a conductive filler, and a semiconductor device containing the silicone-based resin composition, wherein the relative ratio of change in thermal conductivity to change in Shore A hardness of the silicone-based resin composition measured by the following measurement method is 40% or less. [Measurement Method] (See Description of Invention)

Description

[Technical Field]

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

[0002] Most electronic components generate heat during use, and it is necessary to remove that heat for their proper operation. In particular, integrated circuit devices such as CPUs used in personal computers are dissipating more heat due to rising operating frequencies, making heat management an important issue.

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

[0004] However, the hardness of thermally conductive materials varies depending on the process conditions, which causes differences in the thermal conductivity characteristics that appear, resulting in a problem of reduced reliability in product performance. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Korean Patent Publication No. 10-2020-0086307 Summary of the Invention [Problem to be solved by the invention]

[0006] According to aspects of the present invention, the above and other objects can be achieved by providing a silicone-based resin composition having little variation in thermal conductivity and excellent mechanical properties, and a semiconductor device including the silicone-based resin composition. [Means for solving the problem]

[0007] According to an embodiment of the present invention, the above and other objects can be achieved by providing a silicone-based resin composition comprising an organic polysiloxane and a conductive filler, in which the relative ratio of change in thermal conductivity to change in Shore A hardness of the silicone-based resin composition measured by the following measurement method is 40% or less.

[0008] [Measurement method] 1) The silicone resin composition was heated at 165°C and 26 kgf / cm 2 The mixture is hot-pressed for 15 minutes under the condition of a pressure of 0.15 to 0.5 for 15 minutes to prepare a sheet. 2) This sheet is cured at 150°C for 5 minutes to produce a first cured product, which is then subjected to measurement of Shore A hardness in accordance with ASTM D-2240 and thermal conductivity at 25°C in accordance with ISO 22007-2. 3) The first cured product is cured at 150°C for 120 minutes to produce a second cured product. The second cured product is subjected to measurement of Shore A hardness in accordance with ASTM D-2240 and thermal conductivity at 25°C in accordance with ISO 22007-2. 4) The relative ratio of the change in thermal conductivity to the change in Shore A hardness is calculated according to the following formula 1. [Formula 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, and TC H1 indicates the thermal conductivity (W / mK) at H1, and TC H2 indicates the thermal conductivity (W / mK) in H2.

[0009] In an embodiment of the present invention, the silicone-based resin composition may have a thermal conductivity change rate of 30% or less, calculated according to the following Equation 2. [Formula 2] (|TC H2 -TC H1 / TCH2 |)×100 (In the formula, TC H1 and T.C. H2 is as defined in Equation 1 above.)

[0010] In an embodiment of the present invention, the cured product of the silicone resin composition may have a Shore A hardness of 95 or less according to ASTM D-2240.

[0011] In an embodiment of the present invention, the silicone resin composition may satisfy the following mathematical formula 3. [Formula 3] Y=0.0169X+6.5193 (In the formula, X represents the Shore A hardness of the cured product of the silicone resin composition according to ASTM D-2240, and Y represents the thermal conductivity of the cured product of the silicone resin composition at 25°C according to ISO 22007-2, and Y is 6 W / mK to 8 W / mK.)

[0012] In an embodiment of the present invention, X may range from 3 to 57, and the coefficient of determination (R 2 ) is 0.95 or greater.

[0013] In an embodiment of the present invention, the conductive filler may include a conductive powder including flake particles having a thickness of 0.01 μm to 5 μm.

[0014] In an embodiment of the present invention, the conductive powder has a density of 0.1 m 2 / g~1.5m 2 / g specific surface area.

[0015] In an embodiment of the present invention, the conductive powder has an average particle size (D 50 ) can be included.

[0016] In an embodiment of the present invention, the conductive powder may have an ignition loss of 0.4% by weight or less.

[0017] According to another aspect of the present invention, there is provided a semiconductor device comprising: a semiconductor package; a heat dissipation portion disposed on the semiconductor package; and a thermally conductive layer interposed between the semiconductor package and the heat dissipation portion, wherein the thermally conductive layer comprises a silicone-based resin composition, and the silicone-based resin composition comprises an organic polysiloxane and a conductive filler, and wherein the 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.

[0018] [Measurement method] 1) The silicone resin composition was heated at 165°C and 26 kgf / cm 2 The mixture is hot-pressed for 15 minutes under the condition of a pressure of 0.15 to 0.5 for 15 minutes to prepare a sheet. 2) This sheet is cured at 150°C for 5 minutes to produce a first cured product, which is then subjected to measurement of Shore A hardness in accordance with ASTM D-2240 and thermal conductivity at 25°C in accordance with ISO 22007-2. 3) The first cured product is cured at 150°C for 120 minutes to produce a second cured product. The second cured product is subjected to measurement of Shore A hardness in accordance with ASTM D-2240 and thermal conductivity at 25°C in accordance with ISO 22007-2. 4) The relative ratio of the change in thermal conductivity to the change in Shore A hardness is calculated according to the following formula 1. [Formula 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, and TC H1 indicates the thermal conductivity (W / mK) at H1, and TC H2 indicates the thermal conductivity (W / mK) in H2.

[0019] beneficial effects The silicone resin composition of the present invention exhibits a thermal conductivity value that allows it to exhibit an appropriate heat dissipation function even when variations in hardness occur, and the small variation in thermal conductivity allows for improved reliability of product performance.

[0020] In addition, because the silicone resin composition according to the present invention contains relatively thin flake-like conductive particles, it is possible to reduce the void space between the conductive filler particles, thereby mitigating deformation of the conductive filler particle arrangement during the curing process and thereby reducing changes in thermal conductivity caused by changes in hardness.

[0021] Furthermore, the silicone resin composition according to the present invention can exhibit relatively high thermal conductivity with only a small content of conductive filler, thereby improving adhesion reliability and moldability compared to silicone resin compositions with a high content of conductive filler. [Brief explanation of the drawings]

[0022] [Figure 1] FIG. 1 is a diagram sequentially showing the method for measuring the Shore A hardness and thermal conductivity of the silicone resin composition according to the present invention. [Figure 2] FIG. 2 is a diagram illustrating a semiconductor device according to the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0023] The structural or functional descriptions of the embodiments disclosed in this specification or application are merely examples for describing embodiments according to the technical concept of the present invention, and the embodiments according to the technical concept of the present invention may be embodied in various forms other than the embodiments disclosed in this specification or application, and the technical concept of the present invention should not be construed as being limited to the embodiments described in this specification or application.

[0024] In addition, when a certain component is "included" or "comprised" in this specification or application, it may further include other components rather than excluding other components unless otherwise specified. Furthermore, all numerical ranges expressing physical property values, dimensions, etc. of components described in this specification or application should be construed as being modified by the term "about" in all cases unless otherwise specified.

[0025] The silicone resin composition according to the present invention and a semiconductor device containing the silicone resin composition will be described below.

[0026] <Silicone-based resin composition> The silicone resin composition of the present invention comprises an organic polysiloxane and a conductive filler, and the relative ratio of the change in thermal conductivity to the change in Shore A hardness of the silicone resin composition measured by the following measurement method is 40% or less.

[0027] [Measurement method] 1) The silicone resin composition was heated at 165°C and 26 kgf / cm 2 The mixture is hot-pressed for 15 minutes under the condition of a pressure of 0.15 to 0.5 for 15 minutes to prepare a sheet. 2) This sheet is cured at 150°C for 5 minutes to produce a first cured product, which is then subjected to measurement of Shore A hardness in accordance with ASTM D-2240 and thermal conductivity at 25°C in accordance with ISO 22007-2. 3) The first cured product is cured at 150°C for 120 minutes to produce a second cured product. The second cured product is subjected to measurement of Shore A hardness in accordance with ASTM D-2240 and thermal conductivity at 25°C in accordance with ISO 22007-2. 4) The relative ratio of the change in thermal conductivity to the change in Shore A hardness is calculated according to the following formula 1. [Formula 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, and TCH1 indicates the thermal conductivity (W / mK) at H1, and TC H2 indicates the thermal conductivity (W / mK) in H2.

[0028] The silicone resin composition contains an organic polysiloxane.

[0029] The organopolysiloxane can be represented by the following chemical formula 1. [Chemical formula 1] R 1 a SiO b In the formula, R 1 represents one or more groups selected from the group consisting of a hydrogen atom, a hydroxyl group, and a saturated or unsaturated monovalent hydrocarbon group having 1 to 18 carbon atoms; a can be from about 1.8 to about 2.2, and a+b can be from about 3.5 to about 8.

[0030] a+b can be 4.

[0031] In Formula 1, R 1 The saturated or unsaturated monovalent hydrocarbon group having 1 to 18 carbon atoms represented by the formula (I) may be, for example, an alkyl group such as a methyl group, ethyl group, propyl group, hexyl group, octyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group, or octadecyl group; a cycloalkyl group such as a cyclopentyl group or cyclohexyl group; an alkenyl group such as a vinyl group or allyl group; an aryl group such as a phenyl group or tolyl group; an aralkyl group such as a 2-phenylethyl group or 2-methyl-2-phenylethyl group; or a halogenated hydrocarbon group such as a 3,3,3-trifluoropropyl group, a 2-(perfluorobutyl)ethyl group, a 2-(perfluorooctyl)ethyl group, or a p-chlorophenyl group.

[0032] 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 can be measured using polystyrene as a standard.

[0033] The kinematic viscosity of the organic polysiloxane at 25°C is 10 mm 2 / sec~100,000mm 2 / sec, 20,000mm 2 / sec~100,000mm 2 / sec or approximately 30 mm 2 / sec ~ approx. 10,000mm 2 The kinematic viscosity of the organopolysiloxane may be a value measured at 25°C using an Ostwald viscometer.

[0034] When the organic polysiloxane has a weight average molecular weight and kinematic viscosity within the above ranges, it is possible to maintain an appropriate adhesive strength with the adherend, and voids and cracks due to thermal shock are not generated, thereby improving durability.

[0035] The organopolysiloxane can include a first organopolysiloxane.

[0036] The first organopolysiloxane contains alkenyl groups bonded to silicon atoms, and the number of alkenyl groups present in one molecule of the first organopolysiloxane can be at least 2, 2 to 10, 2 to 5, or 2.

[0037] The first organopolysiloxane can be represented by the following Chemical Formula 2: [Chemical formula 2] R 1 a R 2 c SiO b In the formula, R 1is a hydrogen atom, a hydroxyl group, or a saturated or unsaturated monovalent hydrocarbon group having 1 to 18 carbon atoms, and R 2 may be an alkenyl group. In Chemical 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 Chemical Formula 2, a+b+c may be about 4. In Chemical Formula 2, a may be about 1.8 to about 2.2, and c may be 0.0001 to 0.1.

[0038] The first organopolysiloxane can be represented by the following Chemical Formula 3: [Chemical formula 3]

[0039] [ka] In the formula, R 1 is a hydrogen atom, a hydroxyl group, or a saturated or unsaturated monovalent hydrocarbon group having 1 to 18 carbon atoms, and R 2 may be an alkenyl group. In addition, in Chemical Formula 3, n may be 1 to 1,500, and m may be 0 to 20. In Chemical Formula 3, n may be 10 to 1,000, and m may be 0 to 20.

[0040] The first organopolysiloxane can be represented by the following chemical formula 4: [Chemical formula 4]

[0041] [ka] In the formula, n can be 1 to 1,500. n can be 10 to 1,000.

[0042] 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 can be measured using polystyrene as a standard.

[0043] The first organopolysiloxane may have a kinematic viscosity of 10 cPs to 100,000 cPs, 30 cPs to 50,000 cPs, or 10,000 cPs to 40,000 cPs at 23° C. The kinematic viscosity of the first organopolysiloxane may be a value at 25° C. measured with an Ostwald viscometer.

[0044] The organopolysiloxane can include a second organopolysiloxane.

[0045] The second organopolysiloxane may contain hydrogen groups bonded to silicon atoms. The number of hydrogen groups per molecule of the second organopolysiloxane may be 1 to 10, 2 to 10, 2 to 5, or 2.

[0046] The second organopolysiloxane can be represented by the following Chemical Formula 5: [Chemical formula 5]

[0047] [ka] In the formula, R 1 is a hydrogen atom, a hydroxyl group, or a saturated or unsaturated monovalent hydrocarbon group having 1 to 18 carbon atoms, and R 3 may be a hydrogen atom. In Chemical Formula 5, n may be 1 to 1,500, and m may be 0 to 20. In Chemical Formula 5, n may be 10 to 1,000, and m may be 0 to 20. In Chemical Formula 5, n may be 1 to 1,500, and m may be 0.

[0048] The second organopolysiloxane can be represented by the following Chemical Formula 6: [Chemical formula 6]

[0049] [ka]

[0050] At about 23° C., the second organopolysiloxane can 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.

[0051] The organopolysiloxane may further include a third organopolysiloxane, which may be represented by the following formula 7: [Chemical formula 7]

[0052] [ka] In the formula, R 1 is a hydrogen atom, a hydroxyl group, or a saturated or unsaturated monovalent hydrocarbon group having 1 to 18 carbon atoms, and R 3 may be a hydrogen atom. In addition, in Chemical Formula 7, n may be 1 to 1,500, and m may be 1 to 500. In Chemical Formula 7, n may be 10 to 1,000, and m may be 1 to 100.

[0053] The third organopolysiloxane can be represented by the following Chemical Formula 8: [Chemical formula 8]

[0054] [ka] In the formula, n can be 1 to 1,500, and m can be 1 to 500. In Chemical Formula 8, n can be 10 to 1,000, and m can be 1 to 100.

[0055] At about 23° C., the third organopolysiloxane can 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.

[0056] The ratio of the viscosity of the first organopolysiloxane to the viscosity of the second organopolysiloxane can be from 10:1 to 40:1.

[0057] The ratio of the viscosity of the second organopolysiloxane to the viscosity of the third organopolysiloxane may be 2:1 to 10:1.

[0058] The content of the first organopolysiloxane may be 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.

[0059] The content of the second organopolysiloxane can be 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.

[0060] The content of the third organic polysiloxane can be about 3 to about 20 parts by weight, about 3 to about 15 parts by weight, or about 4 to about 10 parts by weight per 100 parts by weight of the first organic polysiloxane.

[0061] When the silicone-based resin composition contains the first organic polysiloxane, and the second organic polysiloxane and the third organic polysiloxane are within the above ranges, the silicone-based resin composition can maintain appropriate adhesion to the adherend and spread uniformly during application.

[0062] The silicone resin composition contains a conductive filler.

[0063] The conductive filler may include a conductive powder including flaked particles. The conductive powder may include flaked silver particles.

[0064] The conductive filler may comprise a conductive powder containing flake 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. By including flake particles within this thickness range, the void space between the conductive filler particles is reduced, mitigating deformation of the conductive filler arrangement during the curing process, thereby reducing changes in thermal conductivity caused by changes in hardness.

[0065] The conductive powder is 0.1 g / cm 3 ~10.0g / cm 3 , 1.0g / cm 3 ~8.0g / cm 3 , 2.0g / cm 3 ~8.0g / cm 3 , 3.0g / cm 3 ~8.0g / cm 3 , 4.0g / cm 3 ~8.0g / cm 3 or 4.0 g / cm 3 ~7.0g / cm 3 The tap density may be

[0066] The tap density is calculated from the volume of the silver powder obtained by weighing 100 g of silver powder, gently dropping it into a 100 ml measuring cylinder using a funnel, placing the cylinder on a tap density meter, and dropping it 600 times at a rate of 60 times / min over a drop distance of 20 mm to compress it.

[0067] The conductive powder has 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 ).

[0068] Average particle size (D 50 ) is defined as the particle size corresponding to 50% of the cumulative volume in the particle size distribution curve of silver powder obtained using the laser diffraction method.

[0069] The conductive powder is 0.1m 2 / g~3.0m 2 / g, 0.1m 2 / g~2.0m 2 / g, 0.1m 2 / g~1.8m 2 / g, 0.1m 2 / g~1.5m 2 / g, 0.1m 2 / g~1.0m 2 / g, 0.1m 2 / g~0.9m 2 / g, 0.1m2 / g~0.8m 2 / g, or 0.1m 2 / g~0.7m 2 / g specific surface area.

[0070] The specific surface area is calculated by using approximately 2 g of silver powder as a sample, degassing it at 60±5°C for 10 minutes, measuring the total surface area using an automatic specific surface area measuring device (BET method), weighing the sample, and calculating using the following formula. Specific surface area (m 2 / g) = total surface area (m 2 ) / sample amount (g)

[0071] The flake particles contained in the conductive powder may have an aspect ratio of about 2-30, about 2-25, about 2-20, or about 2-18.

[0072] The conductive powder may be surface-treated with a surface treatment agent. The surface treatment agent may contain a C10 to C fatty acid. Examples of the fatty acid include capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, myristoleic acid, palmitoleic acid, sapienic acid, oleic acid, elaidic acid, vaccenic acid, linoleic acid, lionelidic acid, arachidonic acid, eicosapentaenoic acid, and α-linolenic acid.

[0073] 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 from about 0.01 wt% to less than about 0.4 wt%. Ig loss can be measured at about 538°C for about 1 hour.

[0074] The conductive powder can be effectively surface-treated with a small amount of surface treatment agent. That is, the conductive powder has a relatively low tap density and a large specific surface area, so it can be surface-treated 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 organic polysiloxane. That is, because the conductive powder has improved dispersibility, it can be added to the organic polysiloxane at a high content. Furthermore, because the conductive powder has a flaky surface area and the coating layer formed by the surface treatment agent is thin, the contact characteristics between the conductive filler particles can be improved. As a result, the conductive powder can improve the thermal conductivity of the silicone-based resin composition.

[0075] The silicone resin composition may contain the first silver powder in an amount of about 300 parts by weight to about 1,000 parts by weight, about 400 parts by weight to about 900 parts by weight, or about 500 parts by weight to about 800 parts by weight based on 100 parts by weight of the organic polysiloxane.

[0076] The conductive powder may further include dendritic silver particles or spherical silver particles.

[0077] The conductive filler includes flaky silver particles and dendritic or spherical silver particles having a different shape from the flaky silver particles, which can improve the formation of an electrical network between the particles, and as a result, can improve thermal conductivity.

[0078] The silicone resin composition may contain the organic polysiloxane 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 satisfied, appropriate adhesion to the adherend can be maintained, and durability can be improved because voids and cracks due to thermal shock do not occur.

[0079] In the silicone resin composition according to the present invention, the relative ratio of the change in thermal conductivity to the change in Shore A hardness measured by the following measurement method is 40% or less.

[0080] [Measurement method] 1) The silicone resin composition was heated at 165°C and 26 kgf / cm 2 The mixture is hot-pressed for 15 minutes under the condition of a pressure of 0.15 to 0.5 for 15 minutes to prepare a sheet. 2) This sheet is cured at 150°C for 5 minutes to produce a first cured product, which is then subjected to measurement of Shore A hardness in accordance with ASTM D-2240 and thermal conductivity at 25°C in accordance with ISO 22007-2. 3) The first cured product is cured at 150°C for 120 minutes to produce a second cured product. The second cured product is subjected to measurement of Shore A hardness in accordance with ASTM D-2240 and thermal conductivity at 25°C in accordance with ISO 22007-2. 4) The relative ratio of the change in thermal conductivity to the change in Shore A hardness is calculated according to the following formula 1. [Formula 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, and TC H1 indicates the thermal conductivity (W / mK) at H1, and TC H2 indicates the thermal conductivity (W / mK) in H2.

[0081] FIG. 1 is a diagram sequentially showing the method for measuring the Shore A hardness and thermal conductivity of the silicone resin composition according to the present invention.

[0082] Referring to FIG. 1(a), a silicone resin composition 10 is supplied to a mold 20 and heated at 165°C and 26 kgf / cm 2 The sheet 11 is produced by hot pressing for 15 minutes under the condition of a pressure of 1000 kJ / cm.

[0083] Next, (b) the sheet 11 is cured at 150° C. for 5 minutes to produce a first cured product 11-1.

[0084] Next, (c) the first cured product 11-1 is subjected to measurement of Shore A hardness in accordance with ASTM D-2240 and measurement of thermal conductivity at a temperature of 25°C in accordance with ISO 22007-2.

[0085] Next, (d) the first cured product 11-1 is cured at 150° C. for 120 minutes to produce a second cured product 11-2.

[0086] Next, (e) the second cured product 11-2 is subjected to measurement of Shore A hardness in accordance with ASTM D-2240 and measurement of thermal conductivity at a temperature of 25°C in accordance with ISO 22007-2.

[0087] The sheet 11 and the first cured product 11-1 are fed into a dry oven 30 and cured therein.

[0088] Next, the measured values ​​of hardness and thermal conductivity of the first cured product 11-1 and the measured values ​​of hardness and thermal conductivity 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.

[0089] In the silicone resin composition, the relative ratio of the change in thermal conductivity to the change in Shore A hardness measured by the above 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.

[0090] The silicone resin composition may have a rate of change in thermal conductivity of 30% or less, as calculated by the following equation 2. [Formula 2] (|TC H2 -TC H1 / TC H2 |)×100 (In the formula, TC H1 and T.C. H2 is as defined in Equation 1 above.)

[0091] The silicone resin composition may have a rate of change in thermal conductivity 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.

[0092] Generally, in the case of silicone-based resin compositions, variations in hardness of products produced from the silicone-based resin composition can occur depending on the curing temperature, curing time, or composition of the silicone-based resin composition. Furthermore, variations in hardness of the product can cause variations in thermal conductivity, which can be problematic when the composition is used in products that require heat dissipation.

[0093] 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 above measurement method is 40% or less, the change in thermal conductivity is significantly reduced compared to the change in hardness, and the composition exhibits a thermal conductivity value that can perform an appropriate heat dissipation function.Even if there is variation in the hardness of products made from the silicone-based resin composition, the variation in thermal conductivity is small, thereby improving reliability when used in products that require a heat dissipation function.

[0094] Furthermore, the silicone-based resin composition according to the present invention can exhibit relatively high thermal conductivity with only a small content of conductive filler, and therefore can improve adhesion reliability and moldability compared to silicone-based resin compositions with a high content of conductive filler.

[0095] The Shore A hardness according to ASTM D-2240 of the cured product of the silicone resin composition may be 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 the above range, the occurrence of wear or cracking during product manufacturing can be minimized.

[0096] The silicone resin composition can satisfy the following formula 3. [Formula 3] Y=0.0169X+6.5193 (In the formula, X represents the Shore A hardness of the cured product of the silicone resin composition according to ASTM D-2240, and Y represents the thermal conductivity of the cured product of the silicone resin composition at 25°C according to ISO 22007-2, and Y is 6 W / mK to 8 W / mK.)

[0097] Coefficient of determination of X (R 2 ) can be 0.95 or more in the range of 3 to 57.

[0098] Equation 3 is a linear trend line with Shore A hardness as the X variable and thermal conductivity as the Y dependent variable depending on the X variable. The linear trend line may be derived using the Microsoft Excel program and the coefficient of determination (R 2 ) may be obtained from this linear trend line. The coefficient of determination is a statistical term that is a measure of the goodness of fit of a regression equation, known as the linear trend line, for a dependent variable Y and data Y. i Y for i It represents the ratio of the sum of the fluctuations to the sum of the fluctuations of the variables. The coefficient of determination is generally expressed as R 2 The closer the coefficient of determination is to 1, the higher the goodness of fit of the regression equation.

[0099] 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 ) corresponds to 0.95 or more. Therefore, even if the hardness fluctuates greatly, the thermal conductivity fluctuates relatively little, which indicates a high degree of fit of the regression equation. Therefore, a silicone-based resin composition that satisfies Equation 3 exhibits small fluctuations in thermal conductivity even when the hardness fluctuates, thereby ensuring reliable product performance.

[0100] The silicone resin composition may further contain a tackifier.

[0101] The tackifier may include an alkoxysilane. The tackifier may also 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.

[0102] The silicone resin composition may contain 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 organic polysiloxane. The tackifier can improve the adhesive strength between the organic polysiloxane and the conductive filler.

[0103] The silicone-based resin composition may further include a curing catalyst, which can accelerate the curing of the silicone-based resin composition.

[0104] The curing catalyst may include a platinum-based catalyst.

[0105] Examples of the curing catalyst include organic titanate esters such as platinum-divinyltetramethyldisiloxane complex, tetrabutyl titanate, tetraisopropyl titanate, organic titanium chelate compounds such as diisopropoxybis(acetylacetate)titanium and diisopropoxybis(ethylacetoacetate)titanium, organic aluminum compounds such as aluminum tris(acetylacetonate) and aluminum tris(ethylacetoacetate), organic zirconium compounds such as zirconium tetra(acetylacetonate) and zirconium tetrabutylate, and organic tin compounds such as di Examples of the additives include butyltin dioctate, dibutyltin dilaurate, and butyltin-2-ethylhexoate, 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, alkali metal salts of lower fatty acids such as potassium acetate, dialkylhydroxylamines such as dimethylhydroxylamine and diethylhydroxylamine, and guanidyl group-containing organosilicon compounds.

[0106] The silicone resin composition may contain a 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 organic polysiloxane.

[0107] The silicone resin composition may further contain a reaction inhibitor, which may be at least one selected from the group consisting of curing reaction inhibitors such as acetylene compounds such as 2-methyl-3-butyn-2-ol, 2-phenyl-3-butyn-2-ol, and 1-ethynyl-1-cyclohexanol, ene-yne ​​compounds such as 3-methyl-3-penten-1-yne and 3,5-dimethyl-3-hexen-1-yne, hydrazine compounds, phosphine compounds, and mercaptan compounds.

[0108] The silicone resin composition may contain a reaction inhibitor in an amount of about 0.0001 to about 10 parts by weight based on 100 parts by weight of the organic polysiloxane.

[0109] <Method for preparing silicone-based resin composition> The method for producing the silicone resin composition is not particularly limited, and may be any known method.

[0110] For example, the silicone-based resin composition can be prepared by mixing an organic polysiloxane, a conductive filler, a tackifier, a curing catalyst, a curing reaction inhibitor, etc. for 30 minutes to 4 hours using a mixer such as Trimix, Twinmix, Planetary Mixer (all manufactured by Inoue Seisakusho, registered trademarks), Ultramixer (manufactured by Mizuho Industries, registered trademark), or Hibis Disper Mix (manufactured by Primix, registered trademark). In the mixing step, the process temperature can be about 0°C to about 25°C.

[0111] <Semiconductor device> FIG. 2 is a diagram illustrating a semiconductor device according to the present invention.

[0112] Referring to FIG. 2, the semiconductor device may include a circuit board 100, a semiconductor package 200, a conductive bump 300, a heat sink 400, and a thermally conductive layer 500.

[0113] The semiconductor device according to the present invention comprises a semiconductor package 200, a heat dissipation section 400 disposed on the semiconductor package 200, and a thermally conductive layer 500 interposed between the semiconductor package 200 and the heat dissipation section 400, wherein the thermally conductive layer 500 comprises a silicone-based resin composition, and the silicone-based resin composition comprises an organic polysiloxane and a conductive filler, and 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.

[0114] [Measurement method] 1) The silicone resin composition was heated at 165°C and 26 kgf / cm 2The mixture is hot-pressed for 15 minutes under the condition of a pressure of 0.15 to 0.5 for 15 minutes to prepare a sheet. 2) This sheet is cured at 150°C for 5 minutes to produce a first cured product, which is then subjected to measurement of Shore A hardness in accordance with ASTM D-2240 and thermal conductivity at 25°C in accordance with ISO 22007-2. 3) The first cured product is cured at 150°C for 120 minutes to produce a second cured product. The second cured product is subjected to measurement of Shore A hardness in accordance with ASTM D-2240 and thermal conductivity at 25°C in accordance with ISO 22007-2. 4) The relative ratio of the change in thermal conductivity to the change in Shore A hardness is calculated according to the following formula 1. [Formula 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, and TC H1 indicates the thermal conductivity (W / mK) at H1, and TC H2 indicates the thermal conductivity (W / mK) in H2.

[0115] The specific method for measuring the hardness and thermal conductivity of the silicone resin composition is the same as the method shown in FIG.

[0116] Since the relative ratio of change in thermal conductivity to change in Shore A hardness of the silicone-based resin composition is 40% or less, the thermal conductive layer 500 containing such a silicone-based resin composition has small variation in thermal conductivity, thereby ensuring reliable product performance. In addition, the thermal conductive layer 500 can maintain appropriate adhesive strength with the semiconductor package 200 and the heat dissipation unit 400.

[0117] The circuit board 100 can support the semiconductor package 200 , the conductive bumps 300 , the heat dissipation portion 400 and the thermally conductive layer 500 .

[0118] The circuit board 100 may include a circuit pattern. The circuit board 100 may include a plurality of circuit patterns disposed inside a flat body made of an insulating and heat-resistant material and having a predetermined strength. The circuit board 100 may also include connection pads disposed on the body and electrically connected to the circuit patterns.

[0119] For example, the main body of the circuit board 100 may include a thermosetting resin substrate such as an epoxy resin substrate or a polyimide substrate, a flat plate, or a flat plate to which a heat-resistant organic film such as a liquid crystal polyester film or a polyamide film is attached. The circuit pattern is arranged in a pattern inside the main body and may include power wiring for power supply, ground wiring, and signal wiring for signal transmission. The wiring may be separated from each other by a plurality of interlayer insulating films formed on the upper and lower surfaces of the main body.

[0120] The connection pads are exposed from the top surface of the main body and can be connected to the circuit pattern, so that an external connector connected to the circuit board 100 can be electrically connected to the internal circuit pattern via the connection pads.

[0121] Various electronic components can be mounted on connection pads included in the circuit board 100. In other words, the circuit board 100 is a system board on which electronic components including the semiconductor package 200 are mounted.

[0122] The semiconductor package 200 is mounted on the circuit board 100. The semiconductor package 200 may be disposed on the circuit board 100. The semiconductor package 200 may be connected to the circuit board 100 via conductive bumps 300.

[0123] The semiconductor package 200 may include a semiconductor chip including an integrated circuit, a semiconductor package substrate connected to the semiconductor chip, conductive solder connecting the semiconductor chip and the semiconductor package substrate, and a sealing part sealing the semiconductor chip and the conductive solder. The sealing part may include a resin composition such as an epoxy molding.

[0124] The semiconductor package 200 may be a memory device, a central processing unit, or the like.

[0125] The conductive bumps 300 can be disposed between the semiconductor package 200 and the circuit board 100. The conductive bumps 300 electrically connect the semiconductor package 200 and the circuit board 100. The conductive bumps 300 are electrically connected to the semiconductor package 200 and the connection pads.

[0126] The heat dissipation part 400 may be disposed on the semiconductor package 200. The heat dissipation part 400 may cover the semiconductor package 200. The heat dissipation part 400 may be coupled to the circuit board 100. The heat dissipation part 400 may cover the side surface of the semiconductor package 200.

[0127] The heat dissipation unit 400 may include a conductor, a metal, or may be thermally connected to an external heat dissipation fin.

[0128] In addition, the heat dissipation unit 400 can protect the semiconductor package 200 from external physical impacts and external electromagnetic waves. That is, the heat dissipation unit 400 can block external electromagnetic waves.

[0129] The thermally conductive layer 500 may be disposed between the semiconductor package 200 and the heat dissipation unit 400. The thermally conductive layer 500 may be in direct contact with the semiconductor package 200 and the heat dissipation unit 400. The thermally conductive layer 500 may be in close contact with the semiconductor package 200 and the heat dissipation unit 400.

[0130] The thermally conductive layer 500 may be thermally connected to the semiconductor package 200 and the heat dissipation unit 400. That is, the thermally conductive layer 500 may transfer heat generated in the semiconductor package 200 to the heat dissipation unit 400.

[0131] The thickness of the thermally conductive layer 500 can be from about 1 μm to about 100 μm, from about 2 μm to about 70 μm, from about 5 μm to about 60 μm, or from about 10 μm to about 40 μm.

[0132] <Method of manufacturing a semiconductor device> The method for manufacturing the semiconductor device is not particularly limited and may be any known manufacturing method.

[0133] First, the semiconductor package 200 is mounted on the circuit board 100 by the conductive bumps 300. Next, the semiconductor package 200 can be coated with a silicone-based resin composition. Alternatively, the lower surface of the heat dissipation part 400 may be coated with the silicone-based resin composition.

[0134] Next, the heat dissipation unit 400 can cover the semiconductor package 200. Therefore, the coated silicone resin composition can be in direct contact with the lower surface of the heat dissipation unit 400 and the upper surface of the semiconductor package 200, and the curable silicone resin composition can be cured at about 80°C or higher under an applied pressure of about 0.01 MPa or higher.

[0135] The pressure in the curing process may be about 0.01 MPa or more. The pressure in the curing process may be about 0.05 MPa to about 100 MPa. The pressure in the curing process may be about 0.1 MPa to about 100 MPa.

[0136] The temperature in the curing process may be about 110°C to about 300°C. The temperature in the curing process may be about 120°C to about 300°C. The temperature in the curing process may be about 140°C to about 300°C. The curing time in the curing process may be about 30 minutes to about 5 hours. The thermally conductive layer 500 can be formed by this process.

[0137] The present invention will be described in more detail below with reference to examples and comparative examples, but 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 and comparative examples. [Example]

[0138] - Organopolysiloxane #1: a compound represented by the above chemical formula 4, having a viscosity of 20,000 cPs at 23°C and containing silicon-bonded alkenyl groups - Organic polysiloxane #2: A compound represented by the above chemical formula 6, having a viscosity of 1,000 cPs at 23°C and a structure in which hydrogen groups are bonded to both ends of the compound. - Organic polysiloxane #3: A compound represented by the above chemical formula 8, having a viscosity of 1000 cPs at 23°C and a structure in which a hydrogen group is bonded to its side chain. - Conductive filler #1: approx. 5.0 g / cm 3 Tap density of approximately 0.42m 2 / g specific surface area, average particle size of about 6.6 μm (D 50 ) Flake silver powder with a thickness of about 2 μm and an Ig-loss of 0.28 wt% at about 538°C - Conductive filler #2: approx. 4.9g / cm 3 Tap density of approximately 0.40m 2 / g specific surface area, average particle size (D 50 ), a flake silver powder with a thickness of approximately 2 μm, an Ig-loss of 0.27 wt% at approximately 538°C, and a surface treatment with fatty acid. - Conductive filler #3: approx. 5.3g / cm 3 Tap density of approximately 0.79m 2 / g specific surface area, average particle size (D 50 ), flake silver powder with a thickness of about 6 μm and an Ig-loss of 0.43 wt% at about 538°C - Tackifier: 3-glycidoxypropyltrimethoxysilane - Curing catalyst: Platinum-divinyltetramethyldisiloxane complex - Reaction inhibitor: 1-ethynyl-1-cyclohexanol

[0139] [Examples 1 to 6 and Comparative Examples 1 and 2] Each of the components shown in Table 1 below was added to a planetary mixer and mixed uniformly at room temperature at a speed of about 40 rpm for 1 hour to prepare a silicone resin composition.

[0140] [Table 1]

[0141] Experimental Example <Seat manufacturing> The silicone resin compositions of Examples 1 to 6 and Comparative Examples 1 and 2 were subjected to a test at 165°C and 26 kgf / cm 2 The mixture was hot-pressed for 15 minutes under a pressure of 0.15 to 0.25 for 15 minutes to prepare a sheet.

[0142] Experimental Example 1 - Measurement of hardness and thermal conductivity of the first cured product Each of the prepared sheets was cured at 150°C for 5 minutes to prepare a first cured product. The Shore A hardness of the first cured product was then measured in accordance with ASTM D-2240, and the units were expressed on the Shore A scale. The thermal conductivity of the first cured product was measured at 25°C in accordance with ISO 22007-2 using a thermal conductivity measuring device (model: TPS-2500S, manufacturer: Hot Disk AB). The results are shown in Table 2 below.

[0143] Experimental Example 2 - Measurement of hardness and thermal conductivity of the second cured product 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.

[0144] Experimental Example 3 - Adhesion evaluation 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 measuring device (manufacturer: ZwickRoell GmbH) in accordance with DIN EN 1465. The results are shown in Table 2 below.

[0145] Experimental Example 4 - Formability evaluation In the process for preparing the silicone resin compositions of Examples 1 to 6 and Comparative Examples 1 and 2 into sheets, cases where the composition could be easily poured into a mold were classified as "O," and cases where the viscosity was too high and handling was difficult, making pouring into a mold difficult, were classified as "X." The results are shown in Table 2 below.

[0146] [Table 2]

[0147] Referring to Tables 1 and 2, it was confirmed that the amount of change in thermal conductivity, the amount of change in thermal conductivity relative to the amount of change in hardness, and the rate of change in thermal conductivity were significantly reduced in Examples 1 to 6 compared to Comparative Examples 1 and 2. Therefore, in Examples 1 to 6, even if the products exhibit different hardness due to differences in processes, the variation in the thermal conductivity of the products is small, and as a result, the reliability of the heat dissipation performance can be improved.

[0148] In Comparative Examples 1 and 2, the relative ratio of the change in thermal conductivity to the change in hardness exceeded 40%, so even though the same silicone-based resin composition was used, the change in thermal conductivity increased relatively significantly, resulting in a large deviation in the heat dissipation performance of the product. Also, in Comparative Example 2, it was confirmed that even if the content of the conductive filler was increased to improve thermal conductivity, the adhesive reliability decreased, and the increased viscosity reduced moldability. [Explanation of symbols]

[0149] 10: Silicone resin composition 11: Sheet 11-1: First hardened material 11-2: Second hardened material 20: Type 30: Dry oven 100: Circuit board 200: Semiconductor packaging 300: Conductive bump 400: Heat radiation part 500: Thermally conductive layer

Claims

1. A silicone-based resin composition, Organic polysiloxane and Contains a conductive filler, A silicone-based resin composition in which the relative ratio of change in thermal conductivity to change in Shore A hardness of the silicone-based resin composition measured by the following measurement method is 40% or less. [Measurement method] 1) The silicone resin composition was heated at 165°C and 26 kgf / cm ２ The mixture is hot-pressed for 15 minutes under a pressure of 0.15 to 0.5 for 15 minutes to prepare a sheet. 2) This sheet is cured at 150°C for 5 minutes to produce a first cured product, which is then subjected to measurement of Shore A hardness in accordance with ASTM D-2240 and thermal conductivity at 25°C in accordance with ISO 22007-2. 3) The first cured product is cured at 150°C for 120 minutes to produce a second cured product. The second cured product is subjected to measurement of Shore A hardness in accordance with ASTM D-2240 and thermal conductivity at 25°C in accordance with ISO 22007-2. 4) The relative ratio of the change in thermal conductivity to the change in Shore A hardness is calculated according to the following formula 1. [Formula 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, and TC Ｈ１ indicates the thermal conductivity (W / mK) at H1, and TC Ｈ２ indicates the thermal conductivity (W / mK) in H2.

2. 2. The silicone resin composition according to claim 1, wherein the silicone resin composition has a rate of change in thermal conductivity calculated by the following equation 2 of 30% or less. [Formula 2] ((|TC Ｈ２ -TC Ｈ１ | TTC Ｈ２ )×100 (In the formula, TC Ｈ１ and T.C. Ｈ２ is as defined in Equation 1 above.)

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

5. When X is in the range of 3 to 57, the coefficient of determination (R ２ 5. The silicone resin composition according to claim 4, wherein the σ is 0.95 or more.

6. 2. The silicone-based resin composition according to claim 1, wherein the conductive filler comprises a conductive powder containing flake-shaped particles having a thickness of 0.01 μm to 5 μm.

7. The conductive powder is 0.1 m ２ / g to 1.5m ２ The silicone resin composition according to claim 6, having a specific surface area of ​​1 / g.

8. The conductive powder has an average particle size (D ５０ 7. The silicone resin composition according to claim 6, wherein

9. 7. The silicone resin composition according to claim 6, wherein the conductive powder has an ignition loss of 0.4% by weight or less.

10. A semiconductor device, A semiconductor package; a heat dissipation portion disposed on the semiconductor package; a thermally conductive layer interposed between the semiconductor package and the heat dissipation portion; Including, the thermally conductive layer contains a silicone-based resin composition, the silicone resin composition contains an organic polysiloxane and a conductive filler; A semiconductor device in which the relative ratio of change in thermal conductivity to change in Shore A hardness of the silicone resin composition measured by the following measurement method is 40% or less. [Measurement method] 1) The silicone resin composition was heated at 165°C and 26 kgf / cm ２ The mixture is hot-pressed for 15 minutes under a pressure of 0.15 to 0.5 for 15 minutes to prepare a sheet. 2) This sheet is cured at 150°C for 5 minutes to produce a first cured product, which is then subjected to measurement of Shore A hardness in accordance with ASTM D-2240 and thermal conductivity at 25°C in accordance with ISO 22007-2. 3) The first cured product is cured at 150°C for 120 minutes to produce a second cured product. The second cured product is subjected to measurement of Shore A hardness in accordance with ASTM D-2240 and thermal conductivity at 25°C in accordance with ISO 22007-2. 4) The relative ratio of the change in thermal conductivity to the change in Shore A hardness is calculated according to the following formula 1. [Formula 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, and TC Ｈ１ indicates the thermal conductivity (W / mK) at H1, and TC Ｈ２ indicates the thermal conductivity (W / mK) in H2.

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