Silicone based resin composition, and semiconductor device comprising the same

Abstract

The present invention provides a silicone resin composition comprising an organic polysiloxane; a first thermally conductive filler; and a curing catalyst, wherein the first thermally conductive filler comprises secondary particles agglomerated therefrom, wherein the first thermally conductive filler satisfies Equation 1 (see specification for details); and a semiconductor device comprising the silicone resin composition.

Description

[Technical Field]

[0001] This invention relates to a silicone-based resin composition and a semiconductor device comprising the same. [Previous Technology]

[0002] Since most electronic components generate heat during their use, it is necessary to remove heat from them for them to function properly. In particular, the heat generated by integrated circuit elements such as CPUs used in personal computers is increasing due to their faster operating frequencies, and heat countermeasures have become an important issue.

[0003] Therefore, many methods for heat dissipation have been proposed, and for electronic components that emit a large amount of heat, a method has been proposed to dissipate heat by inserting a thermally conductive material, such as thermal grease or thermal pad, between the electronic component and a component such as a heat sink.

[0004] Korean Patent Application Publication No. 10-2020-0086307 discloses a semiconductor device including a thermally conductive material.

[0005] [Related Technical Documents] [Patent Documents] (Patent Document 1) Korean Patent Application Publication No. 10-2020-0086307 [Summary of the Invention]

[0006] [Technical Issues]

[0007] Therefore, the present invention was made in view of the above problems. One object of the present invention is to provide a silicone resin composition that minimizes thermal conductivity deviation and provides excellent heat dissipation properties due to improved coverage; and a semiconductor device comprising the silicone resin composition.

[0008] [Technical Solution]

[0009] According to one aspect of the present invention, the above-mentioned and other objectives can be achieved by providing a silicone resin composition comprising: an organic polysiloxane; a first thermally conductive filler; and a curing catalyst, wherein the first thermally conductive filler comprises secondary particles in which the primary particles are agglomerated, and wherein the first thermally conductive filler satisfies the following Equation 1: [Equation 1] 0.3 < A (m2 / g (square meters / gram)) / B (micrometers) < 3.0 where A represents the specific surface area of ​​the first thermally conductive filler and is a unit-free value, and B represents the average particle size (D50) of the first thermally conductive filler and is a unit-free value.

[0010] In one embodiment of the present invention, the primary particles may be flaky particles.

[0011] In one embodiment of the present invention, the aspect ratio of the first thermally conductive filler can be 0.5 to 3.

[0012] In one embodiment of the present invention, the tapped density of the first thermally conductive filler can be from 0.5 g / cm3 to 6 g / cm3.

[0013] In one embodiment of the present invention, the silicone resin composition may further comprise a spherical second thermally conductive filler that is different from the first thermally conductive filler.

[0014] In one embodiment of the present invention, the aspect ratio of the spherical second thermally conductive filler can be 1 to 1.5.

[0015] In one embodiment of the present invention, the weight ratio of the first thermally conductive filler to the spherical second thermally conductive filler can be 1:1 to 1:5.

[0016] In one embodiment of the present invention, the lap shear strength of the silicone resin composition, as measured by DIN EN 1465, can be 1 N / mm2 (Newtons per square millimeter) or greater.

[0017] In one embodiment of the present invention, the coverage of the silicone resin composition measured by the following measurement method 1 can be 90% or greater: [Measurement Method 1] 1) The silicone resin composition is coated on a first silicone substrate with a size of 27 mm × 27 mm at a weight of 0.7 g; 2) A second silicone substrate with a size equal to or larger than the first silicone substrate is placed on the coated silicone resin composition, and then the silicone resin composition is cured under a pressure of 3 kgf; 3) The area of ​​the first silicone substrate in close contact with the second silicone substrate by the cured silicone resin composition is obtained; and 4) The coverage is the ratio of the area of ​​the first silicone substrate in close contact with the second silicone substrate to the planar area of ​​the first silicone substrate.

[0018] In one embodiment of the present invention, the thermal conductivity change rate of the silicone resin composition, measured by the following measurement method 2, can be less than 30%: [Measurement Method 2] 1) A first sheet is manufactured by hot-pressing the silicone resin composition at 165°C and a pressure of 10 kgf / cm² for 15 minutes, and a second sheet is manufactured separately by hot-pressing the silicone resin composition at 165°C and a pressure of 0.1 kgf / cm² for 15 minutes; 2) The first sheet and the second sheet are cured at 150°C for 2 hours to manufacture a first sheet sample and a second sheet sample, respectively; 3) The thermal conductivity of the first sheet sample and the thermal conductivity of the second sheet sample are measured at 25°C according to ISO 22007-2; 4) The thermal conductivity change rate is calculated according to the following equation 2: [Equation 2] The rate of change of thermal conductivity (%) = (|TC10-TC0.1| / TC10)×100 where TC10 is the thermal conductivity of the first sheet sample (W / mK (watts per meter kelvin)) and TC0.1 is the thermal conductivity of the second sheet sample (W / mK).

[0019] According to another aspect of the present invention, a semiconductor device is provided, comprising: a semiconductor package; a heat dissipation part disposed on the semiconductor package; and a thermally conductive layer inserted between the semiconductor package and the heat dissipation part, wherein the thermally conductive layer comprises a silicone resin composition, wherein the silicone resin composition comprises an organic polysiloxane, a first thermally conductive filler and a curing catalyst, wherein the first thermally conductive filler comprises secondary particles agglomerated therein, and the first thermally conductive filler satisfies the following Equation 1: [Equation 1] 0.3 < A (m2 / g) / B (micrometer) < 3.0 where A represents the specific surface area of ​​the first thermally conductive filler and is a unit-free value, and B represents the average particle size (D50) of the first thermally conductive filler and is a unit-free value.

[0020] [Beneficial Effects]

[0021] The silicone resin composition according to the present invention comprises granular secondary particles in which the primary particles are agglomerated as a first thermally conductive filler, and the ratio of the specific surface area to the average particle size of the first thermally conductive filler is greater than 0.3 and less than 3.0.

[0022] Therefore, since the first thermally conductive filler has a large average particle size and a large specific surface area, the first thermally conductive filler contained in the silicone resin composition can exhibit excellent thermal conductivity.

[0023] In addition, even when manufactured under different pressure conditions for commercial use, the silicone resin composition exhibits a thermal conductivity value that allows for proper heat dissipation, and the reliability of product performance can be improved due to the small deviation in thermal conductivity of the silicone resin composition.

[0024] The cured product of the silicone resin composition according to the present invention can achieve high thermal conductivity, while having improved coverage and appropriate spread thickness.

[0025] Therefore, when the silicone resin composition is used in a semiconductor device, the silicone resin composition can be coated to a uniform thickness between the semiconductor package and the heat dissipation component, thereby improving the heat dissipation function.

Implementation Method

[0027] The structural or functional descriptions of the embodiments disclosed in this specification or application are merely for the purpose of explaining the embodiments of the technical concept of the present invention. The embodiments of the technical concept of the present invention may be implemented in various forms different from those disclosed in this specification or application, and should not be construed as the technical concept of the present invention being limited to the embodiments described in this specification or application.

[0028] In this specification or application, unless otherwise disclosed, when a component "includes" a component, it means that the component may include another component rather than exclude another component. In addition, it should be understood that, unless otherwise stated, in all cases, all numerical ranges of physical property values, dimensions, etc. of the components described in this specification or application are modified by the term "about".

[0029] In this specification or application, it should be understood that when each component, surface, layer, or substrate is referred to as being "above" or "below" another component, surface, layer, or substrate, that component, surface, layer, or substrate may be directly on or inserted into the other component, surface, layer, or substrate, and the criteria for "above" and "below" will be provided based on the accompanying drawings. For convenience and clarity, elements in the following drawings may be exaggerated, omitted, or shown schematically, and the dimensions of the elements do not perfectly reflect their actual dimensions.

[0030] The silicone resin composition and semiconductor device comprising the present invention will now be described.

[0031] The silicone resin composition according to the present invention comprises an organic polysiloxane.

[0032] This organopolysiloxane can be represented by the following formula 1: [Formula 1] R1 aSiOb

[0033] In Formula 1, R1 may represent one or two or more groups selected from the group consisting of hydrogen atoms, hydroxyl groups and saturated or unsaturated monovalent hydrocarbon groups having 1 to 18 carbon atoms, and a may be about 1.8 to about 2.2. a+b may be about 3.5 to about 8.

[0034] a+b can be 4.

[0035] In Formula 1, the saturated or unsaturated monovalent hydrocarbon group having 1 to 18 carbon atoms represented by R1 can be, for example: alkyl, such as methyl, ethyl, propyl, hexyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl or octadecyl; cycloalkyl, such as cyclopentyl or cyclohexyl; alkenyl, such as vinyl or allyl; aryl, such as phenyl or tolyl; aralkyl, such as 2-phenylethyl or 2-methyl-2-phenylethyl; or halogenated hydrocarbon group, such as 3,3,3-trifluoropropyl group, 2-(perfluorobutyl)ethyl group, 2-(perfluorooctyl)ethyl group or p-chlorophenyl group.

[0036] The weight average molecular weight of the organopolysiloxane can be from about 40,000 g / mol to about 80,000 g / mol, from about 30,000 g / mol to about 100,000 g / mol, from about 500 g / mol to about 10,000 g / mol, from about 700 g / mol to about 7,000 g / mol, from about 1,000 g / mol to about 5,000 g / mol, or from about 1,500 g / mol to about 3,000 g / mol. The weight average molecular weight can be measured based on polystyrene.

[0037] The kinematic viscosity of organopolysiloxanes at 25°C can range from 10 mm² / s to 100,000 mm² / s, 20,000 mm² / s to 100,000 mm² / s, or about 30 mm² / s to about 10,000 mm² / s. The kinematic viscosity of organopolysiloxanes can be measured at 25°C using an Ostwald viscometer.

[0038] Because organopolysiloxanes have a weight-average molecular weight and kinematic viscosity within this range, they can maintain appropriate adhesion to an adherend and improve durability by preventing voids and cracks from thermal shock.

[0039] Organic polysiloxanes may include a first organopolysiloxane.

[0040] The first organopolysiloxane system includes an alkenyl group bonded to a silicon atom. At least two, two to ten, two to five, or two alkenyl groups may be present in a molecule of the first organopolysiloxane.

[0041] The first organopolysiloxane can be represented by the following formula 2: [Formula 2] R1 aR2 cSiOb

[0042] In Formula 2, R1 can be a hydrogen atom, a hydroxyl group, or a saturated or unsaturated monovalent hydrocarbon group having 1 to 18 carbon atoms, and R2 can be an alkenyl group. In Formula 2, a+c can be about 1.8 to about 2.2, and a+b+c can be about 3.5 to about 8. In Formula 2, a+b+c can be about 4. In Formula 2, a can be about 1.8 to about 2.2. Additionally, c can be 0.0001 to 0.1.

[0043] The first organopolysiloxane can be represented by the following formula 3: [Formula 3]

[0044] In Formula 3, R1 can be a hydrogen atom, a hydroxyl group, or a saturated or unsaturated monovalent hydrocarbon group having 1 to 18 carbon atoms, and R2 can be an alkenyl group. Additionally, in Formula 3, n can be 1 to 1,500, and m can be 0 to 20. In Formula 3, n can be 10 to 1,000, and m can be 0 to 20.

[0045] The first organopolysiloxane can be represented by the following formula 4: [Formula 4]

[0046] In Equation 4, n can be from 1 to 1,500. n can be from 10 to 1,000.

[0047] The weight average molecular weight (Mw) of the first organopolysiloxane may be from about 500 g / mol to about 10,000 g / mol, from about 700 g / mol to about 7,000 g / mol, from about 1,000 g / mol to about 5,000 g / mol, or from about 1,500 g / mol to about 3,000 g / mol. The weight average molecular weight may be measured based on polystyrene.

[0048] The kinematic viscosity of the first organopolysiloxane at 23°C can be from 10 cPs (centipoise seconds) to 100,000 cPs, from 30 cPs to 50,000 cPs, or from 10,000 cPs to 40,000 cPs. The kinematic viscosity of the first organopolysiloxane can be measured at 23°C using an Ostwald viscometer.

[0049] Organopolysiloxanes may include second organopolysiloxanes.

[0050] 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 to 10, 2 to 10, 2 to 5, or 2.

[0051] The second organopolysiloxane can be represented by the following formula 5: [Formula 5]

[0052] In Formula 5, R1 can be a hydrogen atom, a hydroxyl group, or a saturated or unsaturated monovalent hydrocarbon group having 1 to 18 carbon atoms, and R3 can be a hydrogen atom. Additionally, in Formula 5, n can be 1 to 1,500, and m can be 0 to 20. In Formula 5, n can be 10 to 1,000, and m can be 0 to 20. In Formula 5, n can be 1 to 1,500, and m can be 0.

[0053] The second organopolysiloxane can be represented by the following formula 6: [Formula 6]

[0054] The viscosity of the second organopolysiloxane at about 23°C may be 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.

[0055] The organopolysiloxane may further include a third organopolysiloxane. The third organopolysiloxane may be represented by the following formula 7: [Formula 7]

[0056] In Formula 7, R1 can be a hydrogen atom, a hydroxyl group, or a saturated or unsaturated monovalent hydrocarbon group having 1 to 18 carbon atoms, and R3 can be a hydrogen atom. Additionally, in Formula 7, n can be 1 to 1,500, and m can be 1 to 500. In Formula 7, n can be 10 to 1,000, and m can be 1 to 100.

[0057] The third organopolysiloxane can be represented by the following formula 8: [Formula 8]

[0058] In Equation 8, n can be from 1 to 1,500, and m can be from 1 to 500. In Equation 8, n can be from 10 to 1,000, and m can be from 1 to 100.

[0059] The viscosity of the third organopolysiloxane at about 23°C can be about 50 cPs to about 1,000 cPs, about 100 cPs to about 500 cPs, or about 100 cPs to about 500 cPs.

[0060] The ratio of the viscosity of the first organopolysiloxane to the viscosity of the second organopolysiloxane can be from 10:1 to 40:1.

[0061] In addition, the ratio of the viscosity of the second organopolysiloxane to the viscosity of the third organopolysiloxane can be from 2:1 to 10:1.

[0062] Based on 100 parts by weight of total organic polysiloxane, the content of the first organic polysiloxane 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.

[0063] Based on 100 parts by weight of the first organopolysiloxane, the content of the second organopolysiloxane may 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.

[0064] Based on 100 parts by weight of the first organopolysiloxane, the content of the third organopolysiloxane may be from about 3 parts by weight to about 20 parts by weight, from about 3 parts by weight to about 15 parts by weight, or from about 4 parts by weight to about 10 parts by weight.

[0065] When a silicone resin composition contains a first organopolysiloxane, a second organopolysiloxane and a third organopolysiloxane within the range, it can maintain appropriate adhesion to an adhesive and spread evenly during the coating process.

[0066] The silicone resin composition comprises a first thermally conductive filler.

[0067] Conventionally, thermally conductive fillers in the form of spherical primary particles are used to improve the heat dissipation properties of silicone-based resin compositions. However, due to the small surface area of ​​the thermally conductive filler, the contact characteristics between the powders are reduced, thus limiting the achievement of excellent heat dissipation properties.

[0068] To further improve heat dissipation properties, the thermally conductive filler is mixed with a flake-type or dendrite-type thermally conductive filler with a larger specific surface area. However, when the silicone resin composition contains flake-type and / or dendrite-type thermally conductive fillers, the dispersibility with the organic polysiloxane decreases, resulting in a significant reduction in coverage. Therefore, when the silicone resin composition is used as a thermally conductive layer in a semiconductor device, there is a problem of reduced contact area with the semiconductor package and heat dissipation components, and deterioration of heat dissipation properties.

[0069] Therefore, the inventors have confirmed that when the first thermally conductive filler includes granular secondary particles in which the primary particles are agglomerated and the first thermally conductive filler satisfies the following Equation 1, it exhibits excellent thermal conductivity. Since the deviation in thermal conductivity depending on different pressurization conditions is small, the reliability of the product performance is improved, and it exhibits improved coverage, strong adhesion strength, and appropriate joint separation length, thereby exhibiting excellent heat dissipation properties: [Equation 1] 0.3 < A (m² / g) / B (micrometers) < 3.0

[0070] In Equation 1, A represents the specific surface area of ​​the first thermally conductive filler and is a unit-free value, and B represents the average particle size (D50) of the first thermally conductive filler and is a unit-free value.

[0071] Generally, as the average particle size of thermally conductive fillers increases, the dispersibility can be improved, but the thermal conductivity may decrease due to the significant reduction in specific surface area.

[0072] However, the first thermally conductive filler according to the invention comprises granular secondary particles in which the primary particles are agglomerated. Here, as long as the ratio of the specific surface area to the average particle size of the first thermally conductive filler satisfies Equation 1, it can have a larger specific surface area compared to other thermally conductive fillers having the same average particle size.

[0073] Therefore, the silicone resin composition containing the first thermally conductive filler according to the present invention can not only achieve the excellent covering properties of conventional spherical thermally conductive fillers, but also achieve the excellent covering properties of conventional sheet-type and dendritic thermally conductive fillers.

[0074] In Equation 1, A can be from 0.8 m2 / g to 2.0 m2 / g, from 0.8 m2 / g to 1.8 m2 / g, from 0.8 m2 / g to 1.6 m2 / g, or from 0.8 m2 / g to 1.5 m2 / g.

[0075] In Equation 1, B can be 0.5 micrometers to 10 micrometers, 0.5 micrometers to 5 micrometers, 0.5 micrometers to 4 micrometers, or 1 micrometer to 4 micrometers.

[0076] The average particle size is defined as the particle size corresponding to 50% of the cumulative volume in the particle size distribution curve, which is obtained from the thermally conductive powder using the laser diffraction method.

[0077] In Equation 1, A (m² / g) / B (micrometers) can be greater than 0.3 and less than 3.0, greater than 0.3 and 2.5 or less, greater than 0.3 and 2.0 or less, or 0.4 or greater and 2.0 or less. When this range is satisfied, excellent coverage characteristics, improved coverage, and appropriate spread thickness can be provided.

[0078] The primary particles can be flake-shaped particles. When the primary particles are flake-shaped particles, the mechanical strength of the secondary particles agglomerated from the primary particles can be improved, thereby reducing the thermal conductivity deviation and further improving the reliability of product performance.

[0079] The first thermally conductive filler may be an aggregate of secondary particles in which the flake-shaped silver particles are clustered. The secondary particles may have a spherical shape.

[0080] Secondary particles can be formed by spray drying primary particles to be agglomerated and then firing them.

[0081] The average particle size (D50) of the primary particles can be 0.1 micrometer to 1 micrometer, 0.1 micrometer to 0.9 micrometer, 0.1 micrometer to 0.8 micrometer, or 0.1 micrometer to 0.5 micrometer.

[0082] The aspect ratio of the first thermally conductive filler can be 0.5 to 3, 0.6 to 3, 0.6 to 2.8, 0.6 to 2.7, or 0.5 to 2.5.

[0083] The aspect ratio is defined as the length of the major axis of the first thermally conductive filler particle divided by the length of the minor axis of the first thermally conductive filler particle.

[0084] The tap density of the first thermally conductive filler may be 0.5 g / cm3 to 6 g / cm3, 1 g / cm3 to 6 g / cm3, 1.5 g / cm3 to 6 g / cm3, or 2.5 g / cm3 to 6 g / cm3.

[0085] To obtain the tap density, approximately 100 grams of the first thermally conductive powder was weighed and gently dropped into a 100 ml graduated cylinder using a funnel. Next, the graduated cylinder was placed on a tap density meter, and the powder was pressed by dropping it 600 times at a speed of 60 times / minute and a drop distance of 20 mm. The tap density was calculated from the volume of the pressed thermally conductive powder.

[0086] Since the first thermally conductive filler includes granular secondary particles in which the primary particles are agglomerated, the hardness of the first thermally conductive filler can significantly affect its mechanical properties. The Mohs hardness of the first thermally conductive filler can be 2 to 5, 2 to 4.5, 2 to 4, 2 to 3, or 2.5 to 3. The Mohs hardness can be measured using a Mohs hardness tester. When this range is met, the phenomenon of drastic deformation of the shape of the first thermally conductive filler or breakage due to the appearance of multiple cracks during the pressurization process after the silicone resin composition has been cured can be minimized.

[0087] The first thermally conductive filler 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, palmitic acid, sapienic acid, oleic acid, eliadic acid, vaccenic acid, linoleic acid, linolelaidic acid, arachidonic acid, eicosapentaenoic acid, α-linolenic acid, etc.

[0088] The ignition loss (Ig-loss) of the first thermally conductive filler may be 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 greater and less than about 0.4 wt%. The ignition loss may be measured at about 538°C for about 1 hour.

[0089] The surface of the first thermally conductive filler can be effectively treated even with only a small amount of surface treatment agent. That is, the first thermally conductive filler has a relatively low tap density and a large specific surface area, and can be surface treated with a small amount of surface treatment agent. Therefore, the first thermally conductive filler can be uniformly dispersed in the organopolysiloxane and the thermal connection of the thermally conductive filler can be improved. That is, due to the improved dispersibility of the first thermally conductive filler, it can be added to the organopolysiloxane in a high content.

[0090] Based on 100 parts by weight of an organopolysiloxane, a silicone resin composition may contain a first thermally conductive filler 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. When this range is satisfied, proper adhesion to an adhesive can be maintained, and durability can be improved because voids and cracks due to thermal shock do not occur.

[0091] The silicone resin composition may further include a spherical second thermally conductive filler with a shape different from that of the first thermally conductive filler. This second thermally conductive filler may be formed from spherical primary particles. Since the silicone resin composition includes a first thermally conductive filler comprising granular secondary particles and a second thermally conductive filler comprising spherical primary particles, the mechanical strength of the thermally conductive filler, which improves thermal conductivity, can be further improved, thereby reducing thermal conductivity deviation and enhancing the reliability of product performance.

[0092] The aspect ratio of the second thermally conductive filler can be 1 to 1.5, 1 to 1.45, 1 to 1.4, 1 to 1.35, or 1 to 1.3.

[0093] When the aspect ratio is close to 1, the shape of the second thermally conductive filler particles can be interpreted as almost spherical.

[0094] The aspect ratio is defined as the length of the major axis of the second thermally conductive filler particle divided by the length of the minor axis of the second thermally conductive filler particle.

[0095] The roundness of the second thermally conductive filler can be 0.95 to 1, 0.96 to 1, 0.97 to 1, or 0.98 to 1.

[0096] When the roundness is close to 1, the shape of the second thermally conductive filler particles can be interpreted as almost spherical.

[0097] Roundness can be calculated using the following formula: [Formula] Roundness = (4 × Area) / (π × Major Axis Length 2)

[0098] The specific surface area of ​​the second thermally conductive filler may be 0.1 m2 / g to 1.0 m2 / g, 0.1 m2 / g to 0.9 m2 / g, 0.1 m2 / g to 0.8 m2 / g, or 0.1 m2 / g to 0.5 m2 / g.

[0099] Regarding the weight ratio, the ratio of the first thermally conductive filler to the second thermally conductive filler can be 1:1 to 1:5, 1:1 to 1:4.5, 1:1 to 1:4, or 1:1 to 1:3. When this range is satisfied, the cured product made from the silicone-based resin composition can have improved coverage and appropriate spread thickness, while achieving high thermal conductivity.

[0100] Figure 1 is a cross-sectional view showing a method for measuring the lap shear strength and joint separation length of a silicone resin composition.

[0101] Referring to Figure 1, a silicone resin composition 30 with a thickness of approximately 200 micrometers is coated onto a region of the first nickel plate 20, and then a second nickel plate 10 is applied over the coated silicone resin composition 30. Next, the silicone resin composition 30 is cured at approximately 150°C for approximately 2 hours. The coating area of ​​the silicone resin composition 30 can be approximately 2.5 cm × 1.25 cm. Then, the first nickel plate 20 and the second nickel plate 10 are pulled horizontally in opposite directions using a universal testing machine. Here, the stress in the horizontal direction is measured on the first nickel plate 20 and the second nickel plate 10 based on the length of the deformation in the horizontal direction.

[0102] The lap shear strength can be the value obtained by dividing the maximum value of the stress applied to the first nickel plate 20 and the second nickel plate 10 by the coating area of ​​the silicone resin composition 30.

[0103] The separation length at the joint can be the length that changes in the horizontal direction at the maximum value of the stress applied to the first nickel plate 20 and the second nickel plate 10.

[0104] The lap shear strength of the silicone resin composition, as measured by DIN EN 1465, can be 1 N / mm2 or greater, 1.2 N / mm2 or greater, 1.3 N / mm2 or greater, 1.4 N / mm2 or greater, or 1.5 N / mm2 to 2.5 N / mm2.

[0105] The joint separation length measured by DIN EN 1465 can be 0.3 mm or more, 0.4 mm or more, 0.5 mm or more, or 0.5 mm to 1.0 mm.

[0106] When this range is satisfied, the bonding stability and heat dissipation properties of the thermal conductive layer can be improved.

[0107] The shear modulus expressed by the following equation can be 1 N / mm3 (Newtons per cubic millimeter) or greater and less than 3 N / mm3: [Equation] Shear modulus (N / mm3) = LSS (N / mm2) / JSL (mm) Where LSS represents the lap shear strength of the silicone resin composition as measured by DIN EN 1465, and JSL represents the joint separation length of the silicone resin composition as measured by DIN EN 1465.

[0108] The shear modulus may be 1 N / mm3 or greater and less than 3 N / mm3, 1.1 N / mm3 or greater and less than 3 N / mm3, 1.3 N / mm3 or greater and 2.5 N / mm3 or less, or 1.6 N / mm3 or greater and 2.5 N / mm3 or less.

[0109] When this range is satisfied, deformation and peeling caused by shear stress can be suppressed, and deformation caused by external thermal shock can be easily recovered.

[0110] The coverage of the silicone resin composition, measured by the following measurement method 1, can be 90% or greater, 92% or greater, 94% or greater, 96% or greater, or 99% or greater. [Measurement Method 1] 1) A silicone resin composition is coated on a first silicone substrate with dimensions of 27 mm × 27 mm at a weight of 0.7 g. 2) A second silicone substrate with dimensions equal to or greater than the first silicone substrate is placed on the coated silicone resin composition, and then the silicone resin composition is cured under a pressure of 3 kgf. 3) The area of ​​the first silicone substrate in close contact with the second silicone substrate by the cured silicone resin composition is obtained. 4) The coverage is the ratio of the area of ​​the first silicone substrate in close contact with the second silicone substrate to the planar area of ​​the first silicone substrate.

[0111] In addition, the thickness of the cured resin composition layer can be the spreading thickness.

[0112] Because the silicone resin composition has the above-mentioned coverage and spreading thickness, the thermally conductive layer can be in close contact with the semiconductor package and heat dissipation component over a large area, and can have high thermal conductivity when the silicone resin composition is used as the thermally conductive layer of the semiconductor device.

[0113] The viscosity of the silicone resin composition may be from 50,000 cPs to 200,000 cPs, from 50,000 cPs to 180,000 cPs, from 70,000 cPs to 180,000 cPs, or from 70,000 cPs to 150,000 cPs.

[0114] The viscosity of the silicone resin composition can be measured at approximately 25°C using a rheometer MCR302 (manufacturer: Anton Paar GmbH) equipped with a plate of approximately 25 mm in diameter, according to the DIN EN ISO 3219 method. Here, a shear rate of approximately 10 (1 / s) can be applied to measure the viscosity.

[0115] When this range is satisfied, appropriate coverage and paving thickness can be obtained.

[0116] The pot life of the silicone resin composition can be 10 to 16 hours, 10 to 15 hours, 10 to 14 hours, or 10 to 13 hours.

[0117] The applicable period can be measured by the following methods.

[0118] Allow the silicone resin composition to stand at room temperature. Then, measure the time taken for the viscosity of the silicone resin composition to increase by 50% compared to its initial viscosity as the pot life.

[0119] The change rate of thermal conductivity of the silicone resin composition measured by the following measurement method 2 can be less than 30%: [Measurement Method 2] 1) A silicone resin composition is molded to produce a first sheet by hot pressing at 165°C and a pressure of 10 kgf / cm2 for 15 minutes, and separately, a silicone resin composition is molded to produce a second sheet by hot pressing at 165°C and a pressure of 0.1 kgf / cm2 for 15 minutes. 2) The first sheet and the second sheet are cured at 150°C for 2 hours to produce a first sheet sample and a second sheet sample, respectively. 3) The thermal conductivity of the first sheet sample and the thermal conductivity of the second sheet sample are measured at 25°C according to ISO 22007-2. 4) Calculate the rate of change of thermal conductivity according to the following Equation 2: [Equation 2] Rate of change of thermal conductivity (%) = (|TC10-TC0.1| / TC10) × 100

[0120] In Equation 2, TC10 is the thermal conductivity (W / mK) of the first sheet sample and TC0.1 is the thermal conductivity (W / mK) of the second sheet sample.

[0121] The change rate of thermal conductivity of the silicone resin composition measured by measurement method 2 can be less than 30%, 25% or less, 20% or less, 15% or less, or 10% or less.

[0122] Because silicone-based resin compositions have a change in thermal conductivity, even when commercially used under different pressure conditions, the small deviation in the change in thermal conductivity ensures the reliability of product performance. Furthermore, even when thermal shock is applied to products manufactured using silicone-based resin compositions, they maintain appropriate adhesion to an adhesive and prevent the formation of voids and cracks caused by thermal shock.

[0123] 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 3, can be 40% or less: [Measurement Method 3] 1) Molding the silicone resin composition to produce a sheet by hot pressing at 165°C and a pressure of 26 kgf / cm² for 15 minutes. 2) Curing the sheet at 150°C for 5 minutes to produce a first cured product. The Shore A hardness of the first cured product is measured according to ASTM D-2240, and the thermal conductivity of the first cured product is measured 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. The Shore A hardness of the second cured product is measured according to ASTM D-2240, and the thermal conductivity of the second cured product is measured at 25°C according to ISO 22007-2. 4) Calculate the relative ratio of the change in thermal conductivity to the change in Shore A hardness according to the following equation: [Equation] [(│TCH2-TCH1│) / (H2-H1)]×100 where H1 represents the Shore A hardness of the first cured product, H2 represents the Shore A hardness of the second cured product, TCH1 represents the thermal conductivity (W / mK) in terms of H1, and TCH2 represents the thermal conductivity (W / mK) in terms of H2.

[0124] In the silicone resin composition, the relative ratio of the change in thermal conductivity to the change in Shore A hardness, as measured by measurement method 3, can be 35% or less, 30% or less, 25% or less, 20% or less, 10% or less, 5% or less, or 1% or less.

[0125] The hardness of products manufactured from silicone resin compositions can vary depending on the curing temperature, curing time, or composition of the silicone resin composition.

[0126] Since the ratio of the change in thermal conductivity of the silicone resin composition to the change in Shore A hardness is 40% or less as measured by measurement method 3, the change in thermal conductivity is significantly reduced compared to the change in hardness. This results in a thermal conductivity value that can perform appropriate heat dissipation function. Furthermore, when a product that requires heat dissipation function is applied, the reliability can be improved even if the hardness of the product manufactured from the silicone resin composition changes due to the small change in thermal conductivity.

[0127] The cured product of the silicone resin composition may have a Shore A hardness 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 according to ASTM D-2240. When the hardness is within this range, the occurrence of wear or cracking during product manufacturing can be minimized.

[0128] The silicone resin composition can satisfy the following equation: [Equation] Y=0.0169X+6.5193 where X represents the Shore A hardness of the cured product of the silicone resin composition according to ASTM D-2240, 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.

[0129] The coefficient of determination (R²) of X in the range of 3 to 57 can be 0.95 or greater.

[0130] The equation represents a linear trend line with Shore A hardness as the variable X and thermal conductivity as the dependent variable Y, where thermal conductivity is the dependent variable based on X. The linear trend line can be obtained using Microsoft Excel, and the coefficient of determination (R²) can be derived from it. The coefficient of determination, as a statistical term, is a well-known measure of the goodness of fit of a regression equation, representing the ratio of the sum of fluctuations of data Yi relative to the dependent variable Y to the total sum of fluctuations. The coefficient of determination is usually represented by R², and the goodness of fit of the regression equation increases as the coefficient of determination approaches 1.

[0131] For example, in the equation, Y ranges from 6.6 to 7.4 for X in the range of 3 to 57, which means that the thermal conductivity ranges from 6.6 W / mK to 7.4 W / mK for Shore A hardness of 3 to 57. Here, the coefficient of determination (R²) represents 0.95 or greater. Therefore, even with large variations in hardness, the variation in thermal conductivity is not relatively large, which indicates a high degree of fit of the regression equation. Thus, silicone resin compositions that satisfy the equation can meet the reliability requirements of product performance because the variation in thermal conductivity remains small even with variations in hardness.

[0132] The silicone-based resin composition contains a curing catalyst.

[0133] The curing catalyst can accelerate the curing of silicone resin compositions.

[0134] Examples of curing catalysts include: organic titanate esters, such as platinum-divinyltetramethyldisiloxane complex, tetrabutyl titanate, and tetraisopropyl titanate; organic titanium chelate compounds, such as diisopropoxybis(acetylacetate)titanium and diisopropoxybis(ethylacetoacetate)titanium; organoaluminum compounds, such as aluminum tris(acetylacetonate) and aluminum tris(ethylacetoacetate); and organozonium compounds, such as zirconium tetra(acetylacetonate). Zirconium tetrabutylate and tetrabutyrate; organotin compounds, such as dibutyltin dioctoate, 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 their salts; quaternary ammonium salts, such as benzyltriethylammonium acetate; lower fatty acid salts of alkali metals, such as potassium acetate; dialkyl hydroxylamines, such as dimethyl hydroxylamine and diethyl hydroxylamine; and guanidin-containing organosilicon compounds. group-containing organosilicon compound).

[0135] Based on 100 parts by weight of an organopolysiloxane, the silicone resin composition may contain a curing catalyst in an amount of about 0.01 parts by weight to about 5 parts by weight, about 0.03 parts by weight to about 3 parts by weight, or about 0.1 parts by weight to about 2 parts by weight.

[0136] Silicone-based resin compositions may further contain tackifiers.

[0137] The tackifier may include alkoxysilanes. Additionally, the tackifier may include epoxy groups. The tackifier may be selected from at least one of the following groups: 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyl methyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyl methyldimethoxysilane, and 3-glycidoxypropyltriethoxysilane.

[0138] Based on 100 parts by weight of an organopolysiloxane, the silicone resin composition may include a tackifier in amounts of about 1 part by weight to about 20 parts by weight, about 1 part by weight to about 10 parts by weight, or about 2 parts by weight to about 8 parts by weight. The tackifier can improve the adhesion strength between the organopolysiloxane and the thermally conductive filler.

[0139] The silicone resin composition may further include a reaction inhibitor. The reaction inhibitor may be selected from at least one of the following groups: acetylenic 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; curing reaction inhibitors, such as hydrazine-based compounds, phosphine-based compounds and merecaptan-based compounds, etc.

[0140] Based on 100 parts by weight of an organopolysiloxane, a silicone resin composition may contain a reaction inhibitor in an amount of about 0.0001 parts by weight to about 10 parts by weight.

[0141] The method for preparing the silicone resin composition can be any known preparation method and is not particularly limited.

[0142] For example, silicone-based resin compositions can be prepared by mixing organic polysiloxanes, thermally conductive fillers, curing catalysts, tackifiers, reaction inhibitors, etc., for 30 minutes to 4 hours using mixers such as: Trimix (three-arm planetary mixer), Twinmix (two-axis mixer), and planetary mixer (all manufactured by Inoue Seisakusho Co., Ltd., registered trademarks); Ultramixer (a cyclone mixer manufactured by Mizuho Kogyo Co., Ltd., registered trademark); or Hibis Disper Mix (a three-axis planetary dispersion, mixing, and compounding machine manufactured by Primix Co., Ltd., registered trademark). During the mixing process, the process temperature can be from about 0°C to about 25°C.

[0143] FIG2 is a cross-sectional view showing a semiconductor device according to an embodiment of the present invention.

[0144] Referring to FIG2, the semiconductor device according to the present invention includes a semiconductor package 200, a heat dissipation component 400 disposed on the semiconductor package 200, and a thermally conductive layer 500 inserted between the semiconductor package 200 and the heat dissipation component 400.

[0145] A semiconductor device may include a circuit board 100 and thermally conductive bumps 300.

[0146] The circuit board 100 can support the semiconductor package 200, the thermal bump 300, the heat dissipation component 400 and the thermal layer 500.

[0147] The circuit board 100 may include circuit patterns. The circuit board 100 may include multiple circuit patterns disposed within a flat body comprising an insulating and heat-resistant material 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.

[0148] The main body of the circuit board 100 may include a thermosetting resin substrate (e.g., an epoxy resin substrate or a polyimide substrate), a flat plate, or a flat plate with a heat-resistant organic film (e.g., a liquid crystal polyester film or a polyimide film) attached. The circuit pattern may be arranged in a patterned 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 configured to be separated from each other by multiple interlayer insulating films formed on the upper and lower surfaces of the main body.

[0149] The bonding pads can be exposed to the outside from the upper surface of the body and can be connected to the circuit pattern. Therefore, the external connectors connected to the circuit board 100 can be electrically connected to the internal circuit pattern via the bonding pads.

[0150] Various electronic components can be mounted on the connection pads included in the circuit board 100. The circuit board 100 can be a system board on which electronic components, including semiconductor packages 200, are mounted.

[0151] The semiconductor package 200 can be mounted on the circuit board 100. The semiconductor package 200 can be disposed on the circuit board 100. The semiconductor package 200 can be connected to the circuit board 100 by means of thermally conductive bumps 300.

[0152] The semiconductor package 200 may include: a semiconductor wafer including integrated circuitry, a semiconductor package substrate connected to the semiconductor wafer, thermally conductive solder for connecting the semiconductor wafer and the semiconductor package substrate, and a sealing component for sealing the semiconductor wafer and the thermally conductive solder. The sealing component may include a resin composition, such as an epoxy resin molding compound.

[0153] The semiconductor package 200 may be a storage device, a central processing unit, etc.

[0154] A thermally conductive bump 300 may be disposed between the semiconductor package 200 and the circuit board 100. The thermally conductive bump 300 can electrically connect the semiconductor package 200 and the circuit board 100 to each other. The thermally conductive bump 300 can be electrically connected to the semiconductor package 200 and the bonding pads.

[0155] The heat dissipation component 400 may be disposed on the semiconductor package 200. The heat dissipation component 400 may cover the semiconductor package 200. The heat dissipation component 400 may be coupled to the circuit board 100. The heat dissipation component 400 may cover the side surface of the semiconductor package 200.

[0156] The heat dissipation component 400 may include a conductor. The heat dissipation component 400 may include metal. The heat dissipation component 400 may be thermally connected to an external heat dissipation fin.

[0157] The heat dissipation component 400 can protect the semiconductor package 200 from external physical impacts. The heat dissipation component 400 can protect the semiconductor package 200 from the influence of external electromagnetic waves. That is, the heat dissipation component 400 can block external electromagnetic waves.

[0158] The thermally conductive layer 500 may be disposed between the semiconductor package 200 and the heat dissipation component 400. The thermally conductive layer 500 may directly contact the semiconductor package 200 and the heat dissipation component 400. The thermally conductive layer 500 may be in close contact between the semiconductor package 200 and the heat dissipation component 400.

[0159] The thermally conductive layer 500 can be thermally connected to the semiconductor package 200 and the heat dissipation component 400. That is, the thermally conductive layer 500 can transfer the heat generated by the semiconductor package 200 to the heat dissipation component 400.

[0160] The thickness of the thermally conductive layer 500 can be from about 1 micrometer to about 100 micrometers, from about 2 micrometers to about 70 micrometers, from about 5 micrometers to about 60 micrometers, or from about 10 micrometers to about 40 micrometers.

[0161] The thermally conductive layer 500 comprises a silicone-based resin composition. This silicone-based resin composition comprises an organic polysiloxane, a first thermally conductive filler, and a curing catalyst. The first thermally conductive filler comprises secondary particles agglomerated from the primary particles. The first thermally conductive filler satisfies the following Equation 1: [Equation 1] 0.3 < A (m² / g) / B (micrometers) < 3.0

[0162] In Equation 1, A represents the specific surface area of ​​the first thermally conductive filler and is a unit-free value, and B represents the average particle size (D50) of the first thermally conductive filler and is a unit-free value.

[0163] The silicone resin composition can be the same as the silicone resin composition described above. Since the first thermally conductive filler of the silicone composition includes secondary particles in which the primary particles are agglomerated, and the ratio of the specific surface area to the average particle size of the first thermally conductive filler, as expressed by Equation 1, satisfies a value greater than 0.3 and less than 3.0, the thermal conductivity of the thermally conductive layer 500 containing the silicone composition can be improved. In addition, the thermally conductive layer 500 can maintain appropriate adhesion to the semiconductor package 200 and the heat dissipation component 400, thus improving the heat dissipation function.

[0164] The method of manufacturing a semiconductor device can be a known manufacturing method, and there are no particular restrictions.

[0165] First, the semiconductor package 200 can be mounted on the circuit board 100 by means of the thermally conductive bumps 300. Next, a silicone resin composition can be coated onto the semiconductor package 200. Alternatively, the silicone resin composition can be coated onto the lower surface of the heat dissipation component 400.

[0166] Next, the heat dissipation component 400 may cover the semiconductor package 200. Therefore, the coated silicone resin composition can be in direct contact with the lower surface of the heat dissipation component 400 and the upper surface of the semiconductor package 200, and the curable silicone resin composition can be cured at a temperature of about 80°C or higher under a pressure of about 0.01 MPa or greater.

[0167] 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.

[0168] The temperature during the curing process can be from about 110°C to about 300°C. The temperature during the curing process can be from about 120°C to about 300°C. The temperature during the curing process can be from about 140°C to about 300°C. The curing time during the curing process can be from about 30 minutes to about 20 hours. The thermally conductive layer 500 can be formed by this process.

[0169] The present invention will be described in more detail below based on embodiments and comparative examples. However, the following embodiments and comparative examples are merely examples for explaining the present invention in more detail, and the present invention is not limited to the following embodiments and comparative examples.

[0170] Example - Organopolysiloxane #1: A compound represented by Formula 4, having a viscosity of 20,000 cPs at 23°C and comprising silicon-bonded alkenyl groups: [Formula 4] - Organopolysiloxane #2: A compound represented by Formula 6, having a viscosity of 1,000 cPs at 23°C and comprising a structure in which hydrogen groups are bonded to both ends: [Formula 6] - Organopolysiloxane #3: A compound represented by Formula 8, having a viscosity of 1,000 cPs at 23°C and comprising a structure in which hydrogen groups are bonded to its side chains: [Formula 8] - Thermally conductive filler #1: Granular silver powder in which primary particles agglomerate with an average particle size (D50) of about 0.3 micrometers. The granular silver powder has an average particle size (D50) of approximately 2.5 micrometers, an aspect ratio of approximately 2, a specific surface area of ​​approximately 2.5 m² / g, and a tap density of approximately 3 g / cm³. - Thermally conductive filler #2: Granular silver powder with an average particle size (D50) of approximately 1 micrometer, consisting of primary particle agglomerations. The granular silver powder has an average particle size (D50) of approximately 5 micrometers, an aspect ratio of approximately 2, a specific surface area of ​​approximately 2 m² / g, and a tap density of approximately 5 g / cm³. - Thermally conductive filler #3: Granular silver powder with an average particle size (D50) of approximately 0.1 micrometers, consisting of primary particle agglomerations. The granular silver powder has an average particle size (D50) of approximately 1 micrometer, an aspect ratio of approximately 2, a specific surface area of ​​approximately 4 m² / g, and a tap density of approximately 4.5 g / cm³. - Thermally conductive filler #4: Granular silver powder with an average particle size (D50) of approximately 0.4 micrometers, consisting of primary particle agglomerations. The granular silver powder has an average particle size (D50) of approximately 6.5 micrometers, an aspect ratio of approximately 1.5, a specific surface area of ​​approximately 1.5 m² / g, and a tap density of approximately 4 g / cm³. - Thermally conductive filler #5: Spherical silver powder with an average particle size (D50) of approximately 2.5 micrometers, an aspect ratio of approximately 1.1, a specific surface area of ​​approximately 0.3 m² / g, and a tap density of approximately 6.4 g / cm³. - Thermally conductive filler #6: Flake-shaped silver powder with an average particle size (D50) of approximately 1.2 micrometers, an aspect ratio of approximately 11, a specific surface area of ​​approximately 0.4 m² / g, and a tap density of approximately 5 g / cm³. - Tackifier: 3-glycidoxypropyltrimethoxysilane - Curing catalyst: platinum-divinyltetramethyldisiloxane complex. -Reaction inhibitor: 1-ethynyl-1-cyclohexanol

[0171] Examples 1 to 6 and Comparative Examples 1 to 4

[0172] A silicone resin composition was prepared by adding the compositions shown in Table 1 below to a planetary mixer and mixing them uniformly at room temperature at a speed of about 40 rpm for 1 hour.

[0173] [Table 1] category Organic polysiloxane #1 Organic polysiloxane #2 Organic polysiloxane #3 Thermally conductive filler #1 Thermally conductive filler #2 Thermally conductive filler #3 Thermally conductive filler #4 Thermally conductive filler #5 Thermally conductive filler #6 Tackifier Curing catalyst Response inhibitors unit weight Example 1 7.5 1.3 0.5 30 - - - 60 - 0.5 0.1 0.1 Example 2 7.5 1.3 0.5 25 - - - 65 - 0.5 0.1 0.1 Example 3 7.5 1.3 0.5 20 - - - 70 - 0.5 0.1 0.1 Example 4 7.5 1.3 0.5 15 - - - 75 - 0.5 0.1 0.1 Actual example 5 7.5 1.3 0.5 - 30 - - 60 - 0.5 0.1 0.1 Actual example 6 7.5 1.3 0.5 - twenty five - - 65 - 0.5 0.1 0.1 Comparative Example 1 7.5 1.3 0.5 - - - - 90 - 0.5 0.1 0.1 Comparative Example 2 7.5 1.3 0.5 - - - - 65 twenty five 0.5 0.1 0.1 Comparative Example 3 7.5 1.3 0.5 - - 20 - 65 5 0.5 0.1 0.1 Comparative Example 4 7.5 1.3 0.5 - - - 20 60 10 0.5 0.1 0.1

[0174] Experimental Examples

[0175] Experimental Example 1: Measurement of Thermal Conductivity

[0176] The silicone resin compositions of Examples 1 to 6 and Comparative Examples 1 to 4 were molded into 30 mm × 30 mm × 4 mm dimensions by hot pressing. They were then cured at approximately 150°C for 2 hours to produce samples. The thermal conductivity of the samples of Examples 1 to 6 and Comparative Examples 1 to 4 was then measured at 25°C using a thermal conductivity analyzer (model name: TPS-2500S, manufacturer: Hot Disk AB, Sweden) according to ISO 22007-2. The results are shown in Table 2 below.

[0177] Experimental Example 2—Thermal Shock Test

[0178] The silicone resin compositions of Examples 1 to 6 and Comparative Examples 1 to 4 were allowed to stand at -40°C for 30 minutes and then at 125°C for 30 minutes. This cycle was repeated approximately 500 times, and then the thermal conductivity was measured in the same manner as in Experimental Example 1. The results are shown in Table 2 below.

[0179] Experimental Example 3—Measurement of Overlap Shear Strength and Joint Separation Length

[0180] A silicone resin composition of Examples 1 to 6 and Comparative Examples 1 to 4, each with a thickness of approximately 200 micrometers, was coated onto an area of ​​approximately 2.5 cm × 1.25 cm on the first nickel plate, and then covered with a second nickel plate. Next, the first and second nickel plates were pre-cured at 135°C for approximately 10 minutes while being pressed with a weight of 3 kgf. Then, while the first and second nickel plates were stretched in opposite directions using a universal testing machine (tensile strength analyzer, manufactured by ZwickRoell GmbH), the lap shear strength and joint separation length of the first and second nickel plates were measured according to DIN EN 1465. The results are shown in Table 2 below.

[0181] Experimental Example 4—Measurement of Coverage and Spread Thickness

[0182] 0.7 g of the silicone resin composition of Examples 1 to 6 and Comparative Examples 1 to 4 was coated onto a first silicone substrate with a size of about 27 mm × 27 mm, and then covered with a second silicone substrate of the same size as the first silicone substrate. It was then pre-cured at 135°C for about 10 minutes while applying a force of about 3 kgf to the second silicone substrate. It was then cured at 150°C for about 2 hours. The areas of the first and second silicone substrates in close contact with the cured coating were then measured using a SAT ultrasonic inspection device and an image particle analyzer, and the ratio of the contact area to the total planar area was obtained. The results are shown in Table 2 below.

[0183] Experimental Example 5—Viscosity Measurement

[0184] The viscosity of the silicone resin compositions of Examples 1 to 6 and Comparative Examples 1 to 4 was measured using a rheometer (product name: MCR302, manufacturer: Anton Paar GmbH) at approximately 25°C with a circular plate of 25 mm in diameter. Here, the viscosity was measured at a shear rate of approximately 10 (1 / s). The results are shown in Table 2 below.

[0185] Experimental Example 6—Measurement of Pot Life

[0186] The silicone resin compositions of Examples 1 to 6 and Comparative Examples 1 to 4 were allowed to stand at room temperature, and the time taken for the viscosity to increase by 50% compared to the initial viscosity was measured. The results are shown in Table 2 below.

[0187] [Table 2] category unit Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 The presence of granular particles - ○ ○ ○ ○ ○ ○ × × ○ ○ Equation 1 1) 1 1 1 1 0.4 0.4 - - 4 0.2 TC 2) W / mK 11 10.5 10 9.5 11 10.5 2 7 5 8 TC after thermal shock 11 10.5 10 9.5 11 10.5 2 7 5 8 LSS 3) N / mm 2 1.5 1.7 2.0 2.1 1.6 1.7 2.2 0.6 1.4 0.6 JSL 4) millimeters 0.6 0.6 0.7 0.7 0.6 0.6 0.7 0.3 0.2 0.3 Coverage % 99 99 99 99 99 99 99 70 85 70 Spreading thickness micrometer 50 50 50 50 50 50 50 50 50 50 viscosity cPs 110k 110k 110k 110k 110k 110k 100k 110k 100k 110k Applicable period h 12 12 12 12 12 12 12 12 12 12 1) Equation 1: A(m) 2 / g) / B (micrometers), where A represents the specific surface area of ​​the granular particles, and B represents the average particle size (D) of the granular particles. 50 ) 2) TC: Thermal conductivity 3) LSS: Lap Shear Strength 4) JSL: Joint Separation Length

[0188] Experimental Example 7—Measurement of the Rate of Change in Thermal Conductivity

[0189] The silicone resin compositions of Examples 1 to 6 and Comparative Examples 1 to 4 were molded by hot pressing at 165°C and under the pressure conditions shown in Table 3 below to produce sheets. The sheets were then cured at 150°C for 2 hours, and samples with a width of 30 mm, a length of 30 mm, and a thickness of 4 mm were then produced. The thermal conductivity of the samples produced in Examples 1 to 6 and Comparative Examples 1 to 4 was then measured at 25°C using a thermal conductivity analyzer (model name: TPS-2500S, manufacturer: Hot Disk AB) according to ISO 22007-2 method. The results are shown in Table 3 below.

[0190] [Table 3] category unit Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Content of thermally conductive filler 1) weight% 90 90 90 90 90 90 90 90 90 90 TC0.1 2) W / mK 11 10.5 10 9.5 11 10.5 2 7 5 8 TC1.0 3) 11 10.9 10.2 9.7 11.1 10.7 2.1 8.6 6.1 8.7 TC2.0 4) 11.3 11.1 10.8 10.2 11.5 11.2 2.3 13.0 12.1 13.2 TC5.0 5) 11.4 11.1 10.9 10.5 11.7 11.3 2.6 13.7 12.4 13.9 TC10 6) 11.5 11.2 11.1 10.6 11.8 11.4 2.7 14.5 13.0 14.1 TCC 7) % 4.35 6.25 9.91 10.38 6.78 7.89 25.93 51.72 61.54 43.26 1) Content of thermally conductive filler: The content of thermally conductive filler based on the total content of the silicone resin composition. 2) TC0.1: Thermal conductivity at a pressure of 0.1 kgf 3) TC1.0: Thermal conductivity at a pressure of 1.0 kgf 4) TC2.0: Thermal conductivity at a pressure of 2.0 kgf 5) TC5.0: Thermal conductivity at a pressure of 5.0 kgf 6) TC10: Thermal conductivity at a pressure of 10 kgf 7) TCC: Rate of change of thermal conductivity = (|TC10 - TC0.1| / TC10) × 100

[0191] Referring to Tables 1 to 3, the silicone resin compositions of Examples 1 to 6 comprise granular thermally conductive powder in which primary particles are agglomerated, and the ratio of the specific surface area to the average particle size (D50) of the thermally conductive powder is greater than 0.3 and less than 3.0.

[0192] Therefore, it can be confirmed that, compared to the silicone resin compositions of Comparative Examples 1 to 4, the silicone resin compositions of Examples 1 to 6 have excellent thermal conductivity, improved coverage, relatively strong adhesive strength, and appropriate joint separation length. Furthermore, since the silicone resin compositions of Examples 1 to 6 exhibit a low rate of change in thermal conductivity, it can be confirmed that even when manufactured for commercial use under different pressure conditions, they can perform appropriate heat dissipation functions and exhibit improved product performance reliability. [Simplified Explanation of the Diagram]

[0026] Figure 1 is a cross-sectional view showing a method for measuring the lap shear strength and junction separation length of a silicone resin composition. Figure 2 is a cross-sectional view showing a semiconductor device according to an embodiment.

Claims

1. A silicone-based resin composition comprising: an organic polysiloxane; a first thermally conductive filler; and a curing catalyst, wherein the first thermally conductive filler comprises secondary particles in which the primary particles are agglomerated, wherein the first thermally conductive filler satisfies the following Equation 1: [Equation 1] 0.4 ≤ A (m² / g) / B (micrometers) ≤ 2.0 where A represents the specific surface area of ​​the first thermally conductive filler and is a unitless value, B represents the average particle size (D50) of the first thermally conductive filler and is a unitless value, wherein the tapped density of the first thermally conductive filler is from 0.5 g / cm³ to 6 g / cm³.

2. The silicone resin composition as claimed in claim 1, wherein the primary particles are flaky particles.

3. The silicone resin composition as claimed in claim 1, wherein the aspect ratio of the first thermally conductive filler is 0.5 to 3.

4. The silicone resin composition as claimed in claim 1, wherein the silicone resin composition further comprises a spherical second thermally conductive filler different from the first thermally conductive filler.

5. The silicone resin composition as claimed in claim 4, wherein the aspect ratio of the spherical second thermally conductive filler is 1 to 1.

5.

6. The silicone resin composition as claimed in claim 4, wherein the weight ratio of the first thermally conductive filler to the spherical second thermally conductive filler is 1:1 to 1:

5.

7. The silicone resin composition as claimed in claim 1, wherein the lap shear strength of the silicone resin composition, as measured by DIN EN 1465, is 1 N / mm² or greater.

8. The silicone resin composition as claimed in claim 1, wherein the coverage of the silicone resin composition, measured by the following measurement method 1, is 90% or greater: [Measurement Method 1] 1) applying the silicone resin composition at a weight of 0.7 grams onto a first silicone substrate having dimensions of 27 mm × 27 mm; 2) placing a second silicone substrate having dimensions equal to or larger than the first silicone substrate onto the coated silicone resin composition, and then curing the silicone resin composition under a pressure of 3 kgf; 3) obtaining the area of ​​the first silicone substrate in close contact with the second silicone substrate by the cured silicone resin composition; and 4) the coverage is the ratio of the area of ​​the first silicone substrate in close contact with the second silicone substrate to the planar area of ​​the first silicone substrate.

9. The silicone resin composition as claimed in claim 1, wherein the thermal conductivity change rate of the silicone resin composition, measured by the following measurement method 2, is less than 30%: [Measurement Method 2] 1) Molding the silicone resin composition to produce a first sheet by hot pressing at 165°C and a pressure of 10 kgf / cm² for 15 minutes, and separately molding the silicone resin composition to produce a second sheet by hot pressing at 165°C and a pressure of 0.1 kgf / cm² for 15 minutes; 2) Curing the first sheet and the second sheet at 150°C for 2 hours to produce a first sheet sample and a second sheet sample, respectively; 3) Measuring the thermal conductivity of the first sheet sample and the thermal conductivity of the second sheet sample at 25°C according to ISO 22007-2; 4) Calculating the thermal conductivity change rate according to the following equation 2: [Equation 2] Rate of change of thermal conductivity (%) = (|TC10-TC0.1| / TC10)×100 where TC10 is the thermal conductivity of the first sheet sample (W / mK (watts per meter kelvin)) and TC0.1 is the thermal conductivity of the second sheet sample (W / mK).

10. A semiconductor device comprising: A semiconductor package; a heat dissipation part disposed on the semiconductor package; and a thermally conductive layer inserted between the semiconductor package and the heat dissipation part; wherein the thermally conductive layer comprises a silicone resin composition, wherein the silicone resin composition comprises an organic polysiloxane, a first thermally conductive filler, and a curing catalyst, wherein the first thermally conductive filler comprises secondary particles agglomerated from the primary particles, and the first thermally conductive filler satisfies the following Equation 1: [Equation 1] 0.4 ≤ A (m2 / g) / B (micrometers) ≤ 2.0 where A represents the specific surface area of ​​the first thermally conductive filler and is a unitless value, B represents the average particle size (D50) of the first thermally conductive filler and is a unitless value, and the tap density of the first thermally conductive filler is 0.5 g / cm3 to 6 g / cm3.

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