Patent Application
20230365471
The present disclosure relates to a composite sheet and a method for producing the same, a multilayer body and a method for producing the same, and a power device.
Components such as power devices, transistors, thyristors, and CPUs are required to efficiently radiate heat generated during use. In response to such demands, conventionally, it is possible to increase the thermal conductivity of an insulating layer of a printed wiring board on which an electronic component is mounted or attach an electronic component or a printed wiring board to a heat sink via a thermal interface material having electrical insulation. For such an insulating layer and thermal interface material, a composite composed of a resin and a ceramic such as boron nitride is used as a heat radiation member.
As such a composite, a composite obtained by combining a porous sintered ceramic component (for example, a sintered boron nitride component) and a resin by impregnating the ceramic component with the resin has been studied (for example, refer to Patent Literature 1). In addition, in a multilayer body including a metal circuit and a resin-impregnated sintered boron nitride component, bringing primary particles constituting the sintered boron nitride component and the metal circuit into direct contact with each other to reduce the thermal resistance of the multilayer body and improve heat radiation has also been studied (for example, refer to Patent Literature 2).
As a sintered ceramic component impregnated with a resin as described above and used as a composite, a component obtained by molding a raw material powder into a block and additionally performing sintering is generally used. Then, the resin is impregnated to form a composite and the composite is then cut into a sheet having a desired thickness to obtain a composite sheet. A multilayer body is produced by connecting the composite sheet to a metal circuit or the like. In recent years, in order to improve the yield and the like, producing a composite sheet by preparing a thin baked sintered ceramic component sheet in advance and impregnating the obtained sintered component sheet with a resin has been studied.
The inventors have found that the multilayer body using the composite sheet produced as described above may not exhibit sufficient heat radiation.
Here, an object of the present disclosure is to provide a composite sheet which allows a multilayer body having excellent adhesiveness and heat radiation to be produced and a method for producing the same. In addition, an object of the present disclosure is to provide a multilayer body having excellent adhesiveness and heat radiation using the above composite sheet and a method for producing the same. In addition, an object of the present disclosure is to provide a power device having excellent heat radiation.
The inventors conducted extensive studies in order to address the above problem, and found that, in a composite sheet produced by impregnating a sintered ceramic component that has been prepared thinly in advance with a resin, unlike a composite sheet cut from a conventional block-like composite, a resin layer may be formed on the surface of the composite sheet, and if the curing rate of this resin is high, the sintered ceramic component and the metal circuit cannot sufficiently come in contact with each other when the metal circuit and the metal circuit are connected, and the contact thermal resistance tends to increase. The present disclosure is made based on the finding.
One aspect of the present disclosure provides a composite sheet including a porous sintered ceramic component having a thickness of less than 2 mm and a resin filled into pores of the sintered ceramic component, wherein the curing rate of the resin is 10 to 70%.
Although the composite sheet is composed of a relatively thin and porous sintered ceramic component, since the curing rate of the resin constituting the composite sheet is adjusted to be within a predetermined range, the metal circuit can sufficiently come in contact with the sintered ceramic component during adhesion to the metal circuit, it is possible to reduce contact thermal resistance, and thus a multilayer body having excellent heat radiation can be prepared.
The filling rate of the resin may be 85 to 100 volume %.
The average pore size of the pores of the sintered ceramic component may be 0.2 to 10 μm. When the average pore size of the pores is within the above range, the amount of the resin exuded during adhesion to the metal circuit can be appropriate, and a decrease in adhesiveness can also be minimized.
The sintered ceramic component may be a sintered nitride component.
One aspect of the present disclosure provides a multilayer body in which the above composite sheet and a metal sheet are laminated.
Since the multilayer body includes the above composite sheet, because the composite sheet and the metal sheet can sufficiently come in contact with each other, and it is possible to reduce contact thermal resistance, heat radiation becomes excellent.
One aspect of the present disclosure provides a method for producing a composite sheet including an impregnating step of impregnating a resin composition into pores of a porous sintered ceramic component having a thickness of less than 2 mm to obtain a resin composition-impregnated component; and a curing step of heating the resin composition-impregnated component at 70 to 160° C. and semi-curing the resin composition filled into the pores, wherein, in the impregnating step, the curing rate of the resin composition is 5 to 65%.
In the method for producing a composite sheet, since the porous sintered ceramic component having a thickness of less than 2 mm is used and a resin composition having a predetermined curing rate is used, the resin composition can be sufficiently impregnated into pores of the sintered ceramic component and semi-cured under the above specific conditions, and thus the metal circuit can sufficiently come in contact with the sintered ceramic component during adhesion to the metal circuit, and it is possible to obtain a composite sheet that can reduce contact resistance.
The curing step may be a step of semi-curing the resin composition filled into the pores so that the curing rate thereof is 10 to 70%.
The filling rate of the resin may be 85 to 100 volume %.
The average pore size of the pores of the sintered ceramic component may be 0.2 to 10 μm.
The sintered ceramic component may be a sintered nitride component.
One aspect of the present disclosure provides a method for producing a multilayer body including a laminating step of laminating the composite sheet obtained by the above production method and a metal sheet, heating and pressing the laminate.
In the method for producing a multilayer body, since the above composite sheet is used, on the adhesion surface between the composite sheet and the metal sheet, the metal sheet and the sintered ceramic component constituting the composite sheet can sufficiently come in contact with each other, it is possible to reduce contact resistance, and it is possible to produce a multilayer body having excellent heat radiation.
One aspect of the present disclosure is to provide a power device including a multilayer body including the above composite sheet and a metal sheet laminated on the composite sheet.
Since the power device includes the above composite sheet, it can have excellent heat radiation.
According to the present disclosure, it is possible to provide a composite sheet that allows a multilayer body having excellent adhesiveness and heat radiation to be produced and a method for producing the same. In addition, according to the present disclosure, when the above composite sheet is used, it is also possible to provide a multilayer body having excellent adhesiveness and heat radiation and a method for producing the same. According to the present disclosure, it is also possible to provide a power device having excellent heat radiation.
Hereinafter, embodiments of the present disclosure will be described with reference to the drawings in some cases. However, the following embodiments are only examples for describing the present invention, and the present invention is not limited to the following content. In the description, components which are the same or components having the same functions are denoted with the same reference numerals and redundant descriptions will be omitted in some cases. In addition, positional relationships such as above, below, left and right are based on the positional relationship shown in the drawings unless otherwise specified. In addition, the dimensional ratios of respective components are not limited to the illustrated ratios.
Unless otherwise specified, materials exemplified in this specification may be used alone or two or more thereof may be used in combination. When there are a plurality of substances corresponding to components in a composition, the content of the components in the composition means a total amount of the plurality of substances in the composition unless otherwise specified.
A composite sheet according to one embodiment includes a porous sintered ceramic component having a thickness of less than 2 mm and a resin filled into pores of the sintered ceramic component. The curing rate of the resin is 10 to 70%.
A “resin” in the present disclosure is a semi-cured product (B stage) of a resin composition containing a main agent and a curing agent. The semi-cured product is a product in which the curing reaction of the resin composition has partially proceeded. Therefore, the resin may include a thermosetting resin produced by the reaction of the main agent and the curing agent in the resin composition. The semi-cured product may contain monomers of a main agent and a curing agent in addition to the thermosetting resin as a resin component. The fact that the resin contained in the composite sheet is a semi-cured product (B stage) before being completely cured (C stage) can be confirmed with, for example, a differential scanning calorimeter.
The degree of curing of the resin can be confirmed using, for example, the curing rate of the resin composition as an index based on 100% of the curing rate in a completely cured state. The curing rate of the resin is 10 to 70%. The upper limit value of the curing rate of the resin may be, for example, 68% or less, 65% or less, 63% or less, 60% or less, 50% or less, or 45% or less. When the curing rate of the resin is within the above range, the resin can be appropriately softened and can move even when the composite sheet and the metal sheet are adhered, and thus it is possible to secure contact between the sintered ceramic component and the metal sheet constituting the composite sheet, and it is possible to reduce contact resistance at the interface between the composite sheet and the metal sheet in the obtained multilayer body. In addition, the lower limit value of the curing rate of the resin may be, for example, 12% or more, 13% or more, 15% or more, 17% or more, or 20% or more. When the curing rate of the resin is within the above range, it is possible to prevent the resin from flowing out from the composite sheet and the resin can be sufficiently retained in pores of the sintered ceramic component.
The curing rate of the resin composition can be determined by measurement using a differential scanning calorimeter. First, the amount Q of heat generated when 1 g of the uncured resin composition is completely cured is measured. Then, a sample taken from the resin in the composite sheet is heated in the same manner, and the amount R of heat generated when the sample is completely cured is obtained. In this case, the mass of the sample used for measurement using the differential scanning calorimeter is the same as that of the resin composition used for measurement of the heat amount Q. Assuming that the resin contains c (mass %) of a thermosetting component, the curing rate of the resin composition impregnated into the composite sheet is obtained by the following Formula (A). Here, whether the resin is completely cured can be confirmed from the completion of heat generation in a heat generation curve measured using the differential scanning calorimeter.
Curing rate (%) of impregnated resin composition={1−[(R/c)×100]/Q}×100 (A)
The semi-cured product of the resin composition may include, for example, at least one structural unit selected from the group consisting of a structural unit derived from a cyanate group, a structural unit derived from a bismaleimide group, and a structural unit derived from an epoxy group. When the semi-cured product of the resin composition includes a structural unit derived from a cyanate group, a structural unit derived from a bismaleimide group, and a structural unit derived from an epoxy group, it is possible to easily produce the composite sheet and further improve adhesiveness between the composite sheet and the metal sheet.
Examples of structural units having a cyanate group include a triazine ring. Examples of structural units derived from a bismaleimide group include a structure represented by the following Formula (1). Examples of structural units derived from an epoxy group include a structure represented by the following General Formula (2). These structural units can be detected using infrared absorption spectroscopy (IR). Proton nuclear magnetic resonance spectroscopy (1H-NMR) and carbon-13 nuclear magnetic resonance spectroscopy (13C-NMR) can be used for detection. The above structural units may be detected by any of IR, 1H-NMR and 13C-NMR.
In General Formula (2), R1 represents a hydrogen atom or another functional group. Examples of other functional groups include an alkyl group.
The semi-cured product may contain at least one selected from the group consisting of a cyanate resin, a bismaleimide resin and an epoxy resin as a thermosetting resin. The semi-cured product may contain, for example, a phenolic resin, a melamine resin, a urea resin, and an alkyd resin, in addition to the thermosetting resin.
The semi-cured product may contain at least one curing agent selected from the group consisting of a phosphine-based curing agent and an imidazole-based curing agent. The semi-cured product may be a cured product formed by curing the polymerizable compound (for example, a compound having a cyanate group, a compound having an epoxy group, etc.) contained in the resin composition with these curing agents.
The filling rate of the resin in the composite sheet 10 may be, for example, 85 to 100 volume %. When the filling rate of the resin is within the above range, the amount of the resin component exuded can sufficiently increase during adhesion to the metal sheet under heat and pressure, and the composite sheet of the present embodiment has better adhesiveness. In order to further improve the adhesiveness, the lower limit value of the filling rate of the resin may be 88 volume % or more, 90 volume % or more, 92 volume % or more or 94 volume % or more.
The volume proportion of the resin in the composite sheet 10 based on a total volume of the composite sheet 10 may be 30 to 60 volume % or 35 to 55 volume %. The volume proportion of ceramic particles constituting the sintered ceramic component 20 in the composite sheet 10 based on a total volume of the composite sheet 10 may be 40 to 70 volume % or 45 to 65 volume %. The composite sheet 10 having such a volume proportion can achieve both excellent adhesiveness and strength at a high level.
The average pore size of pores of the sintered ceramic component 20 may be, for example, 10 μm or less, 8 μm or less, 5 μm or less, 4 μm or less, or 3.5 μm or less. Since the size of pores of such a sintered ceramic component 20 is small, it is possible to sufficiently increase the contact area between ceramic particles. Therefore, it is possible to increase thermal conductivity. The average pore size of pores of the sintered ceramic component 20 may be, for example, 0.2 μm or more, 0.3 μm or more, 0.5 μm or more, 1.0 μm or more, or 1.5 μm or more. Since such a sintered ceramic component 20 can be sufficiently deformed by pressing during adhesion, it is possible to increase the amount of the resin component exuded. Therefore, it is possible to further improve adhesiveness.
The average pore size of pores of the sintered ceramic component 20 can be measured by the following procedure. First, the composite sheet 10 is heated to remove the resin. Then, using a mercury porosimeter, the pore size distribution is obtained when the sintered ceramic component 20 is pressed while increasing the pressure from 0.0042 MPa to 206.8 MPa. When the horizontal axis represents the pore size and the vertical axis represents the cumulative pore volume, the pore size when the cumulative pore volume reaches 50% of the total pore volume is defined as the average pore size. A mercury porosimeter (commercially available from Shimadzu Corporation) can be used.
The porosity of the sintered ceramic component 20, that is, the volume proportion of pores in the sintered ceramic component 20 may be 30 to 65 volume % or 35 to 55 volume %. If the porosity is too large, the strength of the sintered ceramic component tends to decrease. On the other hand, if the porosity is too small, the amount of the resin exuded tends to decrease when the composite sheet 10 is adhered to other members.
A bulk density [B(kg/m3)] is calculated from the volume and the mass of the sintered ceramic component 20, and the porosity can be obtained from the bulk density and a theoretical density [A(kg/m3)] of a ceramic according to the following Formula (1). In an example in which the sintered ceramic component 20 is a sintered nitride component, at least one selected from the group consisting of boron nitride, aluminum nitride, and silicon nitride may be contained as a nitride. In the case of boron nitride, the theoretical density A is 2,280 kg/m3. In the case of aluminum nitride, the theoretical density A is 3,260 kg/m3. In the case of silicon nitride, the theoretical density A is 3,170 kg/m3.
Porosity (volume %)=[1−(B/A)]×100 (1)
When the sintered ceramic component 20 is a sintered boron nitride component, the bulk density B may be 800 to 1,500 kg/m3 or 1,000 to 1,400 kg/m3. If the bulk density B is too small, the strength of the sintered ceramic component 20 tends to decrease. On the other hand, if the bulk density B is too large, the amount of the resin filled decreases, and the amount of the resin exuded tends to decrease when the composite sheet 10 is adhered to other members.
The thickness t of the sintered ceramic component 20 may be less than 2 mm or less than 1.6 mm. When the sintered ceramic component 20 has such a thickness, the pores can be more easily filled with the resin, and a composite sheet having an excellent filling rate can be more easily prepared. Therefore, it is possible to reduce the size of the composite sheet 10 and improve adhesiveness of the composite sheet 10. Such a composite sheet 10 is suitably used as a component of a semiconductor device. In consideration of ease of production of the sintered ceramic component 20, the thickness t of the sintered ceramic component 20 may be 0.1 mm or more or 0.2 mm or more.
The thickness of the composite sheet 10 may be the same as the thickness t of the sintered ceramic component 20 or may be larger than the thickness t of the sintered ceramic component 20. The thickness of the composite sheet 10 may be less than 2 mm or less than 1.6 mm. The thickness of the composite sheet 10 may be 0.1 mm or more or 0.2 mm or more. The thickness of the composite sheet 10 is measured in a direction perpendicular to main surfaces 10a and 10b. When the thickness of the composite sheet 10 is not constant, the thicknesses are measured at 10 arbitrarily selected locations, and it is acceptable if the average value thereof is within the above range. Even if the thickness of the sintered ceramic component 20 is not constant, the thicknesses are measured at 10 arbitrarily selected locations, and the average value thereof is defined as the thickness t. The size of the main surfaces 10a and 10b of the composite sheet 10 is not particularly limited, and may be, for example, 500 mm2 or more, 800 mm2 or more, or 1,000 mm2 or more.
The main surface 10a and the main surface 10b of the composite sheet 10 are preferably not cut surfaces. Therefore, it is possible to reduce the proportion of the sintered ceramic component 20 exposed on the main surface 10a and the main surface 10b, and it is possible to sufficiently increase the resin coverage. As a result, it is possible to improve adhesiveness with other members laminated on the main surface 10a and the main surface 10b. Since the composite sheet 10 of the present embodiment is adjusted so that the curing rate of the resin is within a predetermined range, even if the surface of the composite sheet 10 is covered with the resin, the resin can be softened and can move due to heat during adhesion to the metal sheet and thus the metal sheet and the sintered ceramic component can sufficiently come in contact with each other, and it is possible to reduce the contact thermal resistance at the interface between the metal sheet and the composite sheet in the obtained multilayer body. Therefore, it is possible to further improve adhesiveness to other members and the like and heat radiation.
The main surface 10a and the main surface 10b of the composite sheet 10 of the present embodiment are quadrangular, but the present invention is not limited to such a shape. For example, the shape of the main surface may be a polygon other than a quadrangle or may be a circle. In addition, a shape with chamfered corners or a shape with a notched part may be used. In addition, the main surface may have a through-hole that penetrates in the thickness direction.
The multilayer body 100 may have a resin layer between the composite sheet 10 and the metal sheets 30 and 40 without departing from the spirit of the present disclosure. The resin layer may be formed by curing the resin exuded from the composite sheet 10. The composite sheet 10 and the metal sheets 30 and 40 in the multilayer body 100 are sufficiently firmly adhered with the exuded resin so that the adhesiveness is excellent. In addition, since the multilayer body 100 is produced using a composite sheet (B stage sheet) having a resin curing rate within a predetermined range, the contact between the sintered ceramic component and the metal sheet is sufficient, the contact thermal resistance at the interface between the sintered ceramic component and the metal sheet is reduced to a low level, and heat radiation is also excellent. Since such a multilayer body is thin and has excellent adhesiveness and heat radiation, for example, it can be suitably used as a heat radiation member for a semiconductor device and the like.
A method for producing a composite sheet according to one embodiment includes a sintering step of preparing a porous sintered ceramic component, an impregnating step of impregnating a resin composition into pores of a sintered ceramic component having a thickness of less than 2 mm to obtain a resin composition-impregnated component, and a curing step of heating the resin composition-impregnated component at 70 to 160° C. and semi-curing the resin composition filled into the pores. Hereinafter, an example in which the sintered ceramic component is a sintered nitride component will be described.
The raw material powder used in the sintering step contains a nitride. The nitride contained in the raw material powder may include, for example, at least one nitride selected from the group consisting of boron nitride, aluminum nitride, and silicon nitride. When boron nitride is contained, the boron nitride may be an amorphous boron nitride or a hexagonal boron nitride. When a sintered boron nitride component is prepared as the sintered ceramic component 20, as the raw material powder, for example, amorphous boron nitride powder particles having an average particle size of 0.5 to 10 μm or hexagonal boron nitride powder particles having an average particle size of 3.0 to 40 μm can be used.
In the sintering step, a formulation containing nitride powder may be molded and sintered to obtain a sintered nitride component. Molding may be performed by uniaxial pressing or a cold isostatic press (CIP) method. A sintering additive may be added to obtain a formulation before molding. Examples of sintering additives include metal oxides such as yttrium oxide, aluminum oxide and magnesium oxide, alkali metal carbonates such as lithium carbonate and sodium carbonate, and boric acid. When a sintering additive is added, the amount of the sintering additive added, for example, with respect to a total amount of 100 parts by mass of the nitride and the sintering additive, may be, for example, 0.01 parts by mass or more, or 0.1 parts by mass or more. The amount of the sintering additive added with respect to a total amount of 100 parts by mass of the nitride and the sintering additive may be, for example, 20 parts by mass or less, 15 parts by mass or less or 10 parts by mass or less. When the amount of the sintering additive added is set to be within the above range, it becomes easier to adjust the average pore size of the sintered nitride component to be within the range to be described below.
The formulation may be formed into a sheet-like molded product by, for example, a doctor blade method. The molding method is not particularly limited, and press molding may be performed using a mold to form a molded product. The molding pressure may be, for example, 5 to 350 MPa. The shape of the molded product may be a sheet shape having a thickness of less than 2 mm. If a sintered nitride component is produced using such a sheet-like molded product, it is possible to produce a sheet-like composite sheet having a thickness of less than 2 mm without cutting the sintered nitride component. In addition, compared to when the block-like sintered nitride component is cut to form a sheet, the material loss due to processing can be reduced by forming a sheet from the stage of the molded product. Therefore, it is possible to produce composite sheets with a high yield.
The sintering temperature in the sintering step may be, for example, 1,600° C. or higher or 1,700° C. or higher. The sintering temperature may be, for example, 2,200° C. or lower or 2,000° C. or lower. The sintering time may be, for example, 1 hour or more or 30 hours or less. The atmosphere during sintering may be, for example, an inert gas atmosphere such as nitrogen, helium, and argon.
For sintering, for example, a batch type furnace or a continuous type furnace can be used. Examples of batch type furnaces include a muffle furnace, a tube furnace, and an atmospheric furnace. Examples of continuous type furnaces include a rotary kiln, a screw conveyor furnace, a tunnel furnace, a belt furnace, a pusher furnace, and a large continuous furnace. Accordingly, a sintered nitride component can be obtained. The sintered nitride component may have a block shape.
When the sintered nitride component has a block shape, a cutting step of cutting the block so that the thickness is less than 2 mm is performed. In the cutting step, the sintered nitride component is cut using, for example, a wire-saw. Examples of wire-saws include a multi-cut wire-saw. According to such a cutting step, for example, it is possible to obtain a sheet-like sintered nitride component having a thickness of less than 2 mm. The sintered nitride component obtained in this manner has a cut surface.
When the sintered nitride component is subjected to the cutting step, fine cracks may occur on the cut surface. On the other hand, since the composite sheet obtained without performing the cutting step on the sintered nitride component does not have a cut surface, it is possible to sufficiently reduce fine cracks. Therefore, the composite sheet obtained without performing the cutting step on the sintered nitride component can sufficiently improve insulation and thermal conductivity while maintaining sufficiently high strength. That is, the composite sheet has excellent reliability as a member of an electronic component and the like. In addition, when processing such as cutting is performed, the material loss occurs. Therefore, the composite sheet having no cut surface of the sintered nitride component can reduce material loss. Thereby, it is possible to improve the yield of the sintered nitride component and the composite sheet.
In the impregnating step, a resin composition is impregnated into pores of the sintered ceramic component 20 having a thickness of less than 2 mm to obtain a resin composition-impregnated component. The curing rate of the resin composition impregnated in this case is 5 to 65%. Since the sintered nitride component (the sintered ceramic component 20) has a sheet shape having a thickness of less than 2 mm, the resin composition is easily impregnated thereinto. In addition, if the curing rate when the resin composition is impregnated into the sintered nitride component is set to be within a predetermined range, it is suitable for impregnation, the filling rate of the resin can be sufficiently increased, and the curing rate of the resin in the obtained composite sheet can be easily adjusted.
For example, when the temperature T1 at which the resin composition is impregnated into the sintered nitride component is the temperature T2 at which the resin composition is semi-cured, it may be equal to or higher than the temperature T3 (=T2 −20° C.) and lower than the temperature T4 (=T2+20° C.). The temperature T3 may be, for example, 80 to 160° C. Impregnation of the resin composition into the sintered nitride component may be performed under pressurization, under a reduced pressure, or under atmospheric pressure. The impregnating method is not particularly limited, and the sintered nitride component may be immersed in the resin composition and the resin composition may be applied to the surface of the sintered nitride component for impregnation.
When the curing rate of the resin composition is within an appropriate range, the resin can be sufficiently filled into the sintered nitride component. The filling rate of the resin may be, for example, 85 to 100 volume %, and the lower limit value of the filling rate of the resin may be, for example, 88 volume % or more, 90 volume % or more, 92 volume % or more, or 94 volume % or more.
The impregnating step may be performed under any condition of a reduced-pressure condition, a pressurized condition and an atmospheric pressure condition or may be performed under a combination of two or more of impregnation under a reduced-pressure condition, impregnation under a pressurized condition, and impregnation under atmospheric pressure. The pressure in the impregnation device when the impregnating step is performed under a reduced-pressure condition may be, for example, 1,000 Pa or less, 500 Pa or less, 100 Pa or less, 50 Pa or less, or 20 Pa or less. The pressure in the impregnation device when the impregnating step is performed under a pressurized condition may be, for example, 1 MPa or more, 3 MPa or more, 10 MPa or more, or 30 MPa or more.
When the pore size of pores in the sintered nitride component is adjusted, it is also possible to promote impregnation of the resin composition according to a capillary phenomenon. In this regard, the average pore size of the sintered nitride component may be 0.2 to 10 μm or 1 to 8 μm.
As the resin composition, for example, one that becomes the resin exemplified in the above description of the composite sheet according to a curing or semi-curing reaction can be used. The resin composition may contain a solvent. The viscosity of the resin composition may be adjusted by changing the amount of the solvent added, or the viscosity of the resin composition may be adjusted by partially causing the curing reaction to proceed. Examples of solvents include aliphatic alcohols such as ethanol and isopropanol, ether alcohols such as 2-methoxyethanol, 1-methoxyethanol, 2-ethoxyethanol, 1-ethoxy-2-propanol, 2-butoxyethanol, 2-(2-methoxyethoxy)ethanol, 2-(2-ethoxyethoxy)ethanol, and 2-(2-butoxyethoxy)ethanol, glycol ethers such as ethylene glycol monomethyl ether, and ethylene glycol monobutyl ether, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and diisobutyl ketone, and hydrocarbons such as toluene and xylene. These may be used alone or two or more thereof may be used in combination.
The resin composition may be thermosetting, and may contain, for example, at least one compound selected from the group consisting of a compound having a cyanate group, a compound having a bismaleimide group and a compound having an epoxy group, and a curing agent.
Examples of compounds having a cyanate group include dimethylmethylenebis(1,4-phenylene)biscyanate, and bis(4-cyanatophenyl)methane. Dimethylmethylenebis(1,4-phenylene)biscyanate is commercially available as, for example, TACN (product name, commercially available from Mitsubishi Gas Chemical Company, Inc.).
Examples of compounds having a bismaleimide group include
Examples of compounds having an epoxy group include a bisphenol F type epoxy resin, a bisphenol A type epoxy resin, a biphenyl type epoxy resin, and a multifunctional epoxy resin. For example, 1,6-bis(2,3-epoxypropan-1-yloxy)naphthalene commercially available as HP-4032D (product name, commercially available from DIC) may be used.
The curing agent may contain a phosphine-based curing agent and an imidazole-based curing agent. The phosphine-based curing agent can promote a triazine formation reaction by trimerization of a compound having a cyanate group or a cyanate resin.
Examples of phosphine-based curing agents include tetraphenylphosphonium tetra-p-tolylborate and tetraphenylphosphonium tetraphenylborate. Tetraphenylphosphonium tetra-p-tolylborate is commercially available as, for example, TPP-MK (product name, commercially available from Hokko Chemical Industry Co., Ltd.).
The imidazole-based curing agent generates oxazoline and promotes a curing reaction of a compound having an epoxy group or an epoxy resin. Examples of imidazole-based curing agents include 1-(1-cyanomethyl)-2-ethyl-4-methyl-1H-imidazole, and 2-ethyl-4-methylimidazole. 1-(1-cyanomethyl)-2-ethyl-4-methyl-1H-imidazole is commercially available as, for example, 2E4MZ-CN (product name, commercially available from Shikoku Chemical Corporation).
The content of the phosphine-based curing agent with respect to a total amount of 100 parts by mass of the compound having a cyanate group, the compound having a bismaleimide group and the compound having an epoxy group may be, for example, 5 parts by mass or less, 4 parts by mass or less or 3 parts by mass or less. The content of the phosphine-based curing agent with respect to a total amount of 100 parts by mass of the compound having a cyanate group, the compound having a bismaleimide group and the compound having an epoxy group may be, for example, 0.1 parts by mass or more or 0.5 parts by mass or more. When the content of the phosphine-based curing agent is within the above range, it is easy to prepare the resin composition-impregnated component, and it is possible to further shorten the time taken for the composite sheet cut out from the resin composition-impregnated component to be adhered to other members.
The content of the imidazole-based curing agent with respect to a total amount of 100 parts by mass of the compound having a cyanate group, the compound having a bismaleimide group and the compound having an epoxy group may be, for example, 0.1 parts by mass or less, 0.05 parts by mass or less or 0.03 parts by mass or less. The content of the imidazole-based curing agent with respect to a total amount of 100 parts by mass of the compound having a cyanate group, the compound having a bismaleimide group and the compound having an epoxy group may be, for example, 0.001 parts by mass or more or 0.005 parts by mass or more. When the content of the imidazole-based curing agent is within the above range, it is easy to prepare the resin composition-impregnated component, and it is possible to further shorten the time taken for the composite sheet cut out from the resin composition-impregnated component to be adhered to an adherend used.
The resin composition may contain components other than the main agent and the curing agent. Other components include, for example, other resins such as a phenolic resin, a melamine resin, a urea resin, and an alkyd resin, and may further include a silane coupling agent, a leveling agent, an antifoaming agent, a surface adjusting agent, and a wetting and dispersing agent. The content of these other components based on a total amount of the resin composition may be, for example, 20 mass % or less, 10 mass % or less, or 5 mass % or less.
After the impregnating step, a curing step in which the resin composition impregnated into pores is semi-cured is provided. The curing step may be a step of semi-curing the resin composition filled into the pores so that the curing rate of the resin composition is 10 to 70%. In the curing step, according to the type of the resin composition (or a curing agent added as necessary), the resin composition is semi-cured by heating, and/or light emission. “Semi-cured state” (also referred to as a B stage) refers to a state in which the component is additionally cured by a subsequent curing treatment. Temporary press-bonding with other members such as a metal sheet is performed using the semi-cured component, and heating is then performed so that the composite sheet and the metal sheet may be adhered. When the semi-cured product is additionally subjected to a curing treatment, it becomes a “completely cured state” (also referred to as a C stage).
In the curing step, the heating temperature when the resin composition is semi-cured by heating may be, for example, 70 to 160° C. The semi-cured product obtained by semi-curing the resin composition may contain, as the resin component, at least one thermosetting resin selected from the group consisting of a cyanate resin, a bismaleimide resin and an epoxy resin, and a curing agent. The semi-cured product may contain, as the resin component, for example, other resins such as a phenolic resin, a melamine resin, a urea resin, and an alkyd resin, and a component derived from a silane coupling agent, a leveling agent, an antifoaming agent, a surface adjusting agent, and a wetting and dispersing agent.
The composite sheet obtained in this manner has, for example, a thickness of 2 mm or less. Therefore, the composite sheet is thin and lightweight, and when it is used as a component of a semiconductor device or the like, it is possible to reduce the size and weight of the device. In addition, since the resin is sufficiently filled into pores of the sintered nitride component, not only adhesiveness but also thermal conductivity and insulation are excellent. In addition, in the above production method, it is possible to produce a composite sheet without cutting the sintered nitride component. Therefore, it is possible to produce a composite sheet having excellent reliability with a high yield. Here, in addition to forming a multilayer body by laminating a metal sheet on a composite sheet, the composite sheet can be directly used as a heat radiation member.
A method for producing a multilayer body according to one embodiment includes a laminating step of laminating a composite sheet and a metal sheet, heating and pressing the laminate. The composite sheet can be produced by the above production method. The metal sheet may be a metal plate or a metal foil.
In the laminating step, a metal sheet is disposed on the main surface of the composite sheet. With the main surfaces of the composite sheet and the metal sheet in contact with each other, pressurization is performed in a direction in which the main surfaces face each other and heating is performed. Here, pressurization and heating need not necessarily be performed at the same time, and heating may be performed after pressurization and press-bonding. The pressurization pressure may be, for example, 2 to 10 MPa. When the temperature at which the resin composition is semi-cured is set as T2, the heating temperature T5 in this case may be T2+20° C. or higher or T2+40° C. or higher. Therefore, the resin constituting the composite sheet can be softened and the sintered ceramic component and the metal sheet can sufficiently come in contact with each other, the resin composition exuded from the composite sheet can be cured at the interface between the composite sheet and the metal sheet, and the two can be firmly adhered. In order to prevent decomposition of the cured product, the heating temperature T5 may be T2+150° C. or lower or T2+100° C. or lower.
The multilayer body obtained in this manner can be used for production of a semiconductor device, a power device and the like. A semiconductor element may be provided on one metal sheet. The other metal sheet may be bonded to a cooling fin.
A power device according to one embodiment includes a multilayer body including the above composite sheet and a metal sheet laminated on the composite sheet.
While several embodiments have been described above, the same descriptions can be applied to common configurations. In addition, the present disclosure is not limited to the above embodiments.
The content of the present disclosure will be described in more detail with reference to examples and comparative examples, but the present disclosure is not limited to the following examples.
100 parts by mass of orthoboric acid (commercially available from Nippon Denko Co., Ltd.), and 35 parts by mass of acetylene black (product name: HS100, commercially available from Denka Co., Ltd.) were mixed using a Henschel mixer. The obtained mixture was filled into a graphite crucible and heated at 2,200° C. for 5 hours in an argon atmosphere in an arc furnace to obtain a mass boron carbide (B4C). The obtained mass was coarsely pulverized with a jaw crusher to obtain a coarse powder. The coarse powder was additionally pulverized with a ball mill having silicon carbide balls (φ10 mm) to obtain a pulverized powder.
The prepared pulverized powder was filled into a boron nitride crucible. Then, using a resistance heating furnace, heating was performed for 10 hours in a nitrogen gas atmosphere under conditions of 2,000° C. and 0.85 MPa. Thus, a fired product containing boron carbonitride (B4CN4) was obtained.
A powder-like boric acid and calcium carbonate were added to prepare a sintering additive. In preparation, 50.0 parts by mass of calcium carbonate was added with respect 100 parts by mass of boric acid. In this case, regarding the atomic ratio of boron and calcium, the proportion of calcium was 17.5 atom % with respect to 100 atom % of boron. 20 parts by mass of the sintering additive was added with respect to 100 parts by mass of the fired product, and mixed using a Henschel mixer to prepare a powder-like formulation.
The formulation was pressed using a powder press machine at 150 MPa for 30 seconds to obtain a sheet-like (length×width×thickness=50 mm×50 mm×0.30 mm) molded product. The molded product was put into a boron nitride container and introduced into a batch-type high-frequency furnace. In the batch-type high-frequency furnace, heating was performed under conditions of atmospheric pressure, a nitrogen flow rate of 5 L/min, and 2,000° C. for 5 hours. Then, the sintered boron nitride component was removed from the boron nitride container. Accordingly, a sheet-like (square prism-shaped) sintered boron nitride component was obtained. The thickness of the sintered boron nitride component was 0.31 mm.
<Measurement of Average Pore Size>
For the obtained sintered boron nitride component, the pore volume distribution was measured while increasing the pressure from 0.0042 MPa to 206.8 MPa using a mercury porosimeter (device name: Autopore IV9500, commercially available from Shimadzu Corporation). The pore size at which the cumulative pore volume reached 50% of the total pore volume was defined as the “average pore size.” The results are shown in Table 1.
<Production of Composite Sheet>
0.5 parts by mass of a commercially available curing agent (product name: Achmex H-84B, commercially available from The Nippon Synthetic Chemical Industry Co., Ltd.) was added to 10 parts by mass of a commercially available bismaleimide (BMI-80 (product name, commercially available from K⋅I Chemical Industry Co., Ltd.), 29.5 parts by mass of an epoxy resin (product name: Epikote 807, commercially available from Mitsubishi Chemical Corporation), and 60 parts by mass of a commercially available cyanate resin (product name: TACN, commercially available from Mitsubishi Gas Chemical Company, Inc.) to prepare a resin composition. The prepared resin composition was heated at 120° C. for 11 hours and the curing rate was adjusted to 64%. While maintaining the temperature, a resin composition having a curing rate of 13% was added dropwise to the main surface of the sintered boron nitride component heated to 160° C. Under atmospheric pressure, the resin composition added dropwise to the main surface of the sintered boron nitride component was applied and spread using a silicon rubber spatula, and the resin composition was applied to and spread on the entire main surface to obtain a resin composition-impregnated component.
The resin composition-impregnated component was heated at 160° C. for 5 minutes under atmospheric pressure and the resin composition was semi-cured. Accordingly, a square prism-shaped composite sheet (length×width×thickness=length width×thickness=50 mm×50 mm×0.31 mm) was produced.
The curing rate of the resin composition contained in the semi-cured product was determined by measurement using a differential scanning calorimeter. First, the amount Q of heat generated when 1 g of the uncured resin composition was completely cured was measured. Then, a sample taken from the semi-cured product of the composite was heated in the same manner and the amount R heat generated when the sample was completely cured was obtained. In this case, the mass of the sample used for measurement using a differential scanning calorimeter was the same as that of the resin composition used for measurement of the heat amount Q. Assuming that the semi-cured product contained c (mass %) of a thermosetting component, the curing rate of the resin composition impregnated into the composite was obtained by the following Formula (A). The curing rate of the impregnated resin composition in Example 1 was 45%.
curing rate (%) of impregnated resin composition={1−[(R/c)*100]/Q}100 (A)
<Measurement of Filling Rate of Resin (Semi-Cured Product)>
The filling rate of the resin contained in the composite sheet was obtained by the following Formula (3). The results are as shown in Table 1.
filling rate (volume %) of resin in composite sheet={(bulk density of composite sheet-bulk density of sintered boron nitride component)/(theoretical density of composite sheet-bulk density of sintered boron nitride component)}×100 (3)
The bulk density of the sintered boron nitride component and the composite sheet was obtained according to “Methods of measuring density and specific gravity by geometric measurement” in JIS Z 8807: 2012 based on the volume calculated from the length (measured with a vernier caliper) of each side of the sintered boron nitride component or the composite sheet, and the mass of the sintered boron nitride component or the composite sheet measured with an electronic scale (refer to Item 9 of JIS Z 8807: 2012). The theoretical density of the composite sheet was obtained by the following Formula (4).
theoretical density of composite sheet=true density of sintered boron nitride component+true density of resin×(1−bulk density of sintered boron nitride component/true density of boron nitride) (4)
The true density of the sintered boron nitride component and the resin was obtained according to “Methods of measuring density and specific gravity by gas replacement method” in JIS Z 8807: 2012 based on the volume and mass of the sintered boron nitride component and the resin measured using a dry automatic density meter (refer to Formulae (14) to (17) in Item 11 of JIS Z 8807: 2012).
<Production of Multilayer Body>
The above composite sheet (length×width×thickness=50 mm×20 mm×0.31 mm) was disposed between a sheet-like copper foil (length×width×thickness=100 mm×20 mm×0.035 mm) and a sheet-like copper plate (length×width×thickness=100 mm×20 mm- 1 mm) to produce a multilayer body including the copper foil, the composite sheet and the copper plate in this order. The multilayer body was heated and pressed under conditions of 200° C. and 5 MPa for 5 minutes and then heated under conditions of 200° C. and atmospheric pressure for 2 hours. Thereby, the multilayer body was obtained.
<Evaluation of Adhesiveness (Adhesive Strength)>
After the above treatment was performed, a 90° peel test was performed according to “adhesive-peeling adhesion strength test method” in JIS K 6854-1: 1999 using a universal testing machine (product name: RTG-1310, commercially available from A&D Co., Ltd.). Here, peeling was performed at the adhesive interface between the sheet-like copper foil and the composite sheet. Measurement was performed under conditions of a test speed of 50 mm/min, a load cell of 5 kN, and a measurement temperature of room temperature (20° C.), the area proportion of the cohesive fracture part on the peeled surface was measured. Based on the measurement results, the adhesiveness was evaluated according to the following criteria. The results are shown in Table 1. Here, the cohesive fracture part was an area of the part in which the composite sheet was fractured, and a higher area proportion indicates better adhesiveness.
<Evaluation of Contact Thermal Resistance>
After the above treatment was performed, the contact thermal resistance was measured according to the method described in ASTM D5470. Based on the measurement results, the contact thermal resistance was evaluated according to the following criteria.
<Evaluation of Heat Radiation (Thermal Resistance)>
After the above treatment was performed, the thermal resistance was measured according to the method described in ASTM D5470. Based on the measurement results, the thermal resistance was evaluated according to the following criteria.
A composite sheet and a multilayer body were produced in the same manner as in Example 1 except that the conditions in which the resin composition in the resin composition-impregnated component was semi-cured were changed to 70° C. and 300 minutes.
A composite sheet and a multilayer body were produced in the same manner as in Example 1 except that a sintered boron nitride component having a thickness and an average pore size shown in Table 1 was used as the sintered ceramic component and the curing rate of the resin composition added dropwise to the main surface of the sintered boron nitride component was 63%.
A composite sheet and a multilayer body were produced in the same manner as in Example 1 except that a sintered boron nitride component having a thickness and an average pore size shown in Table 1 was used as the sintered ceramic component and the curing rate of the resin composition added dropwise to the main surface of the sintered boron nitride component was 30%.
A composite sheet and a multilayer body were produced in the same manner as in Example 1 except that the curing rate of the resin composition added dropwise to the main surface of the sintered boron nitride component was 6%.
A composite sheet and a multilayer body were produced in the same manner as in Example 1 except that a sintered boron nitride component having a thickness and an average pore size shown in Table 1 was used as the sintered ceramic component and the curing rate of the resin composition added dropwise to the main surface of the sintered boron nitride component was 25%.
A composite sheet and a multilayer body were produced in the same manner as in Example 1 except that a sintered boron nitride component having a thickness and an average pore size shown in Table 1 was used as the sintered ceramic component and the curing rate of the resin composition added dropwise to the main surface of the sintered boron nitride component was 64%.
A composite sheet and a multilayer body were produced in the same manner as in Example 1 except that the curing rate of the resin composition added dropwise to the main surface of the sintered boron nitride component was 2%.
A composite sheet and a multilayer body were produced in the same manner as in Example 1 except that the curing rate of the resin composition added dropwise to the main surface of the sintered boron nitride component was 81%.
A composite sheet and a multilayer body were produced in the same manner as in Example 1 except that a sintered boron nitride component having a thickness and an average pore size shown in Table 1 was used as the sintered ceramic component and the curing rate of the resin composition added dropwise to the main surface of the sintered boron nitride component was 22%.
For the composite sheets and multilayer bodies obtained in Examples 2 to 7 and Comparative Examples 1 to 3, in the same manner as in Example 1, the resin curing rate, the resin filling rate, the adhesiveness (adhesive strength), the contact thermal resistance and the heat radiation (thermal resistance) were evaluated. The results are shown in Table 1.
According to the present disclosure, it is possible to provide a composite sheet which allows a multilayer body having excellent adhesiveness and heat radiation to be produced and a method for producing the same. In addition, according to the present disclosure, it is possible to provide a multilayer body having excellent adhesiveness and heat radiation using the above composite sheet and a method for producing the same. According to the present disclosure, it is possible to provide a power device having excellent heat radiation.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2020-163281 | Sep 2020 | JP | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/JP2021/035574 | 9/28/2021 | WO |
