Resin composition, cured product, wafer holder, and semiconductor manufacturing equipment

Abstract

To provide a resin composition which has high cooling performance and has both thermal conductivity and adhesiveness for the requirements of mitigating thermal expansion of a ceramic and a metal cooling plate and adhering closely to and following a substrate.SOLUTION: The resin composition contains (a) a thermoplastic resin, (b) an epoxy resin, (c) a curing agent, and (d) a filler. The thermoplastic resin (a) has a Tg measured by differential scanning calorimetry of -120 to -30°C and a weight average molecular weight of 1,100,000-1,500,000. The thermoplastic resin (a) is contained in an amount of 400-1,000 pts.wt. based on 100 pts.wt. of the total of the epoxy resin (b) and the curing agent (c). The filler (d) is contained in an amount of more than 600 pts.wt. and 4,000 pts.wt. or less based on 100 pts.wt. of the total of the epoxy resin (b) and the curing agent (c).SELECTED DRAWING: None

Description

Technical Field

[0004] , , , , , , , ,

[0001] The present invention relates to a resin composition, a cured product, a wafer holder, and a semiconductor manufacturing apparatus.

Background Art

[0002] In a wafer holder in which a ceramic electrostatic chuck (electrostatic chuck heater, susceptor) and a metal cooling plate are adhered, it is common to use a resinous adhesive tape or an adhesive for adhering the electrostatic chuck and the cooling plate. As an adhesive composition for such applications, an adhesive sheet containing a thermoplastic resin such as a flexible and highly stretchable acrylic copolymer has been proposed (Patent Document 1). An electrostatic chuck used in a semiconductor manufacturing apparatus such as a dry etching apparatus needs to operate while cooling the electrostatic chuck because the temperature of the electrostatic chuck portion rises during operation. The adhesive has the highest thermal resistance among the above members, and in order to improve the cooling performance, it is necessary to reduce the thermal resistance of the adhesive. In order to reduce the thermal resistance, it is necessary to make the adhesive thinner and increase the thermal conductivity of the adhesive. As a method for improving the thermal conductivity, an adhesive containing a thermal conductive filler has been proposed. (Patent Document 2).

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Summary of the Invention

[0005] Therefore, the main objective of the present invention is to provide a resin composition that can be used to manufacture an adhesive sheet for electrostatic chucks that overcomes the above-mentioned drawbacks, has high cooling performance, and possesses both thermal conductivity and adhesive properties to mitigate the thermal expansion of the ceramic and metal cooling plates, thereby ensuring close contact and conformity to the substrate. [Means for solving the problem]

[0006] To solve the above problems, the present invention has the following configuration. (1) a) a thermoplastic resin, b) epoxy resin, c) curing agent, and d) a resin composition containing a filler, The thermoplastic resin a) has a Tg of -120°C to -30°C as measured by differential scanning calorimetry, and a weight-average molecular weight of 1.1 million to 1.5 million. The mixture contains 400 to 1000 parts by weight of the thermoplastic resin a) with respect to a total of 100 parts by weight of the epoxy resin b) and the curing agent c), The resin composition is characterized in that the d) filler is contained in an amount exceeding 600 parts by weight and not exceeding 4000 parts by weight per 100 parts by weight of the total of the b) epoxy resin and the c) curing agent. (2) The a) thermoplastic resin is a constituent unit 1 having a monomer having at least one functional group selected from the group consisting of epoxy groups, hydroxyl groups, amino groups, hydroxyalkyl groups, vinyl groups, silanol groups, and isocyanate groups. and a constituent unit 2 consisting of an acrylic acid ester having a side chain of 1 to 8 carbon atoms and / or a methacrylic acid ester having a side chain of 1 to 8 carbon atoms. The resin composition according to (1) above, which is a polymer containing the above. (3) The resin composition according to (2), wherein the thermoplastic resin a) is a polymer containing 1 mol% to 10 mol% of the constituent unit 1 and 90 mol% to 99 mol% of the constituent unit 2. (4) The resin composition according to any one of (1) to (3) above, wherein the filler (d) comprises at least one selected from the group consisting of aluminum oxide, aluminum nitride, boron nitride, silica, and magnesium oxide. (5) The resin composition according to any one of (1) to (4), wherein the average particle size of the filler in d) is 0.1 μm to 4.5 μm. (6) The resin composition according to any one of (1) to (5), wherein the filler d) has the same composition and comprises at least two fillers with different average particle sizes. (7) The resin composition according to (6), wherein the filler d) has the same composition and comprises at least a filler with an average particle size of 1.0 μm to 4.5 μm (hereinafter referred to as filler 1) and a filler with an average particle size of 0.01 μm to 0.5 μm (hereinafter referred to as filler 2). (8) The resin composition according to (7), wherein the mass ratio of filler 1 to filler 2 is 60:40 to 99:1. (9) A resin composition according to any one of (1) to (8) above, used for bonding metal members and ceramic members. (10) A cured product obtained by curing any of the resin compositions described in (1) to (9) above. (11) A wafer holder comprising a ceramic member, the cured product described in (10) above, and a metal member. (12) A semiconductor manufacturing apparatus including the wafer holder described in (11) above. [Effects of the Invention]

[0007] The resin composition of the present invention provides an adhesive sheet for electrostatic chucks that offers high cooling performance and meets the requirement of mitigating the thermal expansion of ceramic and metal cooling plates, thereby ensuring close adhesion and conformity to the substrate, by possessing both thermal conductivity and adhesive properties. [Modes for carrying out the invention]

[0008] The present invention relates to a resin composition comprising a) a thermoplastic resin, b) epoxy resin, c) curing agent, and d) filler, wherein the a) thermoplastic resin has a Tg of -120°C to -30°C as measured by differential scanning calorimetry, and a weight-average molecular weight of 1.1 million to 1.5 million, and is contained in an amount of 400 to 1000 parts by weight of the a) thermoplastic resin per 100 parts by weight of the total of the b) epoxy resin and c) curing agent, and the d) filler is contained in an amount exceeding 600 parts by weight and not exceeding 4000 parts by weight per 100 parts by weight of the total of the b) epoxy resin and c) curing agent.

[0009] The embodiments for carrying out the present invention will be described in detail below. However, the present invention is not limited to the following embodiments. In the following embodiments, the components (including elemental steps, etc.) are not essential unless otherwise specified. The same applies to numerical values ​​and their ranges, and they do not limit the present invention.

[0010] In this specification, numerical ranges indicated using "~" include the numbers before and after "~" as the minimum and maximum values, respectively.

[0011] In numerical ranges described stepwise within this specification, the upper or lower limit of one numerical range may be replaced with the upper or lower limit of another numerical range described stepwise. Furthermore, in numerical ranges described within this specification, the upper or lower limit of that range may be replaced with the values ​​shown in the examples.

[0012] In this specification, unless otherwise specified, when there are multiple substances corresponding to each component in the resin composition, the content rate of each component in the resin composition means the total content rate of the multiple substances present in the resin composition.

[0013] In this specification, the term "layer" includes not only the case where it is formed over the entire area when observing the area where the layer exists, but also the case where it is formed only in a part of the area.

[0014] In this specification, the term "lamination" indicates stacking layers, and two or more layers may be bonded, and two or more layers may be detachable.

[0015] <Resin Composition> The resin composition of the present invention is a resin composition containing a) a thermoplastic resin, b) an epoxy resin, c) a curing agent, and d) a filler, wherein the a) thermoplastic resin has a Tg measured by differential scanning calorimetry of -120°C to -30°C and a weight average molecular weight of 1.1 million to 1.5 million, and contains 400 to 1000 parts by weight of the a) thermoplastic resin with respect to a total of 100 parts by weight of the b) epoxy resin and the c) curing agent, and the d) filler contains more than 600 parts by weight and 4000 parts by weight or less with respect to a total of 100 parts by weight of the b) epoxy resin and the c) curing agent.

[0016] The resin composition of the present invention is preferably used for bonding a metal member and a ceramic member.

[0017] The metal member is not particularly limited, but from the viewpoint of thermal conductivity, aluminum, copper, gold, and silver are preferable. Titanium is preferable from the viewpoint of the linear expansion difference with the ceramic member. Further, aluminum is more preferable from the cost aspect. The metal member may be sprayed with a ceramic such as aluminum oxide or may be anodized.

[0018] The ceramic member is not particularly limited, but aluminum oxide or aluminum nitride is preferable from the viewpoints of thermal conductivity and plasma resistance. These may be used alone or as a mixture of two or more types.

[0019] <a) Thermoplastic resin> a) The type of polymer of the thermoplastic resin is not particularly limited. The thermoplastic resin has functions such as flexibility, relaxation of thermal stress, and improvement of insulation due to low water absorption. Examples of the thermoplastic resin include acrylonitrile-butadiene copolymer (NBR), acrylonitrile-butadiene-styrene resin (ABS), polybutadiene, styrene-butadiene-ethylene resin (SEBS), acrylic acid and / or methacrylic acid ester resin having a side chain with 1 to 8 carbon atoms (acrylic rubber), polyvinyl butyral, polyamide, polyester, polyimide, polyamideimide, polyurethane, and the like.

[0020] In addition, the thermoplastic resin suitable as the a) thermoplastic resin of the present invention is a resin that softens by heating to the glass transition temperature or melting point as per the general definition. The thermoplastic resin does not have reactive functional groups such as epoxy groups and ethylenic double bonds, or a combination of reactive functional groups such as isocyanate groups and hydroxyl groups, and isocyanate groups and amino groups. Even when having the aforementioned functional groups, those with a functional group content of 2.0 equivalents / kg or less are preferable.

[0021] In the present invention, as the a) thermoplastic resin, a thermoplastic resin having a Tg measured by differential scanning calorimetry of -120°C to -30°C, preferably -100°C to -40°C or lower is used. When the Tg is -100°C to -30°C or lower, it becomes easier to adjust the Tg after curing of the resin composition containing b) epoxy resin, c) curing agent, and d) filler described later to 0°C or lower, and a state with high stress relaxation can be maintained in the range of 0°C to 150°C where an electrostatic chuck is generally used.

[0022] Furthermore, in this invention, a) a thermoplastic resin is used, which has a weight-average molecular weight of 1.1 million to 1.5 million. From the viewpoint of extensibility after heat curing, interlayer insulation, and film strength, and especially from the viewpoint of maintaining film strength in high-temperature regions such as 150°C, the weight-average molecular weight of the thermoplastic resin is 1.1 million or more, preferably 1.2 million or more. Also, from the viewpoint of the handlingability of the paint viscosity, it is 1.5 million or less, preferably 1.4 million or less. The weight-average molecular weight is measured by GPC (gel permeation chromatography) and calculated in polystyrene equivalent.

[0023] a) Preferably, the thermoplastic resin is a polymer comprising: a constituent unit 1, which consists of a monomer having at least one functional group selected from the group consisting of epoxy groups, hydroxyl groups, amino groups, hydroxyalkyl groups, vinyl groups, silanol groups, and isocyanate groups; and a constituent unit 2, which consists of an acrylic acid ester having a side chain having 1 to 8 carbon atoms and / or a methacrylic acid ester having a side chain having 1 to 8 carbon atoms. More preferably, from the viewpoint of low Tg, the number of carbon atoms in the side chain of constituent unit 2 is 3 to 6.

[0024] It is preferable that the constituent unit 1 has functional groups that can react with b) epoxy resin and c) curing agent, as this strengthens the bond with a) thermoplastic resin, improving adhesive strength and film strength. In particular, it is preferable to use epoxy groups as the functional groups in constituent unit 1 from the viewpoint of compatibility with b) epoxy resin and reactivity with curing agent.

[0025] Examples of constituent unit 2 consisting of acrylic acid esters having side chains with 1 to 8 carbon atoms and / or methacrylic acid esters having side chains with 1 to 8 carbon atoms include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, and methacrylic acid. Examples include alkyl acrylates such as propyl acrylate, butyl acrylate, butyl methacrylate, pentyl acrylate, pentyl methacrylate, hexyl acrylate, hexyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, octyl acrylate, and octyl methacrylate; alkyl methacrylates; esters of acrylic acid with alicyclic alcohols such as cyclohexyl acrylate; acrylonitrile; vinyl acetate; styrene; methylstyrene; chlorostyrene; vinylidene chloride; and ethyl α-acetoxyacrylate. Such acrylic acid esters and methacrylate esters can be used individually or in combination.

[0026] Suitable monomers for constituent unit 1 include glycidyl acrylate, glycidyl methacrylate, acrylamide, and methacrylate.

[0027] a) The thermoplastic resin is preferably a polymer containing 1 mol% to 10 mol% of constituent unit 1 and 90 mol% to 99 mol% or less of constituent unit 2. When constituent unit 1 is 1 mol% to 10 mol%, it remains low elasticity after crosslinking, has poor compatibility with epoxy resin, and undergoes phase separation, resulting in high stress relaxation after curing.

[0028] In the resin composition of the present invention, the content of a) thermoplastic resin is 400 to 1000 parts by weight per 100 parts by weight of the total of b) epoxy resin and c) curing agent. Preferably, a) thermoplastic resin is contained in an amount of 400 to 800 parts by weight per 100 parts by weight of the total of b) epoxy resin and c) curing agent. Within this range, in temperature cycling tests, the film strength of the resin composition itself is ensured by the addition of b) epoxy resin and c) curing agent, while sufficient stress relaxation is obtained by a) thermoplastic resin, so that peeling due to shear stress caused by the difference in linear expansion of the adherend does not occur.

[0029] In the resin composition of the present invention, the parts by weight of a) the thermoplastic resin, b) the epoxy resin, and c) the curing agent can be measured not only by the blending ratio but also by dissolving the composition in an organic solvent such as chloroform, subjecting it to GPC fractionation, and performing pyrolysis GC / MS analysis on each fractionated product.

[0030] <b) Epoxy resin> The resin composition of the present invention contains b) an epoxy resin. By including an epoxy resin in the resin composition of the present invention, it is possible to achieve a balance of physical properties such as heat resistance, insulation at high temperatures, chemical resistance, and strength when used as an adhesive layer. The epoxy resin is not particularly limited as long as it has two or more epoxy groups in one molecule. Examples thereof include cresol novolak type epoxy resins, phenol novolak type epoxy resins, epoxy resins containing a biphenyl type skeleton, naphthalene skeleton-containing epoxy resins, bisphenol type epoxy resins, dicyclopentadiene type epoxy resins, linear aliphatic epoxy resins, alicyclic epoxy resins, heterocyclic epoxy resins, spiro ring-containing epoxy resins, and halogenated epoxy resins.

[0031] From the viewpoint of improving the thermal conductivity, the b) epoxy resin is preferably a crystalline epoxy resin. The crystalline epoxy resin is an epoxy resin having a mesogenic skeleton such as a biphenyl group, a naphthalene skeleton, an anthracene skeleton, a phenyl benzoate group, or a benzanilide group. Products corresponding to such epoxy resins include JERYX4000, JERYX4000H, JERYX8800, JERYL6121H, JERYL6640, JERYL6677, JERYX7399 manufactured by Mitsubishi Chemical Corporation, NC3000, NC3000H, NC3000L, CER-3000L manufactured by Nippon Kayaku Co., Ltd., YSLV-80XY, YDC1312 manufactured by Nippon Steel Chemical Co., Ltd., and HP4032, HP4032D, HP4700 manufactured by DIC Corporation.

[0032] Also, from the viewpoint of lowering the elastic modulus of the cured product to improve flexibility and reducing the contact thermal resistance at the contact interface, an epoxy resin containing a siloxane skeleton is preferable. Examples of such epoxy resins include X-40-2695B and X-22-2046 manufactured by Shin-Etsu Chemical Co., Ltd. Examples of flexible epoxy resins that do not contain a siloxane skeleton include YX7400, YX7110, YX7180, and YX7105 manufactured by Mitsubishi Chemical Corporation.

[0033] Also, the epoxy resin used in the present invention may be of one type or a combination of two or more types.

[0034] <C) Curing Agent> The resin composition of the present invention contains a c) curing agent that undergoes a crosslinking reaction with an epoxy group. By containing a curing agent that undergoes a crosslinking reaction with an epoxy group in the resin composition of the present invention, the adhesive strength after curing is improved.

[0035] Examples of curing agents include 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 3,3',5,5'-tetraethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-5,5'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dichloro-4,4'-diaminodiphenylmethane, 2,2',3,3'-tetrachloro-4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminobenzophenone, 3,3'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, and 4,4'-di Examples of known materials include aromatic polyamines such as aminobenzophenone and 3,4,4'-triaminodiphenylsulfone; amine complexes of boron trifluoride such as boron trifluoride triethylamine complex; novolac phenol resins such as phenol novolac and cresol novolac; bisphenol compounds such as bisphenol A; benzotriazole derivatives such as 1,2,3-benzotriazole, 4-methyl-benzotriazole, 5-methyl-benzotriazole, carboxybenzotriazole, and nitro-1H-benzotriazole; organic acids such as phthalic anhydride, trimellitic anhydride, and pyromellitic anhydride; and dicyandiamides. These may be used individually or in combination of two or more.

[0036] Among these, phenolic curing agents such as novolac phenol resins and bisphenol compounds are preferred due to their excellent heat resistance.

[0037] b) The ratio of epoxy resin to c) curing agent is preferably 1.0:0.8 to 1.4 in terms of functional group equivalent ratio. From the viewpoint of reaction with the epoxy groups of the thermoplastic resin, 1.0:1.0 to 1.4 is preferred.

[0038] In addition, known curing accelerators (curing catalysts) such as triphenylphosphine (TPP), 2-alkyl-4-methylimidazole, and 2-phenyl-4-alkylimidazole are also included in c) curing agents in the present invention.

[0039] When a curing accelerator is included alone as a curing agent (c), the ratio of the epoxy resin (b) to the curing agent (c) is preferably 1.0:0.01 to 0.1 by weight.

[0040] <d)フィラー> The resin composition of the present invention contains d) filler. The d) filler is contained in an amount of more than 600 parts by weight and no more than 4000 parts by weight per 100 parts by weight of the total of b) epoxy resin and c) curing agent. If the content of d) filler is 600 parts by weight or less per 100 parts by weight of the total of b) epoxy resin and c) curing agent, the high thermal conductivity effect of the resin composition is low, and if it exceeds 4000 parts by weight, the extensibility of the resin composition decreases.

[0041] From the viewpoint of balancing high thermal conductivity and high extensibility, it is more preferable that d) filler be in an amount of 1,000 to 3,000 parts by weight per 100 parts by weight of the total of b) epoxy resin and c) curing agent.

[0042] The type of filler is not particularly limited, but specific examples include silica, aluminum oxide, boron nitride, magnesium oxide, aluminum nitride, gold, silver, copper, iron, nickel, silicon carbide, titanium nitride, and titanium carbide. Among these, at least one selected from the group consisting of aluminum oxide, aluminum nitride, boron nitride, silica, and magnesium oxide is preferably used from the viewpoint of insulation and thermal conductivity. These fillers may be surface-treated with a silane coupling agent or the like to improve heat resistance, adhesion, etc.

[0043] Furthermore, the shape of the filler is not particularly limited, and crushed, spherical, or flaky fillers can be used, but spherical fillers are preferred from the viewpoint of dispersibility and filling properties in paint.

[0044] The average particle size of the filler in the resin composition of the present invention is not particularly limited, but from the viewpoint of dispersibility and coating properties, d) the average particle size of the filler is preferably 0.1 μm to 4.5 μm. An average particle size of 4.5 μm or less is preferable from the viewpoint of the extensibility of the resin composition.

[0045] In this context, the average particle size of filler d) refers to the peak value obtained when the resin composition is measured using a HORIBA LA500 laser diffraction particle size analyzer. If there are multiple peaks, it indicates the presence of fillers with different average particle sizes. When there are multiple such peaks, the peak value of each peak is read and each is considered the average particle size of filler d). If there are multiple peaks for filler d), it is preferable that the peak value of at least one peak falls within the range of 0.1 μm to 4.5 μm.

[0046] From the viewpoint of coating properties, it is preferable that the filler d) has the same composition and contains at least two fillers with different average particle sizes. Here, "filler d) having the same composition" means that when the fillers in the resin composition are separated according to the peaks of the particle size distribution measured by the aforementioned laser diffraction particle size analyzer by filtration, and each separated particle is identified by SEM-EDX, the top two elements by weight ratio are the same.

[0047] Furthermore, it is preferable that the filler (d) has the same composition and includes at least one filler (hereinafter referred to as "filler 1") with an average particle size of 1.0 μm to 4.5 μm, and one filler (hereinafter referred to as "filler 2") with an average particle size of 0.01 μm to 0.5 μm. In other words, the filler of the same composition preferably has at least one average particle size (average particle size of filler 1) of 1.0 μm to 4.5 μm, more preferably 1.0 μm to 3.0 μm, and another average particle size (average particle size of filler 2) of 0.01 μm to 0.5 μm, more preferably 0.01 μm to 0.3 μm.

[0048] Furthermore, the mass ratio of filler 1 to filler 2 is preferably 60:40 to 99:1, and more preferably 70:30 to 95:5 from the viewpoint of filler filling and dispersibility.

[0049] <Organic solvents> The resin composition of the present invention may further contain at least one organic solvent. The inclusion of an organic solvent allows the resin composition to be adapted to various molding processes. As the organic solvent, those commonly used in resin compositions can be used. Specifically, examples include alcohol solvents, ether solvents, ketone solvents, amide solvents, aromatic hydrocarbon solvents, ester solvents, nitrile solvents, etc. For example, methyl isobutyl ketone, dimethylacetamide, dimethylformamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, γ-butyrolactone, sulfolane, cyclohexanone, and methyl ethyl ketone can be used. These organic solvents may be used individually or in combination of two or more.

[0050] <Other ingredients> The resin composition of the present invention may contain other components in addition to the above components as needed. Examples of other components include dispersants and plasticizers. Examples of dispersants include the DISPERBYK series ("DISPERBYK" is a registered trademark) manufactured by BIC Chemie Japan Co., Ltd., the Azisper series ("Azisper" is a registered trademark) manufactured by Ajinomoto Fine Techno Co., Ltd., the HIPLAAD series ("HIPLAAD" is a registered trademark) manufactured by Kusumoto Kasei Co., Ltd., and the Homogenol series ("Homogenol" is a registered trademark) manufactured by Kao Corporation. These dispersants may be used individually or in combination of two or more types.

[0051] <Cured product> The cured product of the present invention is a product obtained by curing the resin composition of the present invention.

[0052] Cured products can be produced by curing an uncured resin composition. The curing method can be appropriately selected depending on the composition, purpose, etc., but heating and pressurizing treatment is preferred. For example, the heating temperature is preferably 100°C or higher, more preferably 120°C or higher, and even more preferably 150°C or higher. On the other hand, the heating temperature is preferably 400°C or lower, more preferably 300°C or lower, and even more preferably 250°C or lower. The heating time is preferably 30 minutes to 6 hours. The heating temperature may be increased in stages, or a certain temperature range may be selected and the temperature increased continuously. For example, a method of heating at 130°C and 200°C for 30 minutes each can be used, or a method of linearly increasing the temperature from room temperature to 250°C over 2 hours can be used. Examples of heat treatment devices include ovens, hot plates, autoclaves, and heated presses. If the curing temperature exceeds 180°C, curing is preferably carried out under a nitrogen atmosphere or vacuum.

[0053] <Wafer holder> The wafer holder of the present invention includes a ceramic member, a cured product of the present invention, and a metal member. More specifically, the wafer holder of the present invention includes a laminated member in which the ceramic member, the cured product of the present invention, and the metal member are stacked in this order. Hereinafter, a member in which the ceramic member, the cured product of the present invention, and the metal member are stacked in this order will be referred to as a laminated member.

[0054] More specifically, the wafer holder of the present invention includes a laminated member comprising a ceramic Coulomb force type electrostatic chuck having the function of adsorbing and holding a wafer, and a metal cooling plate, with the cured material of the present invention placed between them. Preferably, the wafer holder of the present invention has a temperature control function and a function of uniformly and constantly adjusting the temperature of the object to be adsorbed. Since the wafer holder is used in a wide range of temperatures from low temperatures of 0°C or below to high temperatures of 150°C or above, it is required that the electrostatic chuck and the cooling plate do not peel off even after repeated refrigeration and heating cycles. By providing the cured material of the present invention between member A and member B, thermal stress in refrigeration and heating cycles can be alleviated, and the adhesive state can be maintained well over a wide temperature range and for a long period of time.

[0055] <Semiconductor Manufacturing Equipment> The semiconductor manufacturing apparatus of the present invention includes a wafer holder of the present invention. Therefore, it is preferable that the semiconductor manufacturing apparatus of the present invention has a wafer holder having a plasma source and a temperature control mechanism. In the semiconductor manufacturing apparatus, a substrate to be processed, such as a semiconductor wafer, is placed on a wafer holder provided in a processing chamber, and plasma is generated by applying a high-frequency voltage to the processing chamber in a vacuum environment to perform a dry etching process on the substrate to be processed. As the processing accuracy required for the dry etching process is increasing, adjustments are made to keep the temperature of the substrate to be processed constant in order to improve the uniformity of the plasma treatment within the surface of the substrate to be processed. As described above, by providing the cured product of the present invention, the adhesion state can be maintained well over a wide temperature range and for a long period of time, and consequently, the uniformity of the plasma treatment within the surface of the substrate to be processed can be maintained well. [Examples]

[0056] The present invention will be described in detail below based on examples, but the present invention is not limited thereto. First, the evaluation methods used in Examples 1 to 15 and Comparative Examples 1 to 4 will be described.

[0057] <Preparation of cured sample for evaluation> The 50 μm thick resin compositions with polyethylene terephthalate films on both sides, prepared in the examples and comparative examples described later, were cut into 50 mm squares. One polyethylene terephthalate film was peeled off, and the resin composition surfaces were laminated together under conditions of 70°C and 0.4 MPa. This process was repeated to form 200 μm thick resin compositions with polyethylene terephthalate films on both sides, and then heat-cured at 170°C for 3 hours to obtain cured samples for evaluation.

[0058] (1) Glass transition temperature (Tg) Dynamic viscoelasticity measurements were performed using 5mm x 20mm cut pieces of the above-mentioned cured material sample to determine the glass transition temperature (Tg). The measurement was performed using a Seiko Instruments DMS6100 dynamic viscoelasticity analyzer, with a temperature of -100 to 300°C, a heating rate of 5°C / min, tensile mode, and a frequency of 1Hz. The temperature at which the tanδ peak of the resulting curve was obtained was defined as Tg.

[0059] (2) Shear strain The resin composition described later was cut into 10mm x 10mm pieces, and after peeling off the polyethylene terephthalate film from one side, it was attached to an aluminum plate measuring 50mm (length) x 15mm (width) x 0.5mm (thickness). The polyethylene terephthalate film from the other side was then peeled off and attached to another aluminum plate in a shifted position to create a test specimen for shear testing.

[0060] After heat curing the test specimens for shear testing at 170°C for 3 hours, tensile tests were performed using a MinebeaMitsumi Technograph TG-1kN tensile and compression testing machine, and the displacement at the fracture point was measured. The load cell was set to 1kN and the tensile speed to 5mm / min. The shear strain was defined as the displacement at the fracture point divided by the thickness of the sheet-like composition.

[0061] (3) Thermal conductivity: The above-mentioned cured material sample for evaluation was cut into 10mm squares and used as the cured material sample for thermal conductivity evaluation.

[0062] After blackening cured material samples for thermal conductivity evaluation with graphite spray, the thermal diffusivity was evaluated using the xenon flash method (NETZSCH LFA447 nanoflash). The thermal conductivity in the thickness direction of the cured material was determined from the product of this value, the density of the cured material sample measured by the Archimedes method, and the specific heat of the cured material sample obtained by DSC (Differential Scanning Calorimetry; Perkin Elmer DSC Pyris1). The results are shown in Tables 1 to 4.

[0063] Specific heat was determined by placing 10.0 mg of the hardened sample for evaluation into an aluminum pan, heating it from room temperature to 200°C at a rate of 10°C / min, holding it at 200°C for 5 minutes, and then cooling it at a rate of 10°C / min. Similarly, 26.8 mg of sapphire was placed in an aluminum pan as a reference material and measured under the same conditions. Furthermore, an empty aluminum pan without any sample was measured under the same conditions as a blank. The Heat Flow value at 25°C was read from each DSC curve, and the specific heat capacity was calculated using Equation 1 below.

[0064] Cp represents the specific heat of the hardened sample used for evaluation, C'p represents the specific heat of the reference material (sapphire) at 25°C, h represents the difference in DSC curves between the empty container and the hardened sample used for evaluation, H represents the difference in DSC curves between the empty container and the reference material (sapphire), m represents the mass of the hardened sample used for evaluation (g), and m' represents the mass of the reference material (sapphire) (g). Cp = (h / H) × (m' / m) × C'p ... Equation 1 The thermal conductivity in the thickness direction of the cured sample for thermal conductivity evaluation was determined from the product of the measured thermal diffusivity, density, and specific heat.

[0065] <Composition> The thermoplastic resin, epoxy resin, curing agent, and filler listed below were blended to the compositions shown in Tables 1 to 4, and the mixtures were stirred and dissolved in a DMF / monolbenzene / MIBK mixed solvent at 40°C to a solid content concentration of 35% by weight to prepare an adhesive solution. This adhesive solution was applied using a bar coater to a 38 μm thick polyethylene terephthalate film (Fujimori Kogyo Co., Ltd. "Film Vina" GT) with a silicone release agent to a dry thickness of approximately 50 μm, dried at 150°C for 5 minutes, and then laminated with a 75 μm polyethylene terephthalate film (Fujimori Kogyo Co., Ltd. "Film Vina" GT) to prepare the resin composition of the present invention. The evaluation results are shown in Tables 1 to 4.

[0066] Furthermore, if the thermal conductivity was 0.3 W / m·K or higher and the shear strain was 2 or higher, it was judged as ○, and if either of these characteristics was not met, it was judged as ×.

[0067] Each raw material used in the examples is as follows.

[0068] <a) Thermoplastic resin> In a reactor equipped with a mixer and a cooler, under a nitrogen atmosphere (or under a nitrogen gas flow), monomers and a solvent in the following proportions were put in, heated to 85 °C under atmospheric pressure (1013 hPa), and further a chain transfer agent, a polymerization initiator, etc. were dropped, and polymerization was carried out until the weight-average molecular weight shown below was obtained.

[0069] The weight-average molecular weight of the obtained polymer was measured by the GPC (gel permeation chromatography) method (apparatus: GEL PERMEATION CHROMATOGRAPH manufactured by Tosoh Corporation, column: TSK-GEL GMHXL 7.8 * 300 mm manufactured by Tosoh Corporation), and calculated in terms of polystyrene.

[0070] Also, the Tg of the obtained polymer was measured by differential scanning calorimetry. Using EXTER DSC6100 manufactured by SII, it was measured at a temperature of -70 °C to 200 °C, a heating rate of 10 °C / min, a sample amount of about 10 mg, using an Al open pan, and a nitrogen gas flow of 40 mL / min.

[0071] · Thermoplastic resin 1: Acrylic rubber containing an epoxy group with a weight-average molecular weight of 850,000, Tg -32 °C, monomer polymerization ratio (ethyl acrylate: butyl acrylate: glycidyl acrylate = 65 mol%: 35 mol%: 1 mol%) · Thermoplastic resin 2: Acrylic rubber containing an epoxy group with a weight-average molecular weight of 1,100,000, Tg -32 °C, monomer polymerization ratio (ethyl acrylate: butyl acrylate: glycidyl acrylate = 65 mol%: 35 mol%: 1 mol%) · Thermoplastic resin 3: Acrylic rubber containing an epoxy group with a weight-average molecular weight of 1,400,000, Tg -32 °C, monomer polymerization ratio (ethyl acrylate: butyl acrylate:: glycidyl acrylate = 65 mol%: 35 mol%: 1 mol%) <b) Epoxy resin> · 1001: Bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation) ·EOCN-102S: Cresol novolak type epoxy resin (manufactured by Nippon Kayaku Co., Ltd.) ·YX-7110: Copolymer epoxy resin of bisphenol F and 1,6-hexanediol glycidyl ether (manufactured by Mitsubishi Chemical Corporation) <c) Curing agent> ·HF-4: Novolak phenol resin (manufactured by Meiwafosis Co., Ltd.) ·C17Z: 2-Heptadecyl imidazole (manufactured by Shikoku Chemicals Corporation) <d) Filler> ·AA-18: Aluminum oxide (average particle size: 18 μm, manufactured by Sumitomo Chemical Co., Ltd.) ·AA-3: Aluminum oxide (average particle size: 3 μm, manufactured by Sumitomo Chemical Co., Ltd.) ·LS210B: Aluminum oxide (average particle size: 3 μm, manufactured by Nippon Light Metal Co., Ltd.) ·AO-502: Aluminum oxide (average particle size: 0.2 μm, manufactured by Admatechs Co., Ltd.) ·FAN-f30: Aluminum nitride (average particle size: 3 μm, manufactured by Furukawa Electric Co., Ltd.) ·H: Aluminum nitride (average particle size: 1 μm, manufactured by Tokuyama)

[0072]

Table 1

[0073]

Table 2

[0074]

Table 3

[0075]

Table 4

[0076] Tables 1 to 3 show that Examples 1 to 15 all have a thermal conductivity of 0.3 W / m·K or higher and a shear strain of 2 or higher, exhibiting high thermal conductivity and extensibility, and are adhesives that adhere well to and conform to dissimilar materials. Furthermore, Examples 1 to 4, 7, and 9 to 11, in which the average particle size of the filler is smaller than 5 μm, had the same amount of filler and thermoplastic resin 1, but tended to have a larger shear strain compared to Examples 14 and 15, in which the average particle size of the filler is larger than 5 μm. This suggests that using a filler with an average particle size of 5 μm or less results in an adhesive with high extensibility and good adhesion and conformability to the adherend.

[0077] On the other hand, as shown in Table 4, Comparative Examples 1 and 2, which have less filler than the examples, have high shear strain but low thermal conductivity, resulting in a composition that cannot achieve both. On the other hand, Comparative Example 4, which has more filler than the examples, has high thermal conductivity but has a very small shear strain of less than 2, resulting in insufficient adhesion and conformability to the adherend.

[0078] Furthermore, Comparative Example 3, which contains less thermoplastic resin than the example, exhibits a very small shear strain of less than 2, resulting in insufficient adhesion and conformability to the adherend, similar to Comparative Example 4.

Claims

1. a) a thermoplastic resin, b) epoxy resin, c) curing agent, and d) a resin composition containing a filler, The thermoplastic resin a) has a Tg of -120°C to -30°C as measured by differential scanning calorimetry, and a weight-average molecular weight of 1.1 million to 1.5 million. a) The thermoplastic resin is a constituent unit 1 having a monomer having at least one functional group selected from the group consisting of epoxy groups, hydroxyl groups, amino groups, hydroxyalkyl groups, vinyl groups, silanol groups, and isocyanate groups. and a constituent unit 2 consisting of an acrylic acid ester having a side chain of 1 to 8 carbon atoms and / or a methacrylic acid ester having a side chain of 1 to 8 carbon atoms. A flapper containing this flaps occurs, The thermoplastic resin a) is a polymer containing 1 mol% to 10 mol% of the constituent unit 1 and 90 mol% to 99 mol% of the constituent unit 2. The mixture contains 400 to 1000 parts by weight of the thermoplastic resin a) with respect to a total of 100 parts by weight of the epoxy resin b) and the curing agent c), The d) filler is contained in an amount exceeding 600 parts by weight and not exceeding 4000 parts by weight, based on 100 parts by weight of the total of the b) epoxy resin and c) curing agent. The resin composition is characterized in that the filler (d) comprises at least one selected from the group consisting of aluminum oxide and aluminum nitride.

2. The resin composition according to claim 1, wherein the average particle size of the filler in d) is 0.1 μm to 4.5 μm.

3. The resin composition according to claim 1, wherein the filler d) comprises at least two fillers having the same composition but different average particle sizes.

4. The resin composition according to claim 3, wherein the filler d) comprises at least a filler of the same composition with an average particle size of 1.0 μm to 4.5 μm (hereinafter referred to as filler 1) and a filler with an average particle size of 0.01 μm to 0.5 μm (hereinafter referred to as filler 2).

5. The resin composition according to claim 4, wherein the mass ratio of filler 1 to filler 2 is 60:40 to 99:

1.

6. A resin composition according to claim 1 or 2, used for bonding metal and ceramic members.

7. A cured product obtained by curing the resin composition according to claim 1 or 2.

8. A wafer holder comprising a ceramic member, a cured product according to claim 7, and a metal member.

9. A semiconductor manufacturing apparatus comprising the wafer holder described in claim 8.

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