Laminate, method for manufacturing a laminate, and method for manufacturing a semiconductor substrate

Abstract

The present invention provides: a multilayer body having a bonding layer which enables easy separation of a semiconductor substrate and a supporting substrate from each other after processing of the semiconductor substrate, and which is capable of suppressing deformation of a bump; and the like.　A multilayer body which is provided with: a semiconductor substrate with a bump; a supporting substrate; a bonding layer for protection, the bonding layer being formed to be in contact with the semiconductor substrate with a bump; and a bonding layer for separation, the bonding layer being formed between the bonding layer for protection and the supporting substrate. With respect to this multilayer body, the bonding layer for protection is formed from an adhesive composition for protection; the adhesive composition for protection contains a component (A) which is cured by means of a hydrosilylation reaction, but does not contain a remover agent component (B) which does not cause a curing reaction; the bonding layer for separation is formed from an adhesive composition for separation; and the adhesive composition for separation contains a component (A) which is cured by means of a hydrosilylation reaction and a remover agent component (B) which does not cause a curing reaction.

Description

[Technical Field]

[0001] The present invention relates to a laminate, a method for manufacturing a laminate, and a method for manufacturing a semiconductor substrate. [Background technology]

[0002] Conventionally, semiconductor wafers have been integrated in a two-dimensional planar direction. To achieve even greater integration, there is a need for semiconductor integration technology that integrates (stacks) in a three-dimensional direction as well. This three-dimensional stacking is a technology that integrates multiple layers while connecting them with through silicon vias (TSVs). When integrating multiple layers, the side opposite to the circuit surface (i.e., the back surface) of each wafer to be integrated is thinned by polishing, and the thinned semiconductor wafers are stacked. The semiconductor wafer (also simply called a wafer here) is bonded to a support in order to be polished using a polishing device. The bonding used in this process is called temporary bonding because it must be easily removed after polishing. This temporary bonding must be easily removed from the support, as applying excessive force during removal can cause the thinned semiconductor wafer to cut or deform. Therefore, it must be easily removed to prevent such damage. However, it is undesirable for the bonding to detach or shift due to polishing stress during the back surface polishing of the semiconductor wafer. Consequently, the required performance of temporary bonding is to withstand the stress during polishing and to be easily removed after polishing. For example, the required properties include high stress (strong adhesive strength) in the planar direction during polishing and low stress (weak adhesive strength) in the longitudinal direction during removal.

[0003] As such an bonding process, a wafer support structure has been proposed in which, between a wafer (1), which is a semiconductor wafer, and a support layer (6), which is a support, a silicone oil layer, a separation layer (4), which is a plasma polymer layer, and a layer (5) of partially cured or curable elastomer material are arranged from the wafer (1) side, and the adhesive bond between the support layer system and the separation layer (4) after the elastomer material has fully cured is greater than the adhesive bond between the wafer (1) and the separation layer (4) (see, for example, the example in Patent Document 1).

[0004] When thinning a semiconductor wafer and then removing the thinned wafer from its support, there is always a need for technology that allows for easy removal of the semiconductor wafer from the support without requiring significant force. Furthermore, semiconductor wafers are electrically connected to semiconductor chips via bump balls made of conductive materials such as metal, and the use of chips equipped with such bump balls helps to miniaturize semiconductor packaging. Bump balls made of metals such as copper and tin can be damaged or deformed by external loads such as heating and pressure applied during the semiconductor substrate processing process. With the recent advancements in the semiconductor field, there is a constant need for technologies that can mitigate or prevent such deformation caused by heating and pressure. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Patent No. 5335443 [Overview of the Initiative] [Problems that the invention aims to solve]

[0006] The present invention has been made in view of the above circumstances, and aims to provide a laminate having an adhesive layer that can easily separate a semiconductor substrate from a support substrate and suppress deformation of bumps, a method for manufacturing a semiconductor substrate using the laminate, and a method for manufacturing the laminate. [Means for solving the problem]

[0007] As a result of diligent research to solve the aforementioned problems, the inventors have completed the present invention, which has the following gist.

[0008] In other words, the present invention encompasses the following: [1] A laminate comprising a bumped semiconductor substrate, a support substrate, a protective adhesive layer formed in contact with the bumped semiconductor substrate, and a release adhesive layer formed between the protective adhesive layer and the support substrate, The protective adhesive layer is formed from a protective adhesive composition, the protective adhesive composition containing a component (A) that hardens by a hydrosilylation reaction, and not containing a release agent component (B) that does not undergo a hardening reaction. The aforementioned release adhesive layer is formed from a release adhesive composition, the release adhesive composition comprising a component (A) that hardens by a hydrosilylation reaction and a release agent component (B) that does not undergo a hardening reaction, in a laminate. [2] The component (A) contained in the protective adhesive layer contains a polyorganosiloxane (a1) having alkenyl groups with 2 to 40 carbon atoms bonded to silicon atoms, a polyorganosiloxane (a2) having Si-H groups, and a platinum group metal catalyst (A2), The component (A) contained in the release adhesive layer contains a polyorganosiloxane (a1) having alkenyl groups with 2 to 40 carbon atoms bonded to silicon atoms, a polyorganosiloxane (a2) having Si-H groups, and a platinum group metal catalyst (A2). [1] The laminate described above. [3] The laminate according to [1] or [2], wherein the release agent component (B) contained in the release adhesive layer is a modified polydimethylsiloxane. A step in which the semiconductor substrate in the laminate described in any of [4][1] to [3] is processed, The process involves separating the protective adhesive layer and the release adhesive layer, thereby separating the support substrate and the processed semiconductor substrate. A method for manufacturing a semiconductor substrate, including the method described above. [5] The method for manufacturing a semiconductor substrate according to [4], wherein the processing step includes polishing the surface of the semiconductor substrate opposite to the surface on which the bumps are located, thereby thinning the semiconductor substrate. A method for manufacturing a laminate, comprising manufacturing a laminate according to any of [6][1] to [3], A protective adhesive coating layer formation step, in which a protective adhesive coating layer is formed by applying the protective adhesive composition to the surface of the semiconductor substrate on which the bumps exist, A protective adhesive layer formation step involves heating the protective adhesive coating layer to form the protective adhesive layer, A step of forming a release adhesive coating layer by applying the release adhesive composition onto the support substrate or applying the release adhesive composition onto the protective adhesive layer, A release adhesive layer forming step is performed in which the release adhesive coating layer and the protective adhesive layer are in contact, and the release adhesive coating layer and the support substrate are in contact, and the release adhesive coating layer is heated to form the release adhesive layer. A method for manufacturing a laminate, including the following: [Effects of the Invention]

[0009] According to the present invention, it is possible to provide a laminate having an adhesive layer that allows for easy separation of a semiconductor substrate and a support substrate and suppresses deformation of bumps, a method for manufacturing a semiconductor substrate using the laminate, and a method for manufacturing the laminate. [Brief explanation of the drawing]

[0010] [Figure 1] This is a schematic cross-sectional view of an example of a laminate. [Figure 2A] This is a diagram (part 1) illustrating one method of manufacturing laminates and thinned wafers. [Figure 2B] This is a diagram (part 2) illustrating one method of manufacturing laminates and thinned wafers. [Figure 2C]This is a diagram (part 3) illustrating one method of manufacturing laminates and thinned wafers. [Figure 2D] This is a diagram (part 4) illustrating one method of manufacturing laminates and thinned wafers. [Figure 2E] This is a diagram (part 5) illustrating one method of manufacturing laminates and thinned wafers. [Figure 2F] This is a diagram (part 6) illustrating one method of manufacturing laminates and thinned wafers. [Figure 2G] This is Figure (No. 7) illustrating one method of manufacturing laminates and thinned wafers. [Figure 2H] This is a diagram (number 8) illustrating one method of manufacturing laminates and thinned wafers. [Modes for carrying out the invention]

[0011] (Laminated structure) The laminate of the present invention comprises a support substrate, a semiconductor substrate, a protective adhesive layer, and a release adhesive layer. The semiconductor substrate has bumps on the support substrate side. A protective adhesive layer is interposed between the support substrate and the semiconductor substrate. The protective adhesive layer is in contact with the semiconductor substrate. The release adhesive layer is interposed between the support substrate and the protective adhesive layer. The release adhesive layer preferably comes into contact with the support substrate and the protective adhesive layer. Laminates are used in applications where the semiconductor substrate is separated from the support substrate after processing of the semiconductor substrate within the laminate.

[0012] In a laminate, the protective adhesive layer is formed in contact with the semiconductor substrate, which suppresses deformation of bumps during the manufacturing of the processed semiconductor substrate. This is thought to be because the bumps, which are prone to melting or deformation due to the heat and pressure during semiconductor substrate processing, are protected by the protective adhesive layer, which is resistant to melting and deformation, thus maintaining their shape. Furthermore, in the laminate, since the release adhesive layer is formed between the support substrate and the protective adhesive layer, the two substrates can be separated well without applying excessive load to the substrates when separating the support substrate and the semiconductor substrate. This is thought to be because, as described later, the release adhesive layer contains a release agent component, and when separating the substrates, selective delamination can be achieved well either within the release adhesive layer or at the interface between the release adhesive layer and the adjacent layer or substrate, thereby avoiding excessive load on the substrates.

[0013] <Support substrate> The support substrate is not particularly limited as long as it is a material that can support the semiconductor substrate when the semiconductor substrate is being processed, but examples include glass support substrates and silicon support substrates.

[0014] The shape of the support substrate is not particularly limited, but for example, it can be disc-shaped. The disc-shaped support substrate does not need to have a perfectly circular surface; for example, the outer circumference of the support substrate may have a straight section called an orientation flat, or a notch. The thickness of the disc-shaped support substrate can be appropriately determined according to the size of the semiconductor substrate and is not particularly limited, but for example, it is 500 to 1,000 μm. The diameter of the disc-shaped support substrate can be appropriately determined according to the size of the semiconductor substrate, etc., and is not particularly limited, but for example, it is 100 to 1,000 mm.

[0015] Examples of support substrates include glass wafers or silicon wafers with a diameter of approximately 300 mm and a thickness of approximately 700 μm.

[0016] <Semiconductor substrates> Semiconductor substrates have bumps. Bumps are protruding terminals. In the laminate, the semiconductor substrate has bumps on the support substrate side. In semiconductor substrates, bumps are typically formed on the surface on which circuits are formed. The circuits may be single-layer or multi-layer. The shape of the circuits is not particularly limited. In a semiconductor substrate, the side opposite to the side with bumps (the back surface) is the side that is subjected to processing.

[0017] The main materials that make up the entire semiconductor substrate are not particularly limited as long as they are used in this type of application, but examples include silicon, silicon carbide, and compound semiconductors. The shape of the semiconductor substrate is not particularly limited, but for example, it is disc-shaped. The disc-shaped semiconductor substrate does not need to have a perfectly circular surface; for example, the outer edge of the semiconductor substrate may have a straight section called an orientation flat, or a notch. The thickness of the disc-shaped semiconductor substrate can be determined appropriately depending on the intended use of the semiconductor substrate and is not particularly limited, but for example, it is 500 to 1,000 μm. The diameter of the disc-shaped semiconductor substrate can be determined appropriately depending on the intended use of the semiconductor substrate and is not particularly limited, but examples include 100 to 1,000 mm.

[0018] An example of a semiconductor substrate is a silicon wafer with a diameter of approximately 300 mm and a thickness of approximately 770 μm.

[0019] The material, size, shape, structure, and density of the bumps on the semiconductor substrate are not particularly limited. Examples of bumps include ball bumps, printed bumps, stud bumps, and plated bumps. Typically, the bump height, diameter, and pitch are determined appropriately based on conditions such as a bump height of approximately 1-200 μm, a bump diameter of 1-200 μm, and a bump pitch of 1-500 μm. Examples of materials for the bumps include low-melting-point solder, high-melting-point solder, tin, indium, gold, silver, and copper. The bumps may be composed of a single component or multiple components. More specifically, examples include Sn-based alloy plating such as SnAg bumps, SnBi bumps, Sn bumps, and AuSn bumps. Furthermore, the bump may have a laminated structure that includes a metal layer made of at least one of these components.

[0020] <Protective adhesive layer> A protective adhesive layer is interposed between the support substrate and the semiconductor substrate. The protective adhesive layer is in contact with the semiconductor substrate.

[0021] The protective adhesive layer is formed from a protective adhesive composition, which contains a component (A) that hardens by a hydrosilylation reaction and does not contain a release agent component (B) that does not undergo a hardening reaction. Furthermore, the release agent component (B) specified as not being included in the protective adhesive composition is specified in comparison with the release agent component (B) specified as being included in the release adhesive composition. For detailed information on release agent component (B), please refer to the section "Release Adhesive Composition" in "Release Adhesive Layer" below.

[0022] <<Protective adhesive composition>> The protective adhesive composition contains component (A) which hardens by a hydrosilylation reaction. In a preferred embodiment, the protective adhesive composition used in the present invention contains a polyorganosiloxane. In another preferred embodiment, the protective adhesive composition used in the present invention contains a curing component (A) that serves as an adhesive component. In other preferred embodiments, component (A) may be a component that hardens by a hydrosilylation reaction, or a polyorganosiloxane component (A') that hardens by a hydrosilylation reaction. In another preferred embodiment, component (A) contains, for example, a polyorganosiloxane (a1) having an alkenyl group with 2 to 40 carbon atoms bonded to a silicon atom as an example of component (A’), a polyorganosiloxane (a2) having a Si-H group, and a platinum group metal-based catalyst (A2). Here, the alkenyl group with 2 to 40 carbon atoms may be substituted. Examples of the substituent include a halogen atom, nitro group, cyano group, amino group, hydroxy group, carboxyl group, aryl group, heteroaryl group, and the like. In another preferred embodiment, the polyorganosiloxane component (A’) that cures by a hydrosilylation reaction contains a siloxane unit (Q unit) represented by SiO2, R 1 R 2 R 3 SiO 1 / 2 a siloxane unit (M unit) represented by, R 4 R 5 SiO 2 / 2 a siloxane unit (D unit) represented by, and R 6 SiO 3 / 2 a siloxane unit (T unit) represented by, and comprises a polysiloxane (A1) containing one or more units selected from the group consisting of these units, and a platinum group metal-based catalyst (A2). The polysiloxane (A1) contains a siloxane unit (Q’ unit) represented by SiO2, R 1 ’R 2 ’R 3 ’SiO 1 / 2 a siloxane unit (M’ unit) represented by, R 4 ’R 5 ’SiO 2 / 2 a siloxane unit (D’ unit) represented by, and R 6 ’SiO 3 / 2 a siloxane unit (T’ unit) represented by, and contains one or more units selected from the group consisting of these units, and also contains at least one selected from the group consisting of M’ units, D’ units, and T’ units, a polyorganosiloxane (a1’), and a siloxane unit (Q” unit) represented by SiO2, R 1 ”R 2 ”R 3 ”SiO 1 / 2 a siloxane unit (M” unit) represented by, R 4 ”R5 SiO 2 / 2 Siloxane units (D'' units) and R 6 SiO 3 / 2 The polyorganosiloxane (a2') comprises one or more units selected from the group consisting of siloxane units (T'' units) represented by , and at least one unit selected from the group consisting of M'' units, D'' units, and T'' units. Note that (a1') is an example of (a1), and (a2') is an example of (a2).

[0023] R 1 ~R 6 This group or atom is bonded to a silicon atom and independently represents an optionally substituted alkyl group, an optionally substituted alkenyl group, or a hydrogen atom. Examples of substituents include halogen atoms, nitro groups, cyano groups, amino groups, hydroxyl groups, carboxyl groups, aryl groups, heteroaryl groups, and the like.

[0024] R 1 '~R 6 ' represents a group that bonds to a silicon atom, and each independently represents an optionally substituted alkyl group or an optionally substituted alkenyl group, R 1 '~R 6 At least one of the ' groups is an alkenyl group which may be substituted. Examples of substituents include halogen atoms, nitro groups, cyano groups, amino groups, hydroxyl groups, carboxyl groups, aryl groups, heteroaryl groups, and the like.

[0025] R 1 "~R 6 " represents a group or atom bonded to a silicon atom, and each independently represents an optionally substituted alkyl group or hydrogen atom, but R 1 "~R 6 At least one of the atoms is a hydrogen atom. Examples of substituents include halogen atoms, nitro groups, cyano groups, amino groups, hydroxyl groups, carboxyl groups, aryl groups, heteroaryl groups, etc.

[0026] The alkyl group may be linear, branched, or cyclic, but linear or branched alkyl groups are preferred. The number of carbon atoms is not particularly limited, but is usually 1 to 40, preferably 30 or less, more preferably 20 or less, and even more preferably 10 or less.

[0027] Specific examples of substituted linear or branched alkyl groups include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, tert-butyl group, n-pentyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl-n-propyl group, 1,2-dimethyl-n-propyl group, 2,2-dimethyl-n-propyl group, 1-ethyl-n-propyl group, n-hexyl group, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, 3-methyl-n-pentyl group, 4-methyl-n-pentyl group Examples of suitable groups include the methyl group, 1,1-dimethyl-n-butyl group, 1,2-dimethyl-n-butyl group, 1,3-dimethyl-n-butyl group, 2,2-dimethyl-n-butyl group, 2,3-dimethyl-n-butyl group, 3,3-dimethyl-n-butyl group, 1-ethyl-n-butyl group, 2-ethyl-n-butyl group, 1,1,2-trimethyl-n-propyl group, 1,2,2-trimethyl-n-propyl group, 1-ethyl-1-methyl-n-propyl group, and 1-ethyl-2-methyl-n-propyl group, but are not limited to these. The number of carbon atoms is usually 1 to 14, preferably 1 to 10, and more preferably 1 to 6. Among these, the methyl group is particularly preferred.

[0028] Specific examples of cyclic alkyl groups that may be substituted include cyclopropyl group, cyclobutyl group, 1-methyl-cyclopropyl group, 2-methyl-cyclopropyl group, cyclopentyl group, 1-methyl-cyclobutyl group, 2-methyl-cyclobutyl group, 3-methyl-cyclobutyl group, 1,2-dimethyl-cyclopropyl group, 2,3-dimethyl-cyclopropyl group, 1-ethyl-cyclopropyl group, 2-ethyl-cyclopropyl group, cyclohexyl group, 1-methyl-cyclopentyl group, 2-methyl-cyclopentyl group, 3-methyl-cyclopentyl group, 1-ethyl-cyclobutyl group, 2-ethyl-cyclobutyl group, 3-ethyl-cyclobutyl group, 1,2-dimethyl-cyclobutyl group, 1,3-dimethyl-cyclobutyl group, 2,2-dimethyl-cyclobutyl group, 2,3-dimethyl-cyclobutyl group, 2,4-dimethyl-cyclobutyl group, 3,3-dimethyl-cyclobutyl group Examples of cycloalkyl groups include cycloalkyl groups such as ethyl-cyclobutyl group, 1-n-propyl-cyclopropyl group, 2-n-propyl-cyclopropyl group, 1-i-propyl-cyclopropyl group, 2-i-propyl-cyclopropyl group, 1,2,2-trimethyl-cyclopropyl group, 1,2,3-trimethyl-cyclopropyl group, 2,2,3-trimethyl-cyclopropyl group, 1-ethyl-2-methyl-cyclopropyl group, 2-ethyl-1-methyl-cyclopropyl group, 2-ethyl-2-methyl-cyclopropyl group, and 2-ethyl-3-methyl-cyclopropyl group, as well as bicycloalkyl groups such as bicyclobutyl group, bicyclopentyl group, bicyclohexyl group, bicycloheptyl group, bicyclooctyl group, bicyclononyl group, and bicyclodecyl group, but are not limited to these. The number of carbon atoms is usually 3 to 14, preferably 4 to 10, and more preferably 5 to 6.

[0029] The alkenyl group may be linear or branched, and its carbon number is not particularly limited, but is usually 2 to 40, preferably 30 or less, more preferably 20 or less, and even more preferably 10 or less.

[0030] Specific examples of substituted linear or branched alkenyl groups include, but are not limited to, vinyl, allyl, buttenyl, and pentenyl groups. Their carbon number is typically 2 to 14, preferably 2 to 10, and more preferably 1 to 6. Among these, ethenyl and 2-propenyl groups are particularly preferred. Specific examples of substituted cyclic alkenyl groups include, but are not limited to, cyclopentenyl and cyclohexenyl. The number of carbon atoms is usually 4 to 14, preferably 5 to 10, and more preferably 5 to 6.

[0031] As mentioned above, polysiloxane (A1) contains polyorganosiloxane (a1') and polyorganosiloxane (a2'). The alkenyl groups in polyorganosiloxane (a1') and the hydrogen atoms (Si-H groups) in polyorganosiloxane (a2') form a cross-linked structure through a hydrosilylation reaction with a platinum group metal catalyst (A2), resulting in hardening. As a result, a hardened film is formed.

[0032] Polyorganosiloxane (a1') contains one or more units selected from the group consisting of Q' units, M' units, D' units, and T' units, and also contains at least one unit selected from the group consisting of M' units, D' units, and T' units. As polyorganosiloxane (a1'), two or more polyorganosiloxanes that satisfy these conditions may be used in combination.

[0033] Two or more preferred combinations selected from the group consisting of Q' units, M' units, D' units, and T' units include, but are not limited to, (Q' units and M' units), (D' units and M' units), (T' units and M' units), and (Q' units, T' units, and M' units).

[0034] Furthermore, when polyorganosiloxane (a1') contains two or more polyorganosiloxanes, the combinations of (Q' units and M' units) and (D' units and M' units), (T' units and M' units) and (D' units and M' units), and (Q' units, T' units and M' units) and (T' units and M' units) are preferred, but are not limited to these.

[0035] Polyorganosiloxane (a2') contains one or more units selected from the group consisting of Q'' units, M'' units, D'' units, and T'' units, and also contains at least one unit selected from the group consisting of M'' units, D'' units, and T'' units. As polyorganosiloxane (a2'), two or more polyorganosiloxanes that satisfy these conditions may be used in combination.

[0036] Two or more preferred combinations selected from the group consisting of Q" units, M" units, D" units, and T" units include, but are not limited to, (M" units and D" units), (Q" units and M" units), and (Q" units, T" units, and M" units).

[0037] Polyorganosiloxane (a1') is composed of siloxane units in which an alkyl group and / or an alkenyl group is bonded to the silicon atom, R 1 '~R 6 The proportion of alkenyl groups in the total substituents represented by ' is preferably 0.1 to 50.0 mol%, more preferably 0.5 to 30.0 mol%, and the remaining R 1 '~R 6 ' can be an alkyl group.

[0038] Polyorganosiloxane (a2') is composed of siloxane units in which an alkyl group and / or a hydrogen atom are bonded to the silicon atom, R 1 "~R 6 The proportion of hydrogen atoms in all substituents and substituted atoms represented by " is preferably 0.1 to 50.0 mol%, more preferably 10.0 to 40.0 mol%, and the remaining R 1 "~R6 " can be an alkyl group.

[0039] When component (A) contains (a1) and (a2), in a preferred embodiment of the present invention, the molar ratio of alkenyl groups contained in polyorganosiloxane (a1) to hydrogen atoms constituting the Si-H bond contained in polyorganosiloxane (a2) is in the range of 1.0:0.5 to 1.0:0.66.

[0040] The weight-average molecular weight of polysiloxanes such as polyorganosiloxane (a1) and polyorganosiloxane (a2) is not particularly limited, but is usually 500 to 1,000,000, and is preferably 5,000 to 50,000 from the viewpoint of reproducibly realizing the effects of the present invention. In this invention, the weight-average molecular weight, number-average molecular weight, and degree of dispersion of polyorganosiloxane can be measured, for example, using a GPC instrument (EcoSEC, HLC-8320GPC, manufactured by Tosoh Corporation) and a GPC column (TSKgel SuperMultiporeHZ-N, TSKgel SuperMultiporeHZ-H, manufactured by Tosoh Corporation), with a column temperature of 40°C, tetrahydrofuran as the eluent (elution solvent), a flow rate (flow rate) of 0.35 mL / min, and polystyrene (Shodex, manufactured by Showa Denko K.K.) as the standard sample.

[0041] The viscosity of polyorganosiloxane (a1) and polyorganosiloxane (a2) is not particularly limited, but is usually 10 to 1,000,000 (mPa·s), and is preferably 50 to 20,000 (mPa·s) from the viewpoint of reproducibly realizing the effects of the present invention. The viscosity of polyorganosiloxane (a1) and polyorganosiloxane (a2) is the value measured with an E-type rotational viscometer at 25°C.

[0042] Polyorganosiloxane (a1) and polyorganosiloxane (a2) react with each other via hydrosilylation to form a film. Therefore, the mechanism of curing is different from that mediated by silanol groups, for example, and consequently, neither siloxane needs to contain silanol groups or functional groups that form silanol groups through hydrolysis, such as alkyloxy groups.

[0043] In a preferred embodiment of the present invention, the adhesive composition comprises a platinum group metal catalyst (A2) together with a polyorganosiloxane component (A'). Such platinum-based metal catalysts are catalysts for promoting the hydrosilylation reaction between the alkenyl group of polyorganosiloxane (a1) and the Si-H group of polyorganosiloxane (a2).

[0044] Specific examples of platinum-based metal catalysts include, but are not limited to, platinum-based catalysts such as platinum black, platinum-dic chloride, chloroplatinic acid, reaction products of chloroplatinic acid and monohydric alcohols, complexes of chloroplatinic acid and olefins, and platinum bisacetate. Examples of complexes between platinum and olefins include, but are not limited to, complexes between divinyltetramethyldisiloxane and platinum. The amount of platinum group metal catalyst (A2) is not particularly limited, but is usually in the range of 1.0 to 50.0 ppm relative to the total amount of polyorganosiloxane (a1) and polyorganosiloxane (a2).

[0045] The polyorganosiloxane component (A') may contain a polymerization inhibitor (A3) for the purpose of suppressing the progress of the hydrosilylation reaction. Polymerization inhibitors are not particularly limited as long as they can suppress the progress of the hydrosilylation reaction, and specific examples include alkynyl alcohols such as 1-ethynyl-1-cyclohexanol and 1,1-diphenyl-2-propion-1-ol. The amount of polymerization inhibitor is not particularly limited, but is usually 1000.0 ppm or more relative to the total amount of polyorganosiloxane (a1) and polyorganosiloxane (a2), from the viewpoint of obtaining its effect, and 10000.0 ppm or less from the viewpoint of preventing excessive inhibition of the hydrosilylation reaction.

[0046] The protective adhesive composition used in the present invention may contain a solvent for purposes such as adjusting viscosity. Specific examples of such solvents include, but are not limited to, aliphatic hydrocarbons, aromatic hydrocarbons, and ketones.

[0047] More specifically, examples of solvents include, but are not limited to, hexane, heptane, octane, nonane, decane, undecane, dodecane, isododecane, menthane, limonene, toluene, xylene, mesitylene, cumene, MIBK (methyl isobutyl ketone), butyl acetate, diisobutyl ketone, 2-octanone, 2-nonanone, and 5-nonanone. Such solvents can be used individually or in combination of two or more.

[0048] When the protective adhesive composition used in the present invention contains a solvent, its content is appropriately determined considering the viscosity of the desired composition, the application method used, the thickness of the film to be produced, etc., but is in the range of approximately 10 to 90% by mass of the entire protective adhesive composition.

[0049] The viscosity of the protective adhesive composition used in the present invention is not particularly limited, but is usually 500 to 20,000 mPa·s at 25°C, and preferably 1,000 to 6,000 mPa·s. The viscosity of the protective adhesive composition used in the present invention can be adjusted by changing the type of solvent used, their ratios, the concentration of film components, etc., taking into consideration various factors such as the application method used and the desired film thickness. In this invention, "film component" refers to components other than the solvent contained in the composition.

[0050] An example of a protective adhesive composition used in the present invention can be manufactured by mixing component (A) with a solvent, if used. Furthermore, when preparing the protective adhesive composition, heating may be used as appropriate, provided that the components do not decompose or deteriorate. In the present invention, for the purpose of removing foreign matter, the solvent or solution used may be filtered using a filter or the like during the manufacturing process of the protective adhesive composition or after all components have been mixed.

[0051] The thickness of the protective adhesive layer in the laminate of the present invention is not particularly limited, but from the viewpoint of obtaining a good bump deformation suppression effect with good reproducibility, it is preferably 10 to 100 μm, and more preferably 20 to 50 μm.

[0052] <Release Adhesive Layer> The release adhesive layer is interposed between the support substrate and the protective adhesive layer. The release adhesive layer is preferably in contact with the support substrate and the protective adhesive layer, from the viewpoint of obtaining a good bump deformation suppression effect with good reproducibility.

[0053] The release adhesive layer is formed from a release adhesive composition, which comprises a component (A) that hardens by a hydrosilylation reaction and a release agent component (B) that does not undergo a hardening reaction.

[0054] <<Release Adhesive Composition>> The release adhesive composition contains a component (A) that hardens by a hydrosilylation reaction. In a preferred embodiment, the release adhesive composition used in the present invention contains a polyorganosiloxane. In another preferred embodiment, the release adhesive composition used in the present invention contains a curing component (A) that becomes an adhesive component and a release agent component (B) that does not undergo a curing reaction. Examples of the release agent component (B) that does not undergo a curing reaction include polyorganosiloxanes. In this invention, "does not undergo a curing reaction" does not mean that no curing reaction occurs at all, but rather that the curing reaction that occurs in the curing component (A) does not occur. In other preferred embodiments, component (A) may be a component that hardens by a hydrosilylation reaction, or a polyorganosiloxane component (A') that hardens by a hydrosilylation reaction. The components (A) and polyorganosiloxane component (A') are described in the section on "Protective Adhesive Composition" in the aforementioned "Protective Adhesive Layer". The components (A) and polyorganosiloxane component (A') contained in the protective adhesive composition and the components (A) and polyorganosiloxane component (A') contained in the release adhesive composition may be of the same type or different types. The release adhesive composition contains a release agent component (B) that does not undergo a curing reaction, but the composition as a whole undergoes a crosslinking reaction via hydrosilylation and hardens. It is preferable that the curing component (A) in the release adhesive composition does not contain any components containing aromatic rings.

[0055] An example of a release adhesive composition used in the present invention contains a curing component (A) along with a release agent component (B) that does not undergo a curing reaction. By including such a release agent component (B) in the release adhesive composition, the release adhesive layer can be easily separated from an adjacent layer or substrate. Typical examples of such release agent component (B) include polyorganosiloxanes. In one preferred embodiment, specific examples include, but are not limited to, epoxy group-containing polyorganosiloxanes, methyl group-containing polyorganosiloxanes, and phenyl group-containing polyorganosiloxanes. In other preferred embodiments, the release agent component (B) may be polydimethylsiloxane, which may be modified. Examples of polydimethylsiloxanes that may be modified include, but are not limited to, epoxy group-containing polydimethylsiloxane, unmodified polydimethylsiloxane, and phenyl group-containing polydimethylsiloxane.

[0056] Preferred examples of the polyorganosiloxane, which is the release agent component (B), include, but are not limited to, epoxy group-containing polyorganosiloxane, methyl group-containing polyorganosiloxane, and phenyl group-containing polyorganosiloxane.

[0057] The weight-average molecular weight of the polyorganosiloxane, which is the release agent component (B), is not particularly limited, but is usually 100,000 to 2,000,000, and is preferably 200,000 to 1,200,000, more preferably 300,000 to 900,000, from the viewpoint of reproducibly achieving the effects of the present invention. Furthermore, the degree of dispersion is not particularly limited, but is usually 1.0 to 10.0, and is preferably 1.5 to 5.0, more preferably 2.0 to 3.0, from the viewpoint of reproducibly achieving suitable release. The weight-average molecular weight and degree of dispersion can be measured by the method described above for polysiloxanes. The complex viscosity of polyorganosiloxane, which is the release agent component (B), can be measured at 25°C using a rheometer (for example, the MCR-302 rheometer manufactured by Anton Paar Co., Ltd.).

[0058] Examples of epoxy group-containing polyorganosiloxanes include R 11 R 12 SiO 2 / 2 Siloxane units (D) are represented by these units. 10 Examples include those containing units.

[0059] R 11 R is a group that bonds to a silicon atom and represents an alkyl group. 12 This refers to a group that bonds to a silicon atom, representing an epoxy group or an organic group containing an epoxy group. Specific examples of alkyl groups can be found in the examples mentioned above. In an organic group containing an epoxy group, the epoxy group may be an independent epoxy group that does not condense with other rings, or it may be an epoxy group that forms a fused ring with other rings, such as a 1,2-epoxycyclohexyl group. Specific examples of organic groups containing epoxy groups include, but are not limited to, 3-glycidoxypropyl and 2-(3,4-epoxycyclohexyl)ethyl. In the present invention, a preferred example of an epoxy group-containing polyorganosiloxane is, but is not limited to, epoxy group-containing polydimethylsiloxane.

[0060] Epoxy group-containing polyorganosiloxanes are the aforementioned siloxane units (D 10 It includes units, but D 10 In addition to units, Q units, M units, and / or T units may also be included. In preferred embodiments of the present invention, specific examples of epoxy group-containing polyorganosiloxanes include D 10 Polyorganosiloxanes consisting only of units, D 10 Polyorganosiloxane containing units and Q units, D 10 Polyorganosiloxane containing units and M units, D 10 Polyorganosiloxanes containing units and T units, D 10 Polyorganosiloxane containing units, Q units, and M units, D 10 Polyorganosiloxane containing units, M units, and T units, D 10 Examples include polyorganosiloxanes containing units, Q units, M units, and T units.

[0061] The epoxy group-containing polyorganosiloxane is preferably an epoxy group-containing polydimethylsiloxane with an epoxy value of 0.1 to 5. Its weight-average molecular weight is not particularly limited, but is usually between 1,500 and 500,000, and is preferably 100,000 or less from the viewpoint of suppressing precipitation in the adhesive.

[0062] Specific examples of epoxy group-containing polyorganosiloxanes include, but are not limited to, those represented by formulas (E1) to (E3).

[0063] [ka] (m1 and n1 are positive integers, representing the number of each repeating unit.)

[0064] [ka] (m2 and n2 are positive integers indicating the number of repeating units, and R is an alkylene group with 1 to 10 carbon atoms.)

[0065] [ka] (m3, n3, and o3 represent the number of repeating units and are positive integers; R is an alkylene group with 1 to 10 carbon atoms.)

[0066] Examples of methyl group-containing polyorganosiloxanes include R 210 R 220 SiO 2 / 2 Siloxane units (D) are represented by these units. 200 Units) containing, preferably R 21 R 21 SiO 2 / 2 Siloxane units (D) are represented by these units. 20 Examples include those containing units.

[0067] R 210 and R 220 These are groups that bond to a silicon atom, and each independently represents an alkyl group, but at least one of them is a methyl group. The examples mentioned above can be given as specific examples of alkyl groups. R 21 R is a group that bonds to a silicon atom and represents an alkyl group. Specific examples of alkyl groups include those mentioned above. Among them, R 21 A methyl group is preferred as the component. In the present invention, a preferred example of a methyl group-containing polyorganosiloxane is polydimethylsiloxane, but is not limited thereto.

[0068] Methyl group-containing polyorganosiloxanes are the aforementioned siloxane units (D200 Unit or D 20 units), but D 200 units and D 20 In addition to the units and D units, it may also contain Q units, M units and / or T units.

[0069] In one embodiment of the present invention, specific examples of the methyl group-containing polyorganosiloxane include those consisting of only D 200 units of polyorganosiloxane, D 200 units and Q units of polyorganosiloxane, D 200 units and M units of polyorganosiloxane, D 200 units and T units of polyorganosiloxane, D 200 units and Q units and M units of polyorganosiloxane, D 200 units and M units and T units of polyorganosiloxane, D 200 units and Q units and M units and T units of polyorganosiloxane can be mentioned.

[0070] In a preferred embodiment of the present invention, specific examples of the methyl group-containing polyorganosiloxane include those consisting of only D 20 units of polyorganosiloxane, D 20 units and Q units of polyorganosiloxane, D 20 units and M units of polyorganosiloxane, D 20 units and T units of polyorganosiloxane, D 20 units and Q units and M units of polyorganosiloxane, D 20 units and M units and T units of polyorganosiloxane, D 20 units and Q units and M units and T units of polyorganosiloxane can be mentioned.

[0071] Specific examples of the methyl group-containing polyorganosiloxane include, but are not limited to, those represented by the formula (M1).

[0072]

Chemical formula

[0073] Examples of the phenyl group-containing polyorganosiloxane include, for example, R 31 R 32 SiO 2 / 2 Those containing the siloxane unit (D 30 unit) represented by can be mentioned.

[0074] R 31 is a group bonded to a silicon atom and represents a phenyl group or an alkyl group. R 32 is a group bonded to a silicon atom and represents a phenyl group. Specific examples of the alkyl group can include those exemplified above, but a methyl group is preferred.

[0075] The phenyl group-containing polyorganosiloxane contains the above-mentioned siloxane unit (D 30 unit), but in addition to the D 30 unit, it may also contain a Q unit, an M unit and / or a T unit.

[0076] In a preferred embodiment of the present invention, specific examples of the phenyl group-containing polyorganosiloxane include polyorganosiloxanes consisting only of D 30 units, polyorganosiloxanes containing D 30 units and Q units, polyorganosiloxanes containing D 30 units and M units, polyorganosiloxanes containing D 30 units and T units, polyorganosiloxanes containing D 30 units, Q units and M units, polyorganosiloxanes containing D 30 units, M units and T units, and polyorganosiloxanes containing D 30 units, Q units, M units and T units can be mentioned.

[0077] Specific examples of the methyl group-containing polyorganosiloxane include those represented by formula (P1) or (P2), but are not limited thereto.

[0078] [Chemical formula] (m5 and n5 are positive integers indicating the number of each repeating unit.)

[0079] [ka] (m6 and n6 are positive integers that indicate the number of each repeating unit.)

[0080] The stripping agent component (B), polyorganosiloxane, may be a commercially available product or a synthesized product. Commercially available polyorganosiloxanes include, for example, Wacker Chem's WACKERSILICONE FLUID AK series (AK50, AK 350, AK 1000, AK 10000, AK 1000000) and GENIOPLAST GUM; Shin-Etsu Chemical Co., Ltd.'s dimethyl silicone oil (KF-96L, KF-96A, KF-96, KF-96H, KF-69, KF-965, KF-968) and cyclic dimethyl silicone oil (KF-995); Gelest's epoxy-containing polyorganosiloxanes (product names CMS-227, ECMS-327); Shin-Etsu Chemical Co., Ltd.'s epoxy-containing polyorganosiloxanes (KF-101, KF-1001, KF-1005, X-22-343); and Dow Corning's products. Examples include, but are not limited to, epoxy group-containing polyorganosiloxanes (BY16-839); phenyl group-containing polyorganosiloxanes (PMM-1043, PMM-1025, PDM-0421, PDM-0821) manufactured by Gellest, phenyl group-containing polyorganosiloxanes (KF50-3000CS) manufactured by Shin-Etsu Chemical Co., Ltd., and phenyl group-containing polyorganosiloxanes (TSF431, TSF433) manufactured by Momentive.

[0081] The release adhesive composition used in the present invention contains a curing component (A) and a release agent component (B) that does not undergo a curing reaction, and in a more preferred embodiment, the release agent component (B) is a polyorganosiloxane.

[0082] An example of a release adhesive composition used in the present invention can contain component (A) and release agent component (B) in any ratio. However, considering the balance between adhesion and release properties, the ratio of component (A) to release agent component (B) is preferably 99.995:0.005 to 30:70 by mass ratio [(A):(B)], and more preferably 99.9:0.1 to 75:25. In other words, when a polyorganosiloxane component (A') that hardens by a hydrosilylation reaction is included, the ratio of component (A') to the release agent component (B) is preferably 99.995:0.005 to 30:70 by mass ratio [(A'):(B)], and more preferably 99.9:0.1 to 75:25.

[0083] The release adhesive composition used in the present invention may contain a solvent for purposes such as adjusting viscosity. Specific examples of such solvents include, but are not limited to, aliphatic hydrocarbons, aromatic hydrocarbons, and ketones.

[0084] More specifically, examples of solvents include, but are not limited to, hexane, heptane, octane, nonane, decane, undecane, dodecane, isododecane, menthane, limonene, toluene, xylene, mesitylene, cumene, MIBK (methyl isobutyl ketone), butyl acetate, diisobutyl ketone, 2-octanone, 2-nonanone, and 5-nonanone. Such solvents can be used individually or in combination of two or more.

[0085] When the release adhesive composition used in the present invention contains a solvent, its content is appropriately determined considering the viscosity of the desired composition, the application method used, the thickness of the film to be produced, etc., but is in the range of approximately 10 to 90% by mass of the entire release adhesive composition.

[0086] The viscosity of the release adhesive composition used in the present invention is not particularly limited, but is usually 500 to 20,000 mPa·s at 25°C, and preferably 1,000 to 5,000 mPa·s. The viscosity of the release adhesive composition used in the present invention can be adjusted by changing the type of solvent used, their ratios, the concentration of film components, etc., taking into consideration various factors such as the application method used and the desired film thickness.

[0087] An example of the release adhesive composition used in the present invention can be manufactured by mixing component (A), release agent component (B), and a solvent, if used. The mixing order is not particularly limited, but examples of methods for easily and reproducibly producing a release adhesive composition include, for example, dissolving component (A) and release agent component (B) in a solvent, or dissolving a portion of component (A) and release agent component (B) in a solvent, dissolving the remainder in a solvent, and then mixing the resulting solutions. However, the method is not limited to these. When preparing the release adhesive composition, heating may be used as appropriate, as long as the components do not decompose or deteriorate. In the present invention, for the purpose of removing foreign matter, the solvent or solution used may be filtered using a filter or the like during the manufacturing process of the release adhesive composition or after all components have been mixed.

[0088] The thickness of the release adhesive layer in the laminate of the present invention is not particularly limited, but from the viewpoint of obtaining a good release effect with good reproducibility, it is preferably 10 to 100 μm, and more preferably 20 to 50 μm.

[0089] An example of a laminate is explained below using a diagram. Figure 1 is a schematic cross-sectional view of an example of a laminate. The laminate in Figure 1 comprises, in this order, a semiconductor substrate 1 having bumps 1a, a protective adhesive layer 2, a release adhesive layer 3, and a support substrate 4. The bumps 1a on the semiconductor substrate 1 are located on the support substrate 4 side. The protective adhesive layer 2 is interposed between the semiconductor substrate 1 and the support substrate 4. The protective adhesive layer 2 is in contact with the semiconductor substrate 1. Furthermore, the protective adhesive layer 2 covers the bump 1a. The release adhesive layer 3 is interposed between the protective adhesive layer 2 and the support substrate 4. The release adhesive layer 3 is in contact with both the protective adhesive layer 2 and the support substrate 4.

[0090] The laminate of the present invention can be suitably manufactured, for example, by the following method for manufacturing the laminate of the present invention.

[0091] (Method of manufacturing a laminate) The present invention provides a method for manufacturing a laminate, comprising a step of forming a protective adhesive coating layer, a step of forming a protective adhesive layer, a step of forming a release adhesive coating layer, and a step of forming a release adhesive layer, and further, if necessary, other steps such as a bonding step.

[0092] <Protective adhesive coating layer formation process> The protective adhesive coating layer formation process typically involves applying a protective adhesive composition to the surface of a semiconductor substrate where bumps are present, thereby forming a protective adhesive coating layer. By applying the protective adhesive composition to a semiconductor substrate with bumps, it becomes possible to form a protective adhesive coating layer that follows the irregularities caused by the bumps without creating gaps between the protective adhesive coating layer and the substrate. As a result, even if the thickness of the formed protective adhesive layer is thinner than the bump height, it is possible to suitably form a protective adhesive layer that provides good bump protection without causing the top of the bump to protrude from the protective adhesive layer. It should be noted that this does not prevent the protective adhesive layer in the laminate according to the present invention from being thicker than the bump height of the semiconductor substrate; even in such cases, a protective adhesive layer that provides good bump protection can be suitably formed. In this way, a protective adhesive coating layer is formed on the bumped semiconductor substrate.

[0093] The coating method is not particularly limited, but it is usually the spin coating method. Alternatively, a method can be adopted in which a coating film is formed separately by the spin coating method or the like, and the sheet-like coating film is attached as a protective adhesive coating layer. The thickness of the protective adhesive coating layer is determined appropriately, taking into consideration the desired thickness of the protective adhesive layer in the laminate, the bump height, etc. Because the protective adhesive composition contains a solvent or for other reasons, the applied protective adhesive composition may be heated for the purpose of drying the coating film of the applied protective adhesive composition. The heating temperature of the applied protective adhesive composition cannot be specified in general terms, as it varies depending on the type and amount of adhesive components contained in the protective adhesive composition, whether or not a solvent is included, the boiling point of the solvent used, and the desired thickness of the protective adhesive layer. However, it is usually 80 to 150°C, and the heating time is usually 30 seconds to 5 minutes. Heating can be done using a hot plate, oven, etc.

[0094] <Protective adhesive layer formation process> In the protective adhesive layer formation process, the protective adhesive coating layer is heated to form the protective adhesive layer. The heating temperature and time are not particularly limited, as long as they are the temperature and time required for the protective adhesive coating layer to be converted into a protective adhesive layer. The heating temperature is preferably 120°C or higher, more preferably 150°C or higher, from the viewpoint of achieving a sufficient curing rate, and preferably 250°C or lower, from the viewpoint of preventing deterioration of each layer constituting the laminate (including the support substrate and semiconductor substrate). Even more preferably, it is 180 to 200°C. The heating time is preferably 1 minute or more, more preferably 5 minutes or more, from the viewpoint of achieving suitable bonding of each layer constituting the laminate (including the support substrate and the semiconductor substrate), and preferably 180 minutes or less, more preferably 120 minutes or less, from the viewpoint of suppressing or avoiding adverse effects on each layer due to excessive heating. Even more preferably, from the viewpoint of substrate processing efficiency, it is 1 to 20 minutes. Heating can be done using a hot plate, oven, etc.

[0095] <Process for forming a release adhesive coating layer> The process of forming a release adhesive coating layer is a process of forming a release adhesive coating layer by, for example, applying a release adhesive composition onto a support substrate or applying a release adhesive composition onto a protective adhesive layer. The process for forming the release adhesive coating layer is not particularly limited as long as it is a process for forming a release adhesive coating layer. For example, it may include a process in which a release adhesive composition is applied to a protective adhesive layer or a support substrate, and then heated (preheat treatment) to form a release adhesive coating layer which is an uncured or incompletely cured release adhesive layer. In this way, the release adhesive coating layer is formed on a protective adhesive layer on a semiconductor substrate or on a support substrate.

[0096] The coating method is not particularly limited, but it is usually a spin coating method. Alternatively, a method can be adopted in which a coating film is formed separately by a spin coating method or the like, and the sheet-like coating film is attached as a release adhesive coating layer. The thickness of the release adhesive coating layer is determined appropriately, taking into consideration the desired thickness of the release adhesive layer in the laminate. Because the release adhesive composition contains a solvent or for other reasons, the applied release adhesive composition may be heated for the purpose of drying the coating film of the applied release adhesive composition. The heating temperature of the applied release adhesive composition cannot be specified in general terms, as it varies depending on the type and amount of adhesive components contained in the release adhesive composition, whether or not a solvent is included, the boiling point of the solvent used, the desired thickness of the release adhesive layer, etc. However, it is usually 80 to 150°C, and the heating time is usually 30 seconds to 5 minutes. Heating can be done using a hot plate, oven, etc.

[0097] <Peeling adhesive layer formation process> The release adhesive layer formation process involves heating the release adhesive coating layer to form the release adhesive layer. The process for forming the release adhesive layer is not particularly limited, as long as it involves heating the release adhesive coating layer to form the release adhesive layer (post-heat treatment). For example, a semiconductor substrate and a support substrate on which a protective adhesive layer and a release adhesive coating layer are formed, or a semiconductor substrate on which a protective adhesive layer is formed and a support substrate on which a release adhesive coating layer is formed, can be used to arrange the two substrates (semiconductor substrate and support substrate) so as to sandwich the two layers (protective adhesive layer and release adhesive coating layer), so that the support substrate and the release adhesive coating layer are in contact, and the release adhesive coating layer and the protective adhesive layer are in contact, after which a heat treatment can be performed. The heating temperature and time are not particularly limited, as long as they are the temperature and time required for the release adhesive coating layer to be converted into a release adhesive layer. The heating temperature is preferably 120°C or higher, more preferably 150°C or higher, from the viewpoint of achieving a sufficient curing rate, and preferably 250°C or lower, from the viewpoint of preventing deterioration of each layer constituting the laminate (including the support substrate and semiconductor substrate). Even more preferably, it is 180 to 200°C. The heating time is preferably 1 minute or more, more preferably 5 minutes or more, from the viewpoint of achieving suitable bonding of each layer constituting the laminate (including the support substrate and the semiconductor substrate), and preferably 180 minutes or less, more preferably 120 minutes or less, from the viewpoint of suppressing or avoiding adverse effects on each layer due to excessive heating. Even more preferably, from the viewpoint of substrate processing efficiency, it is 1 to 20 minutes. Heating can be done using a hot plate, oven, etc.

[0098] <Lamination process> Between the process of forming the release adhesive layer and the process of forming the release adhesive layer, it is preferable to perform a bonding process to ensure sufficient bonding between the semiconductor substrate and the support substrate. The bonding process is not particularly limited as long as it allows bonding of the substrate and the layer without damaging the substrate or layer, but typically it is a process in which a load can be applied in the thickness direction of the support substrate and the semiconductor substrate, and more preferably a process in which a load can be applied in the thickness direction of the support substrate and the semiconductor substrate under reduced pressure. The load is not particularly limited as long as it allows the substrate and layer to bond together and does not damage the substrate or layer, but for example, it is between 10 and 1,000 N. The degree of reduced pressure is not particularly limited as long as it allows for bonding of the substrate and the layer without damaging the substrate or the layer, but for example, it is 10 to 10,000 Pa.

[0099] (Method of manufacturing semiconductor substrates) The laminate of the present invention is used for temporary bonding in order to process semiconductor substrates, and is used in applications where the support substrate and the semiconductor substrate are separated after processing of the semiconductor substrate in the laminate. The present invention provides a method for manufacturing a semiconductor substrate, which includes at least a processing step in which the semiconductor substrate is processed, and a peeling step in which the support substrate and the processed semiconductor substrate are separated, and further includes other steps such as a removal step as necessary.

[0100] <Processing process> The processing steps are not particularly limited as long as they involve processing the semiconductor substrate in the laminate of the present invention, but include, for example, polishing and through-electrode formation. For example, various processing steps may involve processing under high temperature and high pressure, but the laminate of the present invention can effectively prevent bump deformation of the semiconductor substrate even when processed under high temperature (e.g., 250-350°C) and high pressure.

[0101] <<Polishing process>> Polishing processes are not particularly limited, but any process that involves polishing the surface of a semiconductor substrate opposite to the surface where bumps are present in order to thin the semiconductor substrate can be used. Examples include physical polishing using abrasives or grinding wheels. The polishing process can be carried out using general polishing equipment used for polishing semiconductor substrates. The polishing process reduces the thickness of the semiconductor substrate, resulting in a semiconductor substrate thinned to a desired thickness. The thickness of the thinned semiconductor substrate is not particularly limited, but for example, it may be 10 to 300 μm or 30 to 100 μm.

[0102] <<Through electrode formation process>> Polished semiconductor substrates may have through-electrodes formed on them to enable electrical conductivity between thinned semiconductor substrates when multiple thinned semiconductor substrates are stacked. Therefore, the method for manufacturing a semiconductor substrate may include a through-electrode formation process in which through-electrodes are formed on the polished semiconductor substrate after the polishing process but before the stripping process. The method for forming through-electrodes in a semiconductor substrate is not particularly limited, but examples include forming through-holes and filling the formed through-holes with a conductive material. The formation of through-holes can be performed, for example, by photolithography. The filling of through-holes with conductive material is carried out, for example, by plating technology.

[0103] <Peeling process> The peeling process is not particularly limited as long as it is a process in which the support substrate and the processed semiconductor substrate are separated after the processing process. For example, one method involves mechanically debonding the substrate using equipment with sharp parts (a so-called debonder). Specifically, for instance, a sharp part is inserted between the semiconductor substrate and the support substrate, and then the semiconductor substrate and the support substrate are separated. Typically, debonding occurs within the release adhesive layer, at the interface between the release adhesive layer and the protective adhesive layer, or at the interface between the release adhesive layer and the support substrate. Often, two or more of these locations combine to cause debonding. Note that debonding occurring within the release adhesive layer means that the release adhesive layer ruptures.

[0104] <Removal process> The removal process is not particularly limited, as long as it involves removing the protective adhesive layer on the semiconductor substrate and the residue of the peeling adhesive layer on top of it after the peeling process. For example, one method is to dissolve and remove them using a cleaning agent composition. Alternatively, removal using a removal tape or the like may be combined with the dissolution removal. When using a cleaning agent composition, for example, a semiconductor substrate with a protective adhesive layer can be immersed in the cleaning agent composition or sprayed onto it. When cleaning semiconductor substrates with a cleaning agent composition, care should be taken to avoid damaging the bumps.

[0105] A suitable example of a detergent composition used in the present invention is a detergent composition comprising a quaternary ammonium salt and a solvent. Quaternary ammonium salts are composed of a quaternary ammonium cation and an anion, and are not particularly limited as long as they are used for this type of application. Typical examples of such quaternary ammonium cations include tetra(hydrocarbon)ammonium cations. On the other hand, the anion that pairs with it is the hydroxide ion (OH - ); fluoride ion (F - ), chloride ions (Cl - ), bromine ions (Br - ), iodide ion (I - ) and other halogen ions; tetrafluoroborate ions (BF4 - ); Hexafluorophosphate ion (PF6 - Examples include, but are not limited to, these.

[0106] In the present invention, the quaternary ammonium salt is preferably a halogen-containing quaternary ammonium salt, and more preferably a fluorine-containing quaternary ammonium salt. In quaternary ammonium salts, halogen atoms may be contained in the cation or the anion, but are preferably contained in the anion.

[0107] In one preferred embodiment, the fluorine-containing quaternary ammonium salt is tetra(hydrocarbon)ammonium fluoride. Specific examples of hydrocarbon groups in tetraammonium fluoride include alkyl groups having 1 to 20 carbon atoms, alkenyl groups having 2 to 20 carbon atoms, alkynyl groups having 2 to 20 carbon atoms, and aryl groups having 6 to 20 carbon atoms. In a more preferred embodiment, tetra(hydrocarbon)ammonium fluoride comprises tetraalkylammonium fluoride. Specific examples of tetraalkylammonium fluoride include, but are not limited to, tetramethylammonium fluoride, tetraethylammonium fluoride, tetrapropylammonium fluoride, and tetrabutylammonium fluoride (also known as tetrabutylammonium fluoride). Among these, tetrabutylammonium fluoride is preferred.

[0108] An example of a method in which the manufacturing of a laminate and the manufacturing of a thinned wafer are carried out in a series will be explained using Figures 2A to 2H. Figures 2A to 2H illustrate one embodiment of the manufacturing process for laminates and thinned wafers. First, prepare a wafer 1 having bumps 1a (Figure 2A). Next, a protective adhesive composition is applied to the surface of wafer 1 where the bumps 1a are present by spin coating using a coating apparatus 11 to form a protective adhesive coating layer 2a (Figure 2B). Next, a heating device (hot plate) 12 is placed on the side of wafer 1 opposite to the side where the bump 1a is located, and the protective adhesive coating layer 2a is heated and cured by the heating device 12 to convert it into the protective adhesive layer 2 (Figure 2C). Next, a release adhesive composition is applied to the protective adhesive layer 2 by spin coating using the coating device 13 to form a release adhesive coating layer 3a (Figure 2D). Next, the support substrate 4 is placed on the release adhesive coating layer 3a (Figure 2E). Next, a load is applied to the wafer 1 and the support substrate 4 in the thickness direction under reduced pressure. Then, a heating device (hot plate) 14 is placed on the side of the wafer 1 opposite to the side where the bump 1a is located, and the release adhesive coating layer 3a is heated and cured by the heating device 14 to convert it into a release adhesive layer 3 (Figure 2F). The laminate is obtained by the process shown in Figures 2A to 2F. Next, we will explain an example of the manufacturing process for thinned wafers. Next, the side of wafer 1 opposite to the side where the bump 1a is located is polished using a polishing device (not shown) to thin the wafer 1 (Figure 2G). The thinned wafer 1 may also be subjected to processes such as the formation of through-electrodes. Next, a peeling device (not shown) is used to separate the thinned wafer 1 from the support substrate 4 (Figure 2H). Next, the thinned wafer 1 is cleaned by using a cleaning apparatus (not shown) to dissolve and remove the protective adhesive layer 2, etc., from the wafer 1 that has been thinned with the cleaning agent composition. The thinned wafer 1 is obtained as a result of the above steps. [Examples]

[0109] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples. The apparatus used is as follows.

[0110] (1) Agitator A: ARE-500, manufactured by Thinky Co., Ltd. (2) Measurement of complex viscosity: Rheometer MCR-302 manufactured by Anton Paar Co., Ltd. (3) Vacuum bonding machine X: Manufactured by Suss Microtech Co., Ltd., manual bonder (4) Vacuum bonding machine Y: Autobonder manufactured by Züss Microtech Co., Ltd. (5) Debonding device X: Manual debonder manufactured by Züss Microtech Co., Ltd.

[0111] The structural formulas of each component used in the examples are shown below.

[0112] [ka]

[0113] [Measurement of molecular weight] The weight-average molecular weight, number-average molecular weight, and dispersion of polydimethylsiloxane were measured using a GPC instrument (EcoSEC HLC-8320GPC, Tosoh Corporation) and GPC columns (TSKgel SuperMultiporeHZ-N, TSKgel SuperMultiporeHZ-H, Tosoh Corporation), with a column temperature of 40°C, tetrahydrofuran as the eluent, and a flow rate of 0.35 mL / min. Polystyrene (Shodex, Showa Denko K.K.) was used as the standard sample.

[0114] [1-1] Preparation of protective adhesive composition [Preparation Example 1] In a 600 mL stirring container of stirrer A, 62.10 g of a vinyl group-containing linear polydimethylsiloxane with a viscosity of 200 mPa·s represented by formula (V) and 82.25 g of a base polymer (manufactured by Wacker Chem Ltd.) consisting of a vinyl group-containing MQ resin was added as component (a1), 15.23 g of a SiH group-containing linear polydimethylsiloxane (manufactured by Wacker Chem Ltd.) with a viscosity of 100 mPa·s was added as component (a2), and 0.42 g of 1-ethynyl-1-cyclohexanol (manufactured by Wacker Chem Ltd.) was added as component (A3). The mixture was stirred with stirrer A for 5 minutes to obtain mixture (I). Mixture (II) was obtained by stirring a 50 mL screw-cap tube with 0.24 g of platinum catalyst (manufactured by Wacker Chem Co., Ltd.) as component (A2) and 10.07 g of vinyl group-containing linear polydimethylsiloxane (manufactured by Wacker Chem Co., Ltd.) with a viscosity of 1000 mPa·s represented by formula (W) as component (a1) using stirrer A for 5 minutes. 7.14 g of the obtained mixture (II) was added to mixture (I), and the mixture was stirred with stirrer A for 5 minutes to obtain mixture (III). Finally, the resulting mixture (III) was filtered through a 300-mesh nylon filter to obtain protective adhesive composition 1. The viscosity of protective adhesive composition 1, as measured using a rotational viscometer, was 9900 mPa·s.

[0115] [1-2] Preparation of release adhesive composition [Preparation Example 2] In a 600 mL stirring container dedicated to stirrer A, 104.14 g of a p-menthane solution (concentration 80.6% by mass) of MQ resin (manufactured by Wacker Chem Co., Ltd.) having a polysiloxane skeleton and vinyl groups was added as component (a1), 58.11 g of polyorganosiloxane represented by formula (M1) (complex viscosity 800 Pa·s, weight-average molecular weight 171,899 (dispersion degree 2.18), manufactured by Wacker Chem Co., Ltd.) was added as component (B), 34.94 g of p-menthane (manufactured by Nippon Terpene Chemical Co., Ltd.) and 6.20 g of n-decane (manufactured by Sankyo Chemical Co., Ltd.) were added, and the mixture was stirred with stirrer A for 5 minutes to obtain mixture (I). To the obtained mixture (I), 16.79 g of SiH group-containing linear polydimethylsiloxane (manufactured by Wacker Chem Ltd.) with a viscosity of 100 mPa·s was added as component (a2), and 24.54 g of vinyl group-containing linear polydimethylsiloxane (manufactured by Wacker Chem Ltd.) with a viscosity of 200 mPa·s represented by formula (V) was added as component (a1), to obtain mixture (II). Mixture (III) was obtained by stirring the aforementioned components (A3) as 1,1-diphenyl-2-propyne-1-ol (manufactured by Tokyo Chemical Industry Co., Ltd.), 1.61 g of 1-ethynyl-1-cyclohexanol (manufactured by Wacker Chem Co., Ltd.), and 3.23 g of p-menthane (manufactured by Nippon Terpene Chemical Co., Ltd.) as a solvent with stirrer A for 60 minutes. 1.29 g of the obtained mixture (III) was added to mixture (II), and the mixture was stirred with stirrer A for 5 minutes to obtain mixture (IV). As component (A2), 0.65 g of platinum catalyst (manufactured by Wacker Chem Co., Ltd.) and as component (a1), 19.37 g of vinyl group-containing linear polydimethylsiloxane (manufactured by Wacker Chem Co., Ltd.) with a viscosity of 1000 mPa·s represented by formula (W) were stirred in stirrer A for 5 minutes to obtain mixture (V). 4.00 g of the obtained mixture (V) was added to mixture (IV), and the mixture was stirred with stirrer A for 5 minutes to obtain mixture (VI). Finally, the obtained mixture (VI) was filtered through a 300-mesh nylon filter to obtain release adhesive composition 1. The viscosity of the obtained release adhesive composition 1 was 3000 mPa·s.

[0116] [Preparation Example 3] In a 600 mL stirring container dedicated to stirrer A, 105.26 g of a p-menthane solution (concentration 80.6% by mass) of MQ resin (manufactured by Wacker Chem Co., Ltd.) having a polysiloxane skeleton and vinyl groups was added as component (a1), 35.24 g of polyorganosiloxane represented by formula (M1) (complex viscosity 6000 Pa·s, weight-average molecular weight 642,000 (dispersion degree 2.6), manufactured by Wacker Chem Co., Ltd., trade name GENIOPLAST GUM), 54.11 g of p-menthane (manufactured by Nippon Terpene Chemical Co., Ltd.), and 8.35 g of n-decane (manufactured by Sankyo Chemical Co., Ltd.) were added as component (B). The mixture was stirred with stirrer A for 5 minutes, with short breaks in between, for a total of 8 times to obtain mixture (I). To the obtained mixture (I), 16.97 g of SiH group-containing linear polydimethylsiloxane (manufactured by Wacker Chem Ltd.) with a viscosity of 100 mPa·s was added as component (a2), and 24.80 g of vinyl group-containing linear polydimethylsiloxane (manufactured by Wacker Chem Ltd.) with a viscosity of 200 mPa·s was added as component (a1), to obtain mixture (II). Mixture (III) was obtained by stirring the following ingredients: 1.63 g of 1,1-diphenyl-2-propyne-1-ol (manufactured by Tokyo Chemical Industry Co., Ltd.) as component (A3), 1.63 g of 1-ethynyl-1-cyclohexanol (manufactured by Wacker Chem Co., Ltd.) as component (A3), and 3.26 g of p-menthane (manufactured by Nippon Terpene Chemical Co., Ltd.) in stirrer A for 5 minutes. 1.31 g of the obtained mixture (III) was added to mixture (II), and the mixture was stirred with stirrer A for 5 minutes to obtain mixture (IV). As component (A2), 0.26 g of platinum catalyst (manufactured by Wacker Chem Co., Ltd.) and as component (a1), 19.58 g of vinyl group-containing linear polydimethylsiloxane (manufactured by Wacker Chem Co., Ltd.) with a viscosity of 1000 mPa·s were stirred in stirrer A for 5 minutes to obtain mixture (V). 3.97 g of the obtained mixture (V) was added to mixture (IV), and the mixture was stirred with stirrer A for 5 minutes to obtain mixture (VI). Finally, the obtained mixture (VI) was filtered through a 300-mesh nylon filter to obtain release adhesive composition 2. The viscosity of the obtained release adhesive composition 2 was 3900 mPa·s.

[0117] [2] Evaluation of adhesion and release properties [Example 1-1] A protective adhesive composition 1 obtained in Preparation Example 1 was applied by spin coating to a 300 mm silicon wafer (thickness: 770 μm) used as the device wafer, and heated at 200°C for 10 minutes to form a protective adhesive layer with a thickness of approximately 32.5 μm on the circuit surface of the wafer. Next, the release adhesive composition 1 obtained in Preparation Example 2 was applied to the protective adhesive layer by spin coating and heated at 120°C for 1.5 minutes (preheat treatment) to form a release adhesive coating layer on the protective adhesive layer such that the thickness of the release adhesive layer in the laminate was approximately 32.5 μm. Subsequently, in a vacuum bonding apparatus Y, a silicon wafer having a protective adhesive layer and a release adhesive coating layer was bonded to a 300 mm glass wafer (thickness: 700 μm) as the carrier wafer (support), with the protective adhesive layer and release adhesive coating layer sandwiched between them. A laminate was then fabricated by heating on a hot plate with the device wafer facing downwards at 200°C for 10 minutes (post-heat treatment). The bonding was performed at a temperature of 23°C, a reduced pressure of 1,000 Pa, and under a load of 30 N.

[0118] [Examples 1-2] A protective adhesive composition 1 obtained in Preparation Example 1 was applied by spin coating to a 300 mm silicon wafer (thickness: 770 μm) used as the device wafer, and heated at 200°C for 10 minutes to form a protective adhesive layer with a thickness of approximately 32.5 μm on the circuit surface of the wafer. Next, the release adhesive composition 2 obtained in Preparation Example 3 was applied to the protective adhesive layer by spin coating and heated at 120°C for 1.5 minutes (preheat treatment) to form a release adhesive coating layer on the protective adhesive layer such that the thickness of the release adhesive layer in the laminate was approximately 32.5 μm. Subsequently, in a vacuum bonding apparatus Y, a silicon wafer having a protective adhesive layer and a release adhesive coating layer was bonded to a 300 mm glass wafer (thickness: 700 μm) as the carrier wafer (support), with the protective adhesive layer and release adhesive coating layer sandwiched between them. A laminate was then fabricated by heating on a hot plate with the device wafer facing downwards at 200°C for 10 minutes (post-heat treatment). The bonding was performed at a temperature of 23°C, a reduced pressure of 1,000 Pa, and under a load of 30 N.

[0119] [Comparative Example 1-1] A protective adhesive coating layer was formed on the circuit surface of the wafer by spin-coating a 300 mm silicon wafer (thickness: 770 μm) used as the device wafer, so that the thickness of the protective adhesive layer in the laminate was approximately 65 μm. Subsequently, in a vacuum bonding apparatus Y, a silicon wafer with a protective adhesive coating layer and a 300 mm glass wafer (thickness: 700 μm) as the carrier wafer (support) were bonded together with the protective adhesive coating layer in between. The laminate was then fabricated by heating on a hot plate with the device wafer facing downwards at 200°C for 10 minutes (post-heat treatment). The bonding was performed at a temperature of 23°C, a reduced pressure of 1,000 Pa, and under a load of 30 N.

[0120] [Comparative Example 1-2] A 300 mm silicon wafer (thickness: 770 μm) was used as the device wafer. The release adhesive composition 1 obtained in Preparation Example 2 was applied by spin coating and heated at 120°C for 1.5 minutes (preheating treatment) to form a release adhesive coating layer on the circuit surface of the wafer such that the thickness of the release adhesive layer in the laminate was approximately 65 μm. Subsequently, in a vacuum bonding apparatus Y, a silicon wafer with a release adhesive coating layer and a 300 mm glass wafer (thickness: 700 μm) as the carrier wafer (support) were bonded together with the release adhesive coating layer in between. The laminate was then fabricated by heating on a hot plate with the device wafer facing downwards at 200°C for 10 minutes (post-heat treatment). The bonding was performed at a temperature of 23°C, a reduced pressure of 1,000 Pa, and under a load of 30 N.

[0121] [Comparative Examples 1-3] A 300 mm silicon wafer (thickness: 770 μm) was used as the device wafer. The release adhesive composition 2 obtained in Preparation Example 3 was applied by spin coating and heated at 120°C for 1.5 minutes (preheating treatment) to form a release adhesive coating layer on the circuit surface of the wafer with a thickness of approximately 65 μm in the release adhesive layer within the laminate. Subsequently, in a vacuum bonding apparatus Y, a silicon wafer with a release adhesive coating layer and a 300 mm glass wafer (thickness: 700 μm) as the carrier wafer (support) were bonded together with the adhesive layer in between. The laminate was then fabricated by heating on a hot plate with the device wafer facing downwards at 200°C for 10 minutes (post-heat treatment). The bonding was performed at a temperature of 23°C, a reduced pressure of 1,000 Pa, and under a load of 30 N.

[0122] The adhesion and peelability of the adhesive layer in each laminate were evaluated using the laminates obtained in Examples 1-1, 1-2, Comparative Example 1-1, Comparative Example 1-2, and Comparative Example 1-3. Adhesion was evaluated by visually checking for voids from the glass wafer (support) side of the laminate. If no voids were found, the result was considered good; if voids were found, the result was considered poor. Here, a void refers to a state where there are air bubbles between the substrate and the layer of the laminate, between two layers, or within a layer. In such a state where undesirable air bubbles are present, sufficient protection of the semiconductor substrate cannot be expected. The peelability was evaluated by measuring the force required to separate the semiconductor substrate from the support substrate. If separation was possible with peeling device X, it was considered good; if separation was not possible, it was considered poor. As a result, no voids were observed in any of the laminates. Regarding peelability, in Examples 1-1 and 1-2, the semiconductor substrate and support substrate could be successfully separated with a force of 15N. It was found that Comparative Example 1-1 could not be peeled using peeling device X. Comparative Examples 1-2 and 1-3 could be peeled with a force of 15N. Thus, it was found that the laminate of the present invention exhibits good peelability even in the presence of the non-peelable protective adhesive composition 1, due to the presence of a peelable adhesive layer.

[0123] [3-1] Confirmation of bump protection performance [Example 2-1] A protective adhesive composition 1 obtained in Preparation Example 1 was applied by spin coating to a PI TEG 4×4cm chip (thickness: 770μm, bump diameter: 0.03mm, bump height: 0.04mm, bump pitch: 0.06×0.1mm) used as the device substrate, and heated at 200°C for 10 minutes to form a protective adhesive layer with a thickness of approximately 32.5μm on the circuit surface of the chip. Next, the release adhesive composition 1 obtained in Preparation Example 2 was applied to the protective adhesive layer by spin coating and heated at 120°C for 1.5 minutes (preheat treatment) to form a release adhesive coating layer such that the thickness of the release adhesive layer in the laminate was approximately 32.5 μm. Subsequently, in a vacuum bonding apparatus X, a chip having a protective adhesive layer and a release adhesive coating layer was bonded to a 100 mm glass wafer (thickness: 770 μm) as the carrier wafer (support), with the protective adhesive layer and release adhesive coating layer sandwiched between them. A laminate was then fabricated by heating on a hot plate with the device wafer facing downwards at 200°C for 10 minutes (post-heat treatment). The bonding was performed at a temperature of 23°C, a reduced pressure of 1,000 Pa, and under a load of 30 N.

[0124] [Example 2-2]~[Example 2-8] In Example 2-1, laminates of Examples 2-2 to 2-8 were obtained by the same method as in Example 2-1, except that the type of adhesive composition and the film thickness of each layer were changed, as shown in Table 1 below.

[0125] [Comparative Example 2-1] A PI TEG 4×4cm chip (thickness: 770μm, bump diameter: 0.03mm, bump height: 0.04mm, bump pitch: 0.06×0.1mm) was used as the substrate for the device side. The release adhesive composition 1 obtained in Preparation Example 2 was applied by spin coating and heated at 120°C for 1.5 minutes (preheat treatment) to form a release adhesive coating layer on the chip such that the thickness of the release adhesive layer in the laminate was approximately 65μm. Subsequently, in a vacuum bonding apparatus X, a chip with a release adhesive coating layer and a 100 mm glass wafer (thickness: 770 μm) serving as the carrier wafer (support) were bonded together with the release adhesive coating layer in between. The laminate was then fabricated by heating on a hot plate with the device wafer facing downwards at 200°C for 10 minutes (post-heat treatment). The bonding was performed at a temperature of 23°C, a reduced pressure of 1,000 Pa, and under a load of 30 N.

[0126] [Comparative Example 2-2] A PI TEG 4×4cm chip (thickness: 770μm, bump diameter: 0.03mm, bump height: 0.04mm, bump pitch: 0.06×0.1mm) was used as the substrate for the device side. The release adhesive composition 2 obtained in Preparation Example 3 was applied by spin coating and heated at 120°C for 1.5 minutes (preheat treatment) to form a release adhesive coating layer on the chip such that the thickness of the release adhesive layer in the laminate was approximately 65μm. Subsequently, in a vacuum bonding apparatus X, a chip with a release adhesive coating layer and a 100 mm glass wafer (thickness: 770 μm) serving as the carrier wafer (support) were bonded together with the release adhesive coating layer in between. The laminate was then fabricated by heating on a hot plate with the device wafer facing downwards at 200°C for 10 minutes (post-heat treatment). The bonding was performed at a temperature of 23°C, a reduced pressure of 1,000 Pa, and under a load of 30 N.

[0127] [Comparative Example 2-3] A protective adhesive coating layer was formed on a PI TEG 4×4cm chip (thickness: 770μm, bump diameter: 0.03mm, bump height: 0.04mm, bump pitch: 0.06×0.1mm) used as the substrate for the device side. The protective adhesive composition 1 obtained in Preparation Example 1 was applied by spin coating, so that the thickness of the protective adhesive layer in the laminate was approximately 65μm. Subsequently, in a vacuum bonding apparatus X, the chip having this adhesive layer and a 100 mm glass wafer (thickness: 770 μm) serving as the carrier wafer (support) were bonded together with the adhesive layer in between. The laminate was then fabricated by heating on a hot plate with the device wafer facing downwards at 200°C for 10 minutes (post-heat treatment). The bonding was performed at a temperature of 23°C, a reduced pressure of 1,000 Pa, and under a load of 30 N.

[0128] [Comparative Example 2-4] A PI TEG 4×4cm chip (thickness: 770μm, bump diameter: 0.03mm, bump height: 0.04mm, bump pitch: 0.06×0.1mm) was used as the substrate for the device side. The release adhesive composition 1 obtained in Preparation Example 2 was applied by spin coating, and the chip was heated at 120°C for 1.5 minutes (preheat treatment) to remove residual solvent on the chip. Further heating at 200°C for 10 minutes formed a release adhesive coating layer on the chip such that the thickness of the release adhesive layer in the laminate was approximately 32.5μm. Next, protective adhesive composition 1 obtained in Preparation Example 1 was applied to the release adhesive coating layer by spin coating, forming a protective adhesive coating layer on top of the release adhesive coating layer such that the thickness of the protective adhesive layer in the laminate was approximately 32.5 μm. Subsequently, in a vacuum bonding apparatus X, a chip having a release adhesive coating layer and a protective adhesive coating layer was bonded to a 100 mm glass wafer (thickness: 770 μm) as the carrier wafer (support), with the release adhesive coating layer and protective adhesive coating layer sandwiched between them. A laminate was then fabricated by heating on a hot plate with the device wafer facing downwards at 200°C for 10 minutes (post-heat treatment). The bonding was performed at a temperature of 23°C, a reduced pressure of 1,000 Pa, and under a load of 30 N.

[0129] [3-2] Evaluation of high-temperature treatment High-temperature treatment was performed on each laminate obtained in Examples 2-1, 2-2, 2-3, 2-4, 2-5, 2-6, 2-7, 2-8, Comparative Examples 2-1, 2-2, 2-3, and 2-4 using a hot plate. High-temperature treatment was performed on each laminate on the day of production (before storage) and 10 days after production (after storage). The high-temperature treatment was carried out in the following procedure. The laminated glass wafer (support substrate) was placed face down on a hot plate set to 270°C and heated for 5 minutes. The condition of the silicon wafer, which is the semiconductor substrate of each laminate after processing, was observed using an optical microscope through the glass wafer, which is the support substrate, to visually confirm whether or not bump deformation was present. There are 5044 bumps in one laminate. If the number of deformed bumps is 0 or more but less than 50, it is marked with ○; if it is 50 or more but less than 100, it is marked with △; and if it is 100 or more, it is marked with ×. The results are shown in Table 1 below. In Table 1, the numbers in parentheses indicate the film thickness of each layer.

[0130] [Table 1]

[0131] As shown in the results in Table 1, the laminates obtained in Examples 2-1 to 2-8 exhibited good bump protection performance. In particular, they maintained good bump protection performance even after being stored for a period of time. On the other hand, in the laminates of Comparative Examples 2-1, 2-2, and 2-4, numerous bump deformations were observed after pre-fabrication. The results from the examples showed that the laminate of the present invention is a laminate that allows for easy separation of the semiconductor substrate and the support substrate, and has excellent bump protection performance that suppresses bump deformation. [Industrial applicability]

[0132] According to the present invention, a laminate can be provided that allows for easy separation of the semiconductor substrate and the support substrate, and that suppresses bump deformation, making it useful for the manufacture of processed semiconductor substrates. [Explanation of symbols]

[0133] 1 wafer 1a Bump 2 Protective adhesive layer 2a Protective adhesive coating layer 3. Release adhesive layer 3a Coating layer for release adhesive 4. Support substrate 11. Coating device 12 Heating device 13. Coating device 14 Heating device

Claims

1. A laminate comprising a bumped semiconductor substrate, a support substrate, a protective adhesive layer formed in contact with the bumped semiconductor substrate, and a release adhesive layer formed between the protective adhesive layer and the support substrate, The protective adhesive layer is formed from a protective adhesive composition, the protective adhesive composition contains a component (A) that hardens by a hydrosilylation reaction, and does not contain a release agent component (B) that does not cause a hardening reaction in the hardening component (A). The release adhesive layer is formed from a release adhesive composition, the release adhesive composition comprising a component (A) that hardens by a hydrosilylation reaction and a release agent component (B) that does not cause the hardening reaction that occurs in the hardening component (A), The component (A) contained in the protective adhesive composition contains a polyorganosiloxane (a1) having alkenyl groups with 2 to 40 carbon atoms bonded to silicon atoms, a polyorganosiloxane (a2) having Si-H groups, and a platinum group metal catalyst (A2). The component (A) contained in the aforementioned release adhesive composition contains a polyorganosiloxane (a1) having alkenyl groups with 2 to 40 carbon atoms bonded to silicon atoms, a polyorganosiloxane (a2) having Si-H groups, and a platinum group metal catalyst (A2). A laminate in which the release agent component (B) contained in the release adhesive composition is a polyorganosiloxane that is one of the following: an epoxy group-containing polyorganosiloxane, a methyl group-containing polyorganosiloxane, and a phenyl group-containing polyorganosiloxane.

2. The laminate according to claim 1, wherein the release agent component (B) contained in the release adhesive composition is a polydimethylsiloxane which is any of epoxy group-containing polydimethylsiloxane, unmodified polydimethylsiloxane, and phenyl group-containing polydimethylsiloxane.

3. A step of processing the semiconductor substrate in the laminate according to claim 1 or 2, The process involves separating the protective adhesive layer and the release adhesive layer, thereby separating the support substrate and the processed semiconductor substrate. A method for manufacturing a semiconductor substrate, including the method described above.

4. The method for manufacturing a semiconductor substrate according to claim 3, wherein the processing step includes polishing the surface of the semiconductor substrate opposite to the surface on which the bumps are located, thereby thinning the semiconductor substrate.

5. A method for manufacturing a laminate according to claim 1 or 2, A protective adhesive coating layer formation step, in which a protective adhesive coating layer is formed by applying the protective adhesive composition to the surface of the semiconductor substrate on which the bumps exist, A protective adhesive layer formation step involves heating the protective adhesive coating layer to form the protective adhesive layer, A step of forming a release adhesive coating layer by applying the release adhesive composition onto the support substrate or applying the release adhesive composition onto the protective adhesive layer, A release adhesive layer forming step is performed in which the release adhesive coating layer and the protective adhesive layer are in contact, and the release adhesive coating layer and the support substrate are in contact, and the release adhesive coating layer is heated to form the release adhesive layer. A method for manufacturing a laminate, including the following:

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