Adhesive composition, laminate, production method for laminate, and production method for processed semiconductor substrate or electronic device substrate

Abstract

Provided is a laminate comprising a supporting substrate, a semiconductor substrate or an electronic device substrate, and an adhesive layer formed between the supporting substrate and the semiconductor substrate or the electronic device substrate. When a semiconductor wafer, which is the semiconductor substrate or the electronic device substrate, is separated from the supporting substrate, device separation occurs at a separation interface that is the interface between the semiconductor wafer and the adhesive layer.　Also provided is an adhesive composition for forming an adhesive layer between a supporting substrate and a semiconductor substrate or an electronic device substrate, the adhesive composition comprising: an adhesive component (A) which cures upon a hydrosilylation reaction; and a silane coupling agent having an ethylenically unsaturated group.

Description

Adhesive composition, laminate, method for manufacturing the laminate, and method for manufacturing a processed semiconductor substrate or electronic device substrate.

[0001] The present invention relates to an adhesive composition, a laminate, a method for manufacturing a laminate, and a method for manufacturing a processed semiconductor substrate or electronic device substrate.

[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 in multiple layers while connecting them with through-silicon vias (TSVs). When integrating in 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.

[0003] Before thinning, the semiconductor wafer (also simply called a wafer here) is bonded to a support in order to be polished using a polishing device. This bonding is called temporary bonding because it must be easily removed after polishing. This temporary bonding must be easily removed from the support, as applying too much force during removal can cause the thinned semiconductor wafer to cut or deform. To prevent this, it must be easily removed. However, it is undesirable for the temporary bonding to detach or shift due to polishing stress during back-side polishing of the semiconductor wafer. Therefore, the required performance of the temporary bonding is to withstand the stress during polishing and to be easily removed after polishing.

[0004] As temporary adhesives used for such temporary bonding, adhesives containing polydimethylsiloxane (Patent Document 1) and temporary adhesives containing epoxy-modified polysiloxane (Patent Document 2) have been proposed.

[0005] International Publication No. 2017 / 221772 Brochure International Publication No. 2018 / 216732 Brochure

[0006] As mentioned above, in temporary bonding of a semiconductor wafer to a support, the adhesive layer formed from the temporary adhesive during temporary bonding must be difficult to peel off from the support and semiconductor wafer, while the adhesive layer must be easily peeled off from the support and semiconductor wafer when peeling the semiconductor wafer from the support. When peeling a semiconductor wafer from a support, the peeling location may be the interface between the semiconductor wafer and the adhesive layer (also called device peeling or device release) or the interface between the support and the adhesive layer (also called carrier peeling or carrier release). For example, if the peeling is carrier peeling, the adhesive layer remains (adheres) to the device side of the semiconductor wafer, which raises concerns that cleaning the adhesive layer after peeling will take longer and increase the process time compared to device peeling, and that the cleaning burden on the semiconductor wafer device substrate will be greater. Therefore, device peeling is preferable to avoid the above concerns. Therefore, when peeling a semiconductor wafer from a support, it is convenient that the peeling site (peeling interface) is the interface between the semiconductor wafer and the adhesive layer, which is the device release.

[0007] The present invention has been made in view of the above circumstances, and aims to provide a laminate having a support substrate, a semiconductor substrate or an electronic device substrate, and an adhesive layer provided between the semiconductor substrate or the electronic device substrate and the support substrate, wherein when a semiconductor wafer, which is a semiconductor substrate or an electronic device substrate, is peeled off from the support substrate, the peeling interface is the interface between the semiconductor wafer and the adhesive layer, which is device peeling.

[0008] The inventors of the present invention conducted diligent research to solve the aforementioned problems and found that by including a specific silane coupling agent in addition to a specific adhesive component in an adhesive composition for forming an adhesive layer, the aforementioned problems can be solved, and thus completed the present invention having the following gist.

[0009] In other words, the present invention encompasses the following: [1] An adhesive composition for forming an adhesive layer provided between a support substrate and a semiconductor substrate or an electronic device substrate, wherein the adhesive composition comprises an adhesive component (A) that hardens by a hydrosilylation reaction and a silane coupling agent having an ethylenically unsaturated group. [2] The adhesive composition according to [1], wherein the silane coupling agent having an ethylenically unsaturated group is a silane compound represented by the following formula (1). (In formula (1), R １ (wherein Q represents a methyl group or an ethyl group, Q represents a monovalent organic group having an ethylenically unsaturated group, and n represents an integer from 0 to 2.) [3] The adhesive composition according to [2], wherein the group represented by Q in formula (1) is a monovalent group represented by the following formula (i-1) or a monovalent group represented by the following formula (ii-1). (In equation (i-1) or equation (ii-1), R ２１ R represents an alkylene group with 1 to 10 carbon atoms. ２２ R represents a hydrogen atom or a methyl group. ２３ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and * represents a bond that is attached to the silicon atom in formula (1).) [4] The adhesive composition according to [2], wherein the silane compound represented by formula (1) is the silane compound represented by the following formula (1a). (In formula (1a), R １ (wherein represents a methyl group or an ethyl group, and Q represents a monovalent organic group having an ethylenically unsaturated group.) [5] The adhesive composition according to [3], wherein the monovalent group represented by formula (ii-1) is the monovalent group represented by the following formula (ii-1a). (In formula (ii-1a), R ２１ represents an alkylene group having 1 to 10 carbon atoms. * represents a bond that attaches to the silicon atom in formula (1).) [6] The adhesive composition according to [4], wherein the silane compound represented by formula (1a) is a silane compound represented by the following formula (11) or a silane compound represented by the following formula (12). (In equations (11) and (12), R １ R represents a methyl group or an ethyl group.２１ represents an alkylene group having 1 to 10 carbon atoms.) [7] The silane compound represented by the formula (1a) is at least one silane compound selected from the following silane compounds, and the adhesive composition according to [6]. [8] The adhesive composition further contains a release agent component (B), and the adhesive composition according to any one of [1] to [7]. [9] The adhesive component (A) cured by the hydrosilylation reaction is SiO ２ a siloxane unit (Q unit) represented by, 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 a polysiloxane (A1) containing a siloxane unit selected from the group consisting of two or more combinations thereof (R １ to R ６ each independently represents a monovalent chemical group which is an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms or a hydrogen atom, provided that R １ to R ６The adhesive composition according to any one of [1] to [8], comprising a (1) which is bonded to a silicon atom by a Si-C bond or a Si-H bond, and a platinum group metal catalyst (A2).

[10] The adhesive composition according to [8], wherein the release agent component (B) comprises an epoxy group-containing polyorganosiloxane.

[11] A laminate having a support substrate, a semiconductor substrate or an electronic device substrate, and an adhesive layer provided between the semiconductor substrate or the electronic device substrate and the support substrate, wherein the adhesive layer is an adhesive layer formed from the adhesive composition according to any one of [1] to

[10] .

[12] A method for manufacturing a laminate having a support substrate, a semiconductor substrate or an electronic device substrate, and an adhesive layer provided between the semiconductor substrate or the electronic device substrate and the support substrate, comprising: a step of applying an adhesive composition according to any one of [1] to

[10] to the semiconductor substrate or the electronic device substrate to form an adhesive coating layer on the semiconductor substrate or the electronic device substrate; a step of arranging a support substrate so as to sandwich the adhesive coating layer formed on the semiconductor substrate or the electronic device substrate, and bonding the semiconductor substrate or the electronic device substrate and the support substrate; and a step of heating the adhesive coating layer to form an adhesive layer, and bonding the semiconductor substrate or the electronic device substrate and the support substrate via the adhesive layer.

[13] A method for manufacturing a processed semiconductor substrate or an electronic device substrate, comprising: a fifth step of processing the semiconductor substrate or the electronic device substrate of the laminate according to

[11] ; and a sixth step of separating the semiconductor substrate or the electronic device substrate processed in the fifth step from the support substrate.

[0010] According to the present invention, in a laminate having a support substrate, a semiconductor substrate or an electronic device substrate, and an adhesive layer provided between the semiconductor substrate or the electronic device substrate and the support substrate, it is possible to provide a laminate in which, when a semiconductor wafer which is a semiconductor substrate or an electronic device substrate is peeled off from the support substrate, the peeling interface becomes a device peel, which is the interface between the semiconductor wafer and the adhesive layer.

[0011] Figure 1 is a schematic cross-sectional view of an example of a laminate. Figure 2 is a schematic cross-sectional view of another example of a laminate. Figure 3A is a schematic cross-sectional view (part 1) illustrating the manufacturing method of the laminate shown in Figure 1. Figure 3B is a schematic cross-sectional view (part 2) illustrating the manufacturing method of the laminate shown in Figure 1. Figure 4A is a schematic cross-sectional view (part 1) illustrating the manufacturing method of the laminate shown in Figure 2. Figure 4B is a schematic cross-sectional view (part 2) illustrating the manufacturing method of the laminate shown in Figure 2. Figure 4C is a schematic cross-sectional view (part 3) illustrating the manufacturing method of the laminate shown in Figure 2.

[0012] (Laminate) The laminate of the present invention is a laminate comprising a support substrate, a semiconductor substrate or electronic device substrate, and an adhesive layer provided between the semiconductor substrate or electronic device substrate and the support substrate, wherein the adhesive layer is formed from a specific adhesive composition described below. The laminate is used in applications where the support substrate and the semiconductor substrate or electronic device substrate are separated after processing of the semiconductor substrate or electronic device substrate in the laminate. In this specification, the semiconductor substrate or electronic device substrate may also be read as a semiconductor wafer.

[0013] The laminate of the present invention is used for temporary bonding when processing semiconductor substrates or electronic device substrates, and is suitably used for processing such as thinning of semiconductor substrates or electronic device substrates (hereinafter, "semiconductor substrates or electronic device substrates" are collectively referred to as "semiconductor substrates, etc."). While the semiconductor substrate, etc. is being processed such as thinning, the semiconductor substrate, etc. is supported by a support substrate. On the other hand, after processing the semiconductor substrate, etc., the semiconductor substrate, etc. and the support substrate are separated. After the semiconductor substrate, etc. and the support substrate are separated, the residue of the adhesive layer remaining on the semiconductor substrate or electronic device substrate can be removed, for example, by a cleaning agent composition for cleaning the semiconductor substrate, etc.

[0014] The individual components that make up the laminate are described below.

[0015] <Adhesive Layer> The adhesive layer is provided between the support substrate and the semiconductor substrate or electronic device substrate (semiconductor substrate, etc.). The adhesive layer is in contact with, for example, the semiconductor substrate, etc. Also, the adhesive layer is in contact with, for example, the support substrate. The adhesive layer is formed from an adhesive composition.

[0016] The thickness of the adhesive layer in the laminate of the present invention is not particularly limited, but is usually 5 to 500 μm. From the viewpoint of maintaining film strength, it is preferably 10 μm or more, more preferably 20 μm or more, and even more preferably 30 μm or more. From the viewpoint of avoiding non-uniformity caused by thick films, it is preferably 200 μm or less, more preferably 150 μm or less, even more preferably 120 μm or less, and still more preferably 100 μm or less.

[0017] The method for forming an adhesive layer from an adhesive composition will be described in detail in the section describing the manufacturing method of the laminate.

[0018] <<Adhesive Composition>> The adhesive composition according to the present invention contains an adhesive component (A) that hardens by a hydrosilylation reaction and a silane coupling agent having an ethylenically unsaturated group. The adhesive composition according to the present invention may contain other components.

[0019] The adhesive composition according to the present invention contains a silane coupling agent having an ethylenically unsaturated group in addition to an adhesive component (A) that hardens by a hydrosilylation reaction, thereby providing a laminate in which the delamination interface when peeling the semiconductor wafer from the support substrate is the interface between the semiconductor wafer and the adhesive layer, resulting in device delamination. The inventors believe this is because: A detailed explanation of the method of manufacturing a laminate by applying the adhesive composition onto a semiconductor substrate, etc., and then placing a support substrate on the adhesive coating layer will be given later, but the inventors believe that the following occurs in such a manufacturing method. After applying the adhesive composition onto a semiconductor substrate, etc., a low-temperature heat treatment (also called soft bake or pre-bake) is performed to evaporate the residual solvent in the coating film and to strengthen the adhesion between the coating film and the semiconductor substrate, etc. However, when a low-temperature heat treatment is performed, the silane coupling agent in the adhesive composition tends to accumulate in large quantities on the surface of the adhesive coating layer that is in contact with air, that is, on the side of the adhesive coating layer that is in contact with the semiconductor substrate, etc. Therefore, after placing the support substrate on the side of the adhesive coating layer that is in contact with air, the semiconductor substrate and the support substrate are bonded together so as to sandwich the adhesive coating layer, and then the adhesive coating layer is post-heated (main heating) to form the adhesive layer, and the semiconductor substrate and the support substrate are bonded together via the adhesive layer, the functional group (Si-OR) of the silane coupling agent molecule １ (R １ The adhesive layer and the support substrate adhere firmly through the reaction of methyl or ethyl groups (such as methyl groups) with hydroxyl groups (-OH) on the surface of the support substrate. Furthermore, the ethylenically unsaturated group of the silane coupling agent molecule reacts with the remaining SiH groups in the adhesive layer, further improving the adhesion between the adhesive layer and the support substrate.

[0020] A preferred embodiment of the adhesive composition according to the present invention is, for example, an adhesive composition containing an adhesive component (A) that hardens by a hydrosilylation reaction, a release agent component (B), and a silane coupling agent having an ethylenically unsaturated group. Here, the release agent component (B) is a component that does not undergo a hydrosilylation reaction and does not undergo a hardening reaction. For example, a non-hardening polyorganosiloxane is an example. In this invention, "does not undergo a hardening reaction" does not mean that no hardening reaction occurs at all, but rather that the hardening reaction that occurs in the hardening adhesive component (A) does not occur.

[0021] <<<<Adhesive component (A)>>> Adhesive component (A) is a component that hardens by a hydrosilylation reaction. Adhesive component (A) may also be a polyorganosiloxane component (A') that hardens by a hydrosilylation reaction. Adhesive component (A) is SiO ２ Siloxane units (Q units) represented by R １ R ２ R ３ SiO １／２ Siloxane units (M units) expressed as R ４ R ５ SiO ２／２ Siloxane units (D units) represented by R ６ SiO ３／２ A polysiloxane (A1) (R) containing siloxane units (T units) represented by the following, and siloxane units selected from the group consisting of two or more combinations thereof. １ ~R ６ Each of these independently represents a monovalent chemical group consisting of an alkyl group with 1 to 10 carbon atoms, an alkenyl group with 2 to 10 carbon atoms, or a hydrogen atom, except R １ ~R ６ Each of these is bonded to a silicon atom by a Si-C bond or a Si-H bond.) A more preferred embodiment of the adhesive component (A) is an adhesive component containing the above polysiloxane (A1) and a platinum group metal catalyst (A2).

[0022] R １ ~R ６This 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.

[0023] <<<<<Polysiloxane component (A1)>>>> Polysiloxane (A1) is, for example, polyorganosiloxane (a1) (the polyorganosiloxane (a1) has alkenyl groups with 2 to 10 carbon atoms and SiO ２ Siloxane units (Q' units) represented by R ６ 'SiO ３／２ It contains at least one of the siloxane units (T' units) represented by R ６ ' represents a monovalent chemical group which is an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms.) and polyorganosiloxane (a2) (the polyorganosiloxane (a2) has a Si-H group and SiO ２ Siloxane units (Q'' units) expressed as R １ "R ２ "R ３ "SiO １／２ Siloxane units (M'' units) expressed as R ４ "R ５ "SiO ２／２ Siloxane units (D'' units) represented by R ６ "SiO ３／２ The siloxane unit (T'' unit) represented by R is included, and the siloxane unit selected from the group consisting of two or more combinations thereof. １ “~R ６ (Each of these independently represents an alkyl group or hydrogen atom having 1 to 10 carbon atoms.) It contains the following:

[0024] Polysiloxane (A1) is further composed of polyorganosiloxane (a3) ​​(the polyorganosiloxane (a3) ​​is R １ 'R ２ 'R ３ 'SiO １／２ Siloxane units (M' units) represented by R４ 'R ５ 'SiO ２／２ It contains at least one of the siloxane units (D' units) represented by R １ '~R ５ Each of these independently represents a monovalent chemical group which is an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms. It is preferable that it contains ). Note that polyorganosiloxane (a3) ​​is different from polyorganosiloxane (a1).

[0025] The above polyorganosiloxane (a1) has alkenyl groups with 2 to 10 carbon atoms, and SiO ２ Siloxane units (Q' units) represented by R ６ 'SiO ３／２ It contains at least one of the siloxane units (T' units) represented by R １ 'R ２ 'R ３ 'SiO １／２ Siloxane units (M' units) expressed as R ４ 'R ５ 'SiO ２／２ It includes siloxane units (D' units) represented by and siloxane units selected from the group consisting of two or more combinations thereof, R １ '~R ６ Preferably, the polyorganosiloxane is one in which each of the following independently represents a monovalent chemical group that is an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms.

[0026] 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.

[0027] R １ "~R６ " represents a group or atom bonded to a silicon atom, and each independently represents an optionally substituted alkyl group or hydrogen atom, 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.

[0028] 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.

[0029] 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, and 4-methyl-n-pentyl group. Examples of methyl groups include, but are not limited to, 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. 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.

[0030] Specific examples of cyclic alkyl groups, whether substituted or not, 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, and 3,3-dimethyl-cyclobutyl group. Examples of cycloalkyl groups include cycloalkyl groups such as 2-cyclobutyl, 1-n-propyl-cyclopropyl, 2-n-propyl-cyclopropyl, 1-i-propyl-cyclopropyl, 2-i-propyl-cyclopropyl, 1,2,2-trimethyl-cyclopropyl, 1,2,3-trimethyl-cyclopropyl, 2,2,3-trimethyl-cyclopropyl, 1-ethyl-2-methyl-cyclopropyl, 2-ethyl-1-methyl-cyclopropyl, 2-ethyl-2-methyl-cyclopropyl, and 2-ethyl-3-methyl-cyclopropyl; bicycloalkyl groups such as bicyclobutyl, bicyclopentyl, bicyclohexyl, bicycloheptyl, bicyclooctyl, bicyclononyl, and bicyclodecyl. However, the number of carbon atoms is usually 3 to 14, preferably 4 to 10, and more preferably 5 to 6.

[0031] The alkenyl group may be linear or branched, and its number of carbon atoms 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.

[0032] Specific examples of the linear or branched alkenyl group which may be substituted include a vinyl group, an allyl group, a butenyl group, a pentenyl group, etc., but are not limited thereto. The number of carbon atoms thereof is usually 2 to 14, preferably 2 to 10, more preferably 1 to 6. Among them, an ethenyl group and a 2-propenyl group are particularly preferred. Specific examples of the cyclic alkenyl group which may be substituted include cyclopentenyl, cyclohexenyl, etc., but are not limited thereto. The number of carbon atoms thereof is usually 4 to 14, preferably 5 to 10, more preferably 5 to 6.

[0033] As described above, the polysiloxane (A1) contains a polyorganosiloxane (a1) and a polyorganosiloxane (a2), and more preferably contains a polyorganosiloxane (a1), a polyorganosiloxane (a3), and a polyorganosiloxane (a2). In the present specification, the combination of the polyorganosiloxane (a1) and the polyorganosiloxane (a3) is also referred to as "polyorganosiloxane (a1) etc.". The alkenyl group contained in the polyorganosiloxane (a1) etc. and the hydrogen atom (Si-H group) contained in the polyorganosiloxane (a2) form a crosslinked structure and are cured by a hydrosilylation reaction with a platinum group metal-based catalyst (A2). As a result, a cured film is formed.

[0034] The polyorganosiloxane (a1) etc. is composed of siloxane units in which an alkyl group and / or an alkenyl group is bonded to the silicon atom, but １ ’ to R ６ ’ The proportion of the alkenyl group in all the substituents represented by is preferably 0.1 to 50.0 mol%, more preferably 0.5 to 30.0 mol%, and the remaining R １ ’ to R ６ ’ can be an alkyl group.

[0035] The polyorganosiloxane (a2) is composed of siloxane units in which an alkyl group and / or a hydrogen atom is bonded to the silicon atom, but R １ '' to R ６The 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 "~R ６ " can be an alkyl group.

[0036] Polysiloxane (A1) is composed of polyorganosiloxane (a2) relative to the total amount of polyorganosiloxane (a1) and polyorganosiloxane (a3). For example, the molar ratio of alkenyl groups contained in polyorganosiloxane (a1), etc., to hydrogen atoms constituting the Si-H bond in polyorganosiloxane (a2) is in the range of 1.0:0.5 to 1.0:0.66.

[0037] The weight-average molecular weight of the polysiloxanes in polyorganosiloxane (a1), polyorganosiloxane (a3), and polyorganosiloxane (a2) is not particularly limited, but is usually 500 to 1,000,000 each, 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 velocity) of 0.35 mL / min, and polystyrene (Shodex manufactured by Showa Denko K.K.) as the standard sample.

[0038] The viscosities of polyorganosiloxane (a1), polyorganosiloxane (a3), and polyorganosiloxane (a2) are not particularly limited, but are typically 10 to 1,000,000 (mPa·s), and preferably 50 to 10,000 (mPa·s) from the viewpoint of reproducibly realizing the effects of the present invention. The viscosities of polyorganosiloxane (a1), polyorganosiloxane (a3), and polyorganosiloxane (a2) are values ​​measured with an E-type rotational viscometer at 25°C.

[0039] Polyorganosiloxane (a1), polyorganosiloxane (a3), and polyorganosiloxane (a2) react with each other via hydrosilylation. Therefore, the mechanism of curing is different from that mediated by, for example, silanol groups, and thus none of the siloxanes need to contain silanol groups or functional groups that form silanol groups through hydrolysis, such as alkyloxy groups.

[0040] <<<<<Platinum Group Metal Catalyst (A2)>>>>> The adhesive composition of the present invention may contain a platinum group metal catalyst (A2) together with the polyorganosiloxane component (A'). The platinum group metal catalyst is a platinum-based metal catalyst. Such a platinum-based metal catalyst is a catalyst for promoting the hydrosilylation reaction between an alkenyl group and a Si-H group.

[0041] Specific examples of platinum-based metal catalysts include known platinum-based compounds (platinum or compounds containing platinum). Specific examples include platinum powder, platinum black, chloroplatinic acid, alcohol-modified chloroplatinic acid, complexes of chloroplatinic acid with diolefins, platinum-olefin complexes, platinum-carbonyl complexes (e.g., platinum-bis(acetacetate), platinum-bis(acetylacetonate)), chloroplatinic acid-alkenylsiloxane complexes (e.g., chloroplatinic acid-divinyltetramethyldisiloxane complex, chloroplatinic acid-tetravinyltetramethylcyclotetrasiloxane complex), platinum-alkenylsiloxane complexes (e.g., platinum-divinyltetramethyldisiloxane complex, platinum-tetravinyltetramethylcyclotetrasiloxane complex), and complexes of chloroplatinic acid with acetylene alcohols. Among these, platinum-alkenylsiloxane complexes are particularly preferred due to their high efficacy in promoting hydrosilylation reactions. These hydrosilylation catalysts may be used individually or in combination of two or more.

[0042] The alkenylsiloxane used in the platinum-alkenylsiloxane complex is not particularly limited, but examples include 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, alkenylsiloxane oligomers obtained by substituting some of the methyl groups of these alkenylsiloxanes with ethyl groups, phenyl groups, etc., and alkenylsiloxane oligomers obtained by substituting the vinyl groups of these alkenylsiloxanes with allyl groups, hexenyl groups, etc. In particular, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane is preferred because the resulting platinum-alkenylsiloxane complex has good stability.

[0043] The content of the platinum group metal catalyst (A2) in the adhesive composition is not particularly limited, but is, for example, in the range of 0.1 to 50.0 ppm relative to the total mass of polyorganosiloxane (a1), polyorganosiloxane (a3), and polyorganosiloxane (a2).

[0044] <<

[0045] <<<Release Agent Component (B)>>> Examples of release agent component (B) include non-curing polyorganosiloxanes, and specific examples include epoxy group-containing polyorganosiloxanes, methyl group-containing polyorganosiloxanes, and phenyl group-containing polyorganosiloxanes. From the viewpoint of more favorably obtaining the effects of the present invention, epoxy group-containing polyorganosiloxanes are preferred. Polyorganosiloxanes as release agent components do not usually react with adhesive components. For example, polyorganosiloxanes as release agent components are components that do not undergo hydrosilylation reactions.

[0046] Furthermore, polydimethylsiloxane can be used as the release agent component (B). The polydimethylsiloxane may be modified. Examples of polydimethylsiloxane that may be modified include, but are not limited to, epoxy group-containing polydimethylsiloxane, polydimethylsiloxane, and phenyl group-containing polydimethylsiloxane.

[0047] The adhesive composition of the present invention may contain two or more release agent components.

[0048] 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 polyorganosiloxane. The viscosity of the polyorganosiloxane, which is the release agent component (B), is not particularly limited, but is usually 1,000 to 2,000,000 mm². ２ The value is / s. The viscosity of the release agent component (B), polyorganosiloxane, is expressed as kinematic viscosity, centistokes (cSt) = mm². ２ It is / s. Viscosity (mPa·s) is compared to density (g / cm³). ３It can also be obtained by dividing by (). That is, the value can be obtained from the viscosity and density measured with an E-type rotational viscometer at 25°C, and the kinematic viscosity (mm ２ / s) = viscosity (mPa·s) / density (g / cm ３ ), and can be calculated from the formula.

[0049] <<<< Epoxy group-containing polyorganosiloxane >>>> The epoxy group-containing polyorganosiloxane contained in the adhesive composition is not particularly limited. The epoxy group-containing polyorganosiloxane is a component that does not cause a hydrosilylation reaction.

[0050] Examples of the epoxy group-containing polyorganosiloxane include, for example, R １１ R １２ SiO ２／２ The siloxane unit (D １０ unit) represented by is included.

[0051] R １１ is a group bonded to a silicon atom and represents an alkyl group, and R １２ is a group bonded to a silicon atom and represents an epoxy group or an organic group containing an epoxy group. Specific examples of the alkyl group can include the above examples. The epoxy group in the organic group containing an epoxy group may be an independent epoxy group without condensing with other rings, or may be an epoxy group forming a condensed ring with other rings, such as a 1,2-epoxycyclohexyl group. Specific examples of the organic group containing an epoxy group include, but are not limited to, 3-glycidoxypropyl and 2-(3,4-epoxycyclohexyl)ethyl. In the present invention, a preferred example of the epoxy group-containing polyorganosiloxane can include, but is not limited to, epoxy group-containing polydimethylsiloxane.

[0052] The epoxy group-containing polyorganosiloxane contains the above siloxane unit (D １０ unit), but in addition to the D １０ unit, it may also contain a Q unit, an M unit, and / or a T unit. In a preferred embodiment of the present invention, specific examples of the epoxy group-containing polyorganosiloxane include D１０ 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.

[0053] The epoxy group-containing polyorganosiloxane is preferably an epoxy group-containing polydimethylsiloxane having an epoxy value of 0.1 to 5. Its weight-average molecular weight is not particularly limited, but is usually 1,500 to 500,000, and is preferably 100,000 or less from the viewpoint of suppressing precipitation in the composition.

[0054] Specific examples of epoxy group-containing polyorganosiloxanes include, but are not limited to, those represented by formulas (E1) to (E3).

[0055] (m １ and n １ (This indicates the number of each repeating unit and is a positive integer.)

[0056] (m ２ and n ２ R is a positive integer indicating the number of repeating units, and R is an alkylene group having 1 to 10 carbon atoms, which may be interrupted by at least one of the oxygen atoms and unsaturated bonds (e.g., carbon-carbon double bond, carbon-carbon triple bond, -N=N-).

[0057] (m ３ , n ３ and o ３ R is a positive integer indicating the number of repeating units, and R is an alkylene group having 1 to 10 carbon atoms, which may be interrupted by at least one of the oxygen atoms and unsaturated bonds (e.g., carbon-carbon double bond, carbon-carbon triple bond, -N=N-).

[0058] In the above general formula, m １ , m ２ , m ３ , and o ３ If there are two or more of these repeating units, they may be arranged adjacent to each other to form a block, or they may be arranged randomly.

[0059] Furthermore, the polyorganosiloxane represented by formula (E3) is an epoxy group-containing polyorganosiloxane and a phenyl group-containing polyorganosiloxane, since it has both an epoxy group and a phenyl group. The epoxy group-containing polyorganosiloxane may or may not have a phenyl group.

[0060] <<<<<<Methyl group-containing polyorganosiloxane>>>>> 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.

[0061] R ２１０ and R ２２０ R is a group that bonds to a silicon atom, and each independently represents an alkyl group, but at least one of them is a methyl group, and the above examples can be given as specific examples of alkyl groups. 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. In the present invention, a preferred example of a methyl group-containing polyorganosiloxane is polydimethylsiloxane, but is not limited thereto.

[0062] Methyl group-containing polyorganosiloxanes are the siloxane units (D) mentioned above. ２００ Unit or D ２０It includes units, but D ２００ Units and D ２０ In addition to units, Q units, M units, and / or T units may also be included.

[0063] In one embodiment of the present invention, a specific example of a methyl group-containing polyorganosiloxane is D ２００ Polyorganosiloxanes consisting only of units, D ２００ Polyorganosiloxane containing units and Q units, D ２００ Polyorganosiloxane containing units and M units, D ２００ Polyorganosiloxanes containing units and T units, D ２００ Polyorganosiloxane containing units, Q units, and M units, D ２００ Polyorganosiloxane containing units, M units, and T units, D ２００ Examples include polyorganosiloxanes containing units, Q units, M units, and T units.

[0064] In a preferred embodiment of the present invention, a specific example of a methyl group-containing polyorganosiloxane is D ２０ Polyorganosiloxanes consisting only of units, D ２０ Polyorganosiloxane containing units and Q units, D ２０ Polyorganosiloxane containing units and M units, D ２０ Polyorganosiloxanes containing units and T units, D ２０ Polyorganosiloxane containing units, Q units, and M units, D ２０ Polyorganosiloxane containing units, M units, and T units, D ２０ Examples include polyorganosiloxanes containing units, Q units, M units, and T units.

[0065] Specific examples of methyl group-containing polyorganosiloxanes include, but are not limited to, those represented by formula (M1).

[0066] (n ４ (This indicates the number of repeating units and is a positive integer.)

[0067] <<<<<Phenyl group-containing polyorganosiloxane>>>>> Examples of phenyl group-containing polyorganosiloxanes include R３１ R ３２ SiO ２／２ Siloxane units (D) are represented by these units. ３０ Examples include those containing units.

[0068] R ３１ R is a group that bonds to a silicon atom and represents a phenyl group or an alkyl group. ３２ This is a group that bonds to a silicon atom, representing a phenyl group. Specific examples of alkyl groups include those mentioned above, but a methyl group is preferred.

[0069] Phenyl group-containing polyorganosiloxanes are the siloxane units (D) described above. ３０ It includes units, but D ３０ In addition to units, Q units, M units, and / or T units may also be included.

[0070] In a preferred embodiment of the present invention, a specific example of a phenyl group-containing polyorganosiloxane is D ３０ Polyorganosiloxanes consisting only of units, D ３０ Polyorganosiloxane containing units and Q units, D ３０ Polyorganosiloxane containing units and M units, D ３０ Polyorganosiloxanes containing units and T units, D ３０ Polyorganosiloxane containing units, Q units, and M units, D ３０ Polyorganosiloxane containing units, M units, and T units, D ３０ Examples include polyorganosiloxanes containing units, Q units, M units, and T units.

[0071] Specific examples of phenyl group-containing polyorganosiloxanes include, but are not limited to, those represented by formula (P1) or (P2).

[0072] (m ５ and n ５ (This indicates the number of each repeating unit and is a positive integer.)

[0073] (m ６ and n ６ (This indicates the number of each repeating unit and is a positive integer.)

[0074] <<<Silane Coupling Agent>>> The adhesive composition according to the present invention contains a silane coupling agent having an ethylenically unsaturated group. By including a silane coupling agent having an ethylenically unsaturated group in addition to the above-mentioned specific adhesive component in the adhesive composition, as described above, it is possible to provide a laminate in which, when peeling a semiconductor wafer, such as a semiconductor substrate, from a support substrate, the peeling interface becomes the interface between the semiconductor wafer, such as a semiconductor substrate, and the adhesive layer, resulting in device peeling.

[0075] The silane coupling agent having the above-mentioned ethylenically unsaturated group is preferably a silane compound represented by the following formula (1).

[0076] In formula (1), R １ Q represents a methyl or ethyl group, n represents a monovalent organic group having an ethylenically unsaturated group, and n represents an integer from 0 to 2.

[0077] The group represented by Q in formula (1) is preferably a monovalent group represented by the following formula (i-1) or a monovalent group represented by the following formula (ii-1).

[0078] In equation (i-1) or equation (ii-1), R ２１ R represents an alkylene group with 1 to 10 carbon atoms. ２２ R represents a hydrogen atom or a methyl group. ２３ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and * represents a bond to the silicon atom in formula (1).

[0079] The silane compound represented by formula (1) is preferably the silane compound represented by the following formula (1a).

[0080] In formula (1a), R １ represents a methyl group or an ethyl group, and Q represents a monovalent organic group having an ethylenically unsaturated group.

[0081] The monovalent group represented by formula (ii-1) is preferably the monovalent group represented by the following formula (ii-1a).

[0082] In formula (ii-1a), R ２１ represents an alkylene group having 1 to 10 carbon atoms. * represents a bond attached to the silicon atom in formula (1).

[0083] The silane compound represented by formula (1a) is preferably a silane compound represented by the following formula (11) or a silane compound represented by the following formula (12).

[0084] In equations (11) and (12), R １ R represents a methyl group or an ethyl group. ２１ This represents an alkylene group with 1 to 10 carbon atoms.

[0085] It is preferable that the silane compound represented by formula (1a) is at least one silane compound selected from the following silane compounds.

[0086] The content of the silane coupling agent in the adhesive composition is not particularly limited, but for example, it is preferably 0.01 to 10% by mass, more preferably 0.5 to 5% by mass, and even more preferably 0.1 to 1% by mass, relative to the adhesive component (A).

[0087] <<<Solvent>>> The adhesive composition may contain a solvent for purposes such as adjusting viscosity. Specific examples include, but are not limited to, aliphatic hydrocarbons, aromatic hydrocarbons, and ketones. More specifically, examples include, but are not limited to, hexane, heptane, octane, nonane, isononane, decane, undecane, dodecane, isododecane, menthane, limonene, toluene, xylene, mesitylene, cumene, MIBK (methyl isobutyl ketone), butyl acetate, diisobutyl ketone, 2-octanone, 2-nonanone, 5-nonanone, cyclohexanone, propylene glycol monomethyl ether acetate, and propylene glycol monomethyl ether. Such solvents can be used individually or in combination of two or more.

[0088] If the adhesive composition contains a solvent, its content is appropriately set considering the viscosity of the desired composition, the application method used, the thickness of the thin film to be produced, etc., but is typically in the range of about 10 to 90% by mass of the entire composition.

[0089] The viscosity of the 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 10,000 mPa·s.

[0090] <<<Preparation of Adhesive Composition>>> An example of the adhesive composition used in the present invention can be produced by mixing an adhesive component (A), a silane coupling agent, and a solvent. In a more preferred embodiment, it can be produced by mixing an adhesive component (A), a release agent component (B), a silane coupling agent, and a solvent. As an example of a more preferred embodiment of the method for producing the adhesive composition used in the present invention, the adhesive component (A), the release agent component (B), and the solvent are mixed, and then the silane coupling agent is added to the resulting mixture and mixed. The mixing order of the adhesive component (A) and the release agent component (B) is not particularly limited, but as an example of a method that can easily and reproducibly produce the adhesive composition, for example, a method in which the adhesive component (A) and the release agent component (B) are dissolved in the solvent, or a method in which a part of the adhesive component (A) and the release agent component (B) are dissolved in the solvent, the remainder is dissolved in the solvent, and the resulting solutions are mixed, but are not limited to these. When preparing the adhesive composition, heating may be applied as appropriate, within a range that does not cause the components to 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 adhesive composition or after all components have been mixed.

[0091] <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.

[0092] 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, etc., 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.

[0093] An example of a support substrate is a glass wafer or silicon wafer with a diameter of approximately 300 mm and a thickness of approximately 700 μm.

[0094] <Semiconductor Substrate or Electronic Device Substrate> <<Semiconductor Substrate>> The main material constituting the entire semiconductor substrate is not particularly limited as long as it is used for this type of application, but examples include silicon, silicon carbide, compound semiconductors, and glass substrates with organic resin. The shape of the semiconductor substrate is not particularly limited, but for example it is disc-shaped. Note that the surface shape of the disc-shaped semiconductor substrate does not need to be a perfect circle, for example the outer edge of the semiconductor substrate may have a straight section called an orientation flat or a cut called a notch. The thickness of the disc-shaped semiconductor substrate is not particularly limited and can be appropriately determined according to the intended use of the semiconductor substrate, but for example it is 500 to 1,000 μm. The diameter of the disc-shaped semiconductor substrate is not particularly limited and can be appropriately determined according to the intended use of the semiconductor substrate, but for example it is 100 to 1,000 mm.

[0095] A semiconductor substrate may have bumps. A bump is a protruding terminal. In a laminate, if the semiconductor substrate has bumps, the semiconductor substrate has the bumps on the support substrate side. In a semiconductor substrate, bumps are usually 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 surface opposite to the surface with bumps (the back surface) is the surface used for processing. 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 height, radius, and pitch of the bumps are appropriately determined from conditions such as a bump height of about 1 to 200 μm, a bump radius of 1 to 200 μm, and a bump pitch of 1 to 500 μm. Examples of bump materials include low-melting-point solder, high-melting-point solder, tin, indium, gold, silver, and copper. The bump may consist 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. The bump may also have a laminated structure including a metal layer made of at least one of these components.

[0096] An example of a semiconductor substrate is a silicon wafer with a diameter of approximately 300 mm and a thickness of approximately 770 μm.

[0097] <<Electronic Device Substrate>> An electronic device substrate refers to a substrate having an electronic device. In the present invention, for example, it refers to a substrate consisting of a layer in which a plurality of semiconductor chip substrates are embedded in a sealing resin, that is, a substrate consisting of a plurality of semiconductor chip substrates and a sealing resin disposed between the semiconductor chip substrates. Here, "electronic device" means a component that constitutes at least a part of an electronic component. The electronic device is not particularly limited and may have various mechanical structures or circuits formed on the surface of a semiconductor substrate. Preferably, the electronic device is a composite of a component made of metal or semiconductor and a resin that seals or insulates the component. The electronic device may have a single-layer or multi-layer structure, and the redistribution layer and / or semiconductor elements or other elements described later may be sealed or insulated with a sealing material or insulating material.

[0098] <Layer Structure of the Laminate> Below, an example of the structure of the laminate will be explained using a diagram. Figure 1 shows a schematic cross-sectional view of an example of the laminate. The laminate in Figure 1 has a semiconductor substrate 1, an adhesive layer 2, and a support substrate 3 in this order. That is, the adhesive layer 2 is provided between the semiconductor substrate 1 and the support substrate 3.

[0099] Figure 2 shows a schematic cross-sectional view of another example of a laminate. The laminate in Figure 2 has a support substrate 23, an adhesive layer 22, and an electronic device substrate 26 in that order. The electronic device substrate 26 has a plurality of semiconductor chip substrates 21 and a sealing resin 25, which is a sealing material, disposed between the semiconductor chip substrates 21. The adhesive layer 22 is provided between the electronic device substrate 26 and the support substrate 23.

[0100] (Method for manufacturing a laminate) The present invention provides a method for manufacturing a laminate comprising: a support substrate; a semiconductor substrate or an electronic device substrate; and an adhesive layer provided between the semiconductor substrate or the electronic device substrate and the support substrate, the method comprising: applying the adhesive composition of the present invention described above to the semiconductor substrate or the electronic device substrate to form an adhesive coating layer on the semiconductor substrate or the electronic device substrate; arranging the support substrate so as to sandwich the adhesive coating layer formed on the semiconductor substrate or the electronic device substrate, and bonding the semiconductor substrate or the electronic device substrate and the support substrate together; and heating the adhesive coating layer to form an adhesive layer, thereby bonding the semiconductor substrate or the electronic device substrate and the support substrate together via the adhesive layer.

[0101] The manufacturing method of the laminate shown in Figure 1 will be described below using the laminate shown in Figure 1 as an example. An example of the laminate of the present invention can be manufactured by a method including the following first to third steps. First step: A step of applying an adhesive composition onto a semiconductor substrate to form an adhesive coating layer. In this step, it is preferable to apply a low-temperature heat treatment (soft bake) to the adhesive coating layer in order to evaporate the residual solvent in the adhesive coating layer and to strengthen the adhesion between the adhesive coating layer and the semiconductor substrate. Second step: A step of arranging a support substrate so as to sandwich the adhesive coating layer formed on the semiconductor substrate and bonding the semiconductor substrate and the support substrate. In this step, it is preferable to bond the semiconductor substrate and the support substrate while performing at least one of a heat treatment and a reduced-pressure treatment. Third step: A step of forming an adhesive layer (cured film) by post-heating (main heating) the adhesive coating layer and bonding the semiconductor substrate and the support substrate via the adhesive layer.

[0102] The method of applying the adhesive composition is not particularly limited, but is usually done by spin coating. Alternatively, a method can be adopted in which a coating film is formed separately by spin coating or the like to form a sheet-like coating film, and this sheet-like coating film is then applied as the adhesive coating layer. The heating temperature of the applied adhesive composition cannot be specified in general terms, as it varies depending on the type and amount of adhesive components contained in the adhesive composition, whether or not a solvent is included, the boiling point of the solvent used, and the desired thickness of the adhesive layer, but is usually 80 to 150°C, and the heating time is usually 30 seconds to 5 minutes. If the adhesive composition contains a solvent, the applied adhesive composition is usually heated. The thickness of the adhesive coating layer obtained by applying the adhesive composition and heating it if necessary is usually about 5 to 500 μm, and is ultimately determined appropriately so that it falls within the aforementioned range of adhesive layer thickness.

[0103] In this invention, a laminate can be obtained by bonding a semiconductor substrate and a support substrate together by applying a load in the thickness direction while performing heat treatment, vacuum treatment, or both, and then performing a post-heat treatment. The choice of which treatment conditions to adopt—heat treatment, vacuum treatment, or a combination of both—is determined appropriately after considering various factors such as the type of adhesive composition, film thickness, and desired adhesive strength.

[0104] The heat treatment during the bonding process is usually appropriately determined from a range of 20 to 160°C, from the viewpoint of removing solvents from the composition. In particular, from the viewpoint of suppressing or avoiding excessive hardening or unwanted deterioration of the adhesive component (A), it is preferably 150°C or lower, more preferably 130°C or lower. The heating time is appropriately determined depending on the heating temperature and the type of adhesive, but from the viewpoint of reliably achieving suitable adhesion, it is usually 30 seconds or more, preferably 1 minute or more, but from the viewpoint of suppressing deterioration of the adhesive layer and other members, it is usually 10 minutes or less, preferably 5 minutes or less.

[0105] The vacuum treatment can be performed by exposing the adhesive coating layers that are in contact with each other to a pressure of 10 to 10,000 Pa. The vacuum treatment time is usually 1 to 30 minutes.

[0106] The load in the thickness direction of the semiconductor substrate and the support substrate is not particularly limited as long as it does not adversely affect the semiconductor substrate, the support substrate and the layers between them, and can firmly adhere them together, but it is usually in the range of 10 to 50,000 N.

[0107] The temperature for post-heating (main heating) is preferably 120°C or higher from the viewpoint of achieving a sufficient curing rate, and preferably 260°C or lower from the viewpoint of preventing deterioration of the substrate and each layer. The post-heating time is usually 1 minute or more, preferably 5 minutes or more, from the viewpoint of achieving suitable bonding of the substrate and layers constituting the laminate, and usually 180 minutes or less, preferably 120 minutes or less, from the viewpoint of suppressing or avoiding adverse effects on each layer due to excessive heating. Heating can be carried out using a hot plate, oven, etc. When post-heating using a hot plate, heating may be done with either the semiconductor substrate or the support substrate of the laminate facing downwards, but from the viewpoint of achieving suitable peeling with good reproducibility, it is preferable to post-heat with the semiconductor substrate facing downwards. One of the purposes of the post-heating treatment is to realize an adhesive layer that is a more suitable self-supporting film, and in particular to suitably achieve curing by hydrosilylation reaction.

[0108] Figures 3A and 3B illustrate one method for manufacturing the laminate shown in Figure 1. First, a laminate is prepared in which an adhesive coating layer 2a is formed on a semiconductor substrate 1 (Figure 3A). This laminate can be obtained, for example, by applying an adhesive composition to the semiconductor substrate 1 and then performing a low-temperature heat treatment (soft bake) on the adhesive coating layer 2a. Next, the laminate consisting of the support substrate 3 shown in Figure 3B and the semiconductor substrate 1 having the adhesive coating layer 2a shown in Figure 3A is bonded together via the adhesive coating layer 2a. Then, after applying a load in the thickness direction of the semiconductor substrate 1 and the support substrate 3 under reduced pressure, a heating device (not shown; hot plate) is placed on the side of the semiconductor substrate 1 opposite to the side where the adhesive coating layer 2a is in contact, and the adhesive coating layer 2a is post-heated (main heating) by the heating device to form an adhesive layer (cured film) (Figure 3B). The laminate shown in Figure 1 is obtained by the process shown in Figures 3A and 3B.

[0109] Furthermore, the manufacturing method of the laminate shown in Figure 2 will be described below using the laminate shown in Figure 2 as an example. An example of the laminate of the present invention can be manufactured by a method including the following first (D) to fourth (D) steps. First (D) step: A step of applying an adhesive composition onto a semiconductor chip substrate to form an adhesive coating layer. In this step, it is preferable to apply a low-temperature heat treatment (soft bake) to the adhesive coating layer in order to evaporate the residual solvent in the adhesive coating layer and to strengthen the adhesion between the adhesive coating layer and the semiconductor chip substrate. Second (D) step: A step of arranging a support substrate so as to sandwich the adhesive coating layer formed on the semiconductor chip substrate and bonding the semiconductor chip substrate and the support substrate. In this step, it is preferable to bond the semiconductor chip substrate and the support substrate while performing at least one of a heat treatment and a reduced-pressure treatment. Third (D) step: A step of forming an adhesive layer (cured film) by post-heating (main heating) the adhesive coating layer and bonding the semiconductor chip substrate and the support substrate via the adhesive layer. Fourth (D) step: A step of sealing the semiconductor chip substrate fixed on the adhesive layer using a sealing resin.

[0110] Figures 4A to 4C illustrate one embodiment of the manufacturing process for the laminate shown in Figure 2. First, an adhesive composition is applied to the semiconductor chip substrate 21 to form an adhesive coating layer 22a (Figure 4A). The adhesive coating layer 22a is subjected to a low-temperature heat treatment (soft bake). Next, the laminate consisting of the support substrate 23 shown in Figure 4B and the semiconductor chip substrate 21 having the adhesive coating layer 22a shown in Figure 4A is bonded together via the adhesive coating layer 22a. Then, after applying a load in the thickness direction between the semiconductor chip substrate 21 and the support substrate 23 under reduced pressure, a heating device (not shown; hot plate) is placed on the side of the semiconductor chip substrate 21 opposite to the side where the adhesive coating layer 22a is in contact, and the adhesive coating layer 22a is post-heated (main heating) by the heating device to form an adhesive layer 22 (cured film) (Figure 4B). Next, as shown in Figure 4C, the semiconductor chip substrate 21 fixed on the adhesive layer 22 is sealed using a sealing resin 25. In Figure 4C, multiple semiconductor chip substrates 21, temporarily bonded to a support substrate 23 via an adhesive layer 22, are sealed with a sealing resin 25. An electronic device substrate 26 is formed on the adhesive layer 22, having semiconductor chip substrates 21 and sealing resin 25 placed between them. Thus, the electronic device substrate 26 is a base layer in which multiple semiconductor chip substrates are embedded in the sealing resin. The laminate shown in Figure 2 is obtained by the process shown in Figures 4A to 4C.

[0111] <Sealing Process> The semiconductor chip substrate 21 is sealed using a sealing material. The sealing material used to seal the semiconductor chip substrate 21 is a material that can insulate or seal a component made of metal or semiconductor. In the present invention, for example, a resin composition (sealing resin) is used as the sealing material. The type of sealing resin is not particularly limited as long as it can seal and / or insulate metal or semiconductor, but for example, epoxy resin or silicone resin is preferred. In addition to the resin component, the sealing material may also contain other components such as fillers. Examples of fillers include spherical silica particles. In the sealing process, for example, a sealing resin heated to 130 to 170°C is supplied onto the adhesive layer 22 so as to cover the semiconductor chip substrate 21 while maintaining a high viscosity state, and a layer made of sealing resin 25 is formed on the adhesive layer 22 by compression molding. At that time, the temperature condition is, for example, 130 to 170°C. The pressure applied to the semiconductor chip substrate 21 is, for example, 50 to 500 N / cm ２ That is the case.

[0112] (Method for manufacturing a processed semiconductor substrate or electronic device substrate) By using the laminate according to the present invention, a method for manufacturing a processed semiconductor substrate or a method for manufacturing a processed electronic device substrate can be provided. The method for manufacturing a processed semiconductor substrate or an electronic device substrate according to the present invention is characterized by comprising: a fifth step in which the semiconductor substrate or electronic device substrate (semiconductor substrate, etc.) in the laminate of the present invention is processed; and a sixth step in which the semiconductor substrate or electronic device substrate (semiconductor substrate, etc.) processed in the fifth step is separated from a support substrate. Thus, the method for manufacturing a processed semiconductor substrate according to the present invention includes the following fifth step and the following sixth step. The method for manufacturing a processed electronic device substrate may further include the following seventh step. Fifth step: A step of processing the semiconductor substrate or electronic device substrate (semiconductor substrate, etc.) in the laminate of the present invention. Sixth step: A step of separating the semiconductor substrate or electronic device substrate (semiconductor substrate, etc.) processed in the fifth step from a support substrate. Seventh step: A step of cleaning the processed semiconductor substrate or electronic device substrate after the sixth step.

[0113] In the fifth step, the processing applied to the semiconductor substrate or electronic device substrate (semiconductor substrate, etc.) is, for example, processing on the side opposite the circuit surface of the wafer, such as thinning the wafer by polishing the back surface of the wafer. Subsequently, for example, through-silicon electrodes (TSVs) are formed, and then the thinned wafer is peeled off the support substrate to form a wafer laminate, which is then 3D mounted. Alternatively, for example, back-side electrodes may be formed before or after this. During the wafer thinning and TSV processes, heat of approximately 250 to 350°C is applied while the wafer is bonded to the support substrate. The laminate of the present invention usually has heat resistance to this load, including the adhesive layer. Note that the processing is not limited to those described above, and also includes, for example, the implementation of a semiconductor component mounting process when the substrate is temporarily bonded to the support substrate to support the substrate for mounting semiconductor components.

[0114] In particular, if the laminate is a laminate having an electronic device substrate, the processing applied to the electronic device substrate in the fifth step includes, for example, the grinding step and the wiring layer formation step described below.

[0115] <Grinding Process> The grinding process involves grinding the resin portion of the sealing resin layer 25 on the electronic device substrate 26 so that a portion of the semiconductor chip substrate 21 is exposed.

[0116] <Wiring Layer Formation Process> The wiring layer formation process is a process of forming a wiring layer on the exposed semiconductor chip substrate 21 after the grinding process described above. The wiring layer is also called an RDL (Reduction Layer) and is a thin film wiring body that constitutes the wiring connected to the substrate, and may have a single-layer or multi-layer structure. The wiring layer is made of dielectric material (silicon oxide (SiO2) ｘ The wiring may be formed between layers of a conductor (for example, metals such as aluminum, copper, titanium, nickel, gold, and silver, and alloys such as silver-tin alloys) such as photosensitive epoxy resins, but is not limited to this. For example, the following method can be used to form the wiring layer. First, silicon oxide (SiO2) is formed on the layer of sealing resin 25. ｘA dielectric layer, such as a photosensitive resin, is formed. The dielectric layer made of silicon oxide can be formed by, for example, sputtering or vacuum deposition. The dielectric layer made of a photosensitive resin can be formed by, for example, applying the photosensitive resin onto the layer of sealing resin 25 by methods such as spin coating, dipping, rollerblade coating, spray coating, or slit coating. Next, wiring is formed on the dielectric layer using a conductor such as a metal. As a method for forming the wiring, known semiconductor process techniques such as lithography (photolithography) and etching can be used. Examples of such lithography processes include lithography using positive-type resist materials and lithography using negative-type resist materials.

[0117] In the sixth step, the method for separating (peeling) the semiconductor substrate or electronic device substrate from the support substrate (semiconductor substrate, etc.) is not particularly limited. For example, one method is to mechanically peel them apart using equipment with a sharp part (a so-called debonder). Specifically, for example, a sharp part may be inserted between the semiconductor substrate or electronic device substrate (semiconductor substrate, etc.) and the support substrate, and then the semiconductor substrate or electronic device substrate (semiconductor substrate, etc.) and the support substrate may be separated.

[0118] The substrates can be cleaned by spraying the cleaning agent composition onto at least one of the surfaces of the separated semiconductor substrate or electronic device substrate (semiconductor substrate, etc.) and the support substrate, or by immersing the separated semiconductor substrate or electronic device substrate (semiconductor substrate, etc.) or the support substrate in the cleaning agent composition. Alternatively, the surface of the processed semiconductor substrate, etc. may be cleaned using a removal tape or the like. As an example of substrate cleaning, a seventh step may be performed after the sixth step to clean the processed semiconductor substrate, etc. Examples of cleaning agent compositions used for cleaning include the following.

[0119] Detergent compositions typically contain a solvent. Examples of solvents include lactones, ketones, polyhydric alcohols, compounds having ester bonds, derivatives of polyhydric alcohols, cyclic ethers, esters, and aromatic organic solvents. Examples of lactones include γ-butyrolactone. Examples of ketones include acetone, methyl ethyl ketone, cyclohexanone, methyl-n-pentyl ketone, methyl isopentyl ketone, and 2-heptanone. Examples of polyhydric alcohols include ethylene glycol, diethylene glycol, propylene glycol, and dipropylene glycol. Examples of compounds having ester bonds include ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, and dipropylene glycol monoacetate. Examples of derivatives of polyhydric alcohols include monoalkyl ethers such as monomethyl ether, monoethyl ether, monopropyl ether, and monobutyl ether, or compounds having ether bonds such as monophenyl ether, which are monomethyl ethers, monoethyl ether, monopropyl ether, and monobutyl ether of the above polyhydric alcohols or compounds having ester bonds. Among these, propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) are preferred. Examples of cyclic ethers include dioxane. Examples of esters include methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, and ethyl ethoxypropionate. Examples of aromatic organic solvents include anisole, ethyl benzyl ether, cresyl methyl ether, diphenyl ether, dibenzyl ether, phenethole, butylphenyl ether, ethylbenzene, diethylbenzene, pentylbenzene, isopropylbenzene, toluene, xylene, cymene, and mesitylene. These can be used individually or in combination of two or more.Among these, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), cyclohexanone, and ethyl lactate (EL) are preferred.

[0120] Furthermore, a mixed solvent obtained by mixing PGMEA and a polar solvent is also preferred. The mixing ratio (mass ratio) can be appropriately determined considering the compatibility of PGMEA and the polar solvent, but it is preferably in the range of 1:9 to 9:1, more preferably 2:8 to 8:2. For example, when EL is used as the polar solvent, the mass ratio of PGMEA:EL is preferably 1:9 to 9:1, more preferably 2:8 to 8:2. When PGME is used as the polar solvent, the mass ratio of PGMEA:PGME is preferably 1:9 to 9:1, more preferably 2:8 to 8:2, and even more preferably 3:7 to 7:3. When PGME and cyclohexanone are used as the polar solvent, the mass ratio of PGMEA:(PGME + cyclohexanone) is preferably 1:9 to 9:1, more preferably 2:8 to 8:2, and even more preferably 3:7 to 7:3.

[0121] The cleaning agent composition may or may not contain salt, but it is preferable that it does not contain salt in order to increase its versatility when processing semiconductor substrates using laminates and to reduce costs.

[0122] An example of a detergent composition containing a salt is a detergent composition containing a quaternary ammonium salt and a solvent. The quaternary ammonium salt is composed of a quaternary ammonium cation and an anion, and is not particularly limited as long as it is 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 ion (Cl － ), bromide ions (Br － ), iodide ion (I － ) and other halogen ions; tetrafluoroborate ions (BF４ － ); Hexafluorophosphate ion (PF ６ － Examples include, but are not limited to, these.

[0123] The quaternary ammonium salt is preferably a halogen-containing quaternary ammonium salt, and more preferably a fluorine-containing quaternary ammonium salt. In the quaternary ammonium salt, the halogen atom may be contained in the cation or in the anion, but is preferably contained in the anion.

[0124] In one preferred embodiment, the fluorine-containing quaternary ammonium salt is tetra(hydrocarbon)ammonium fluoride. Specific examples of hydrocarbon groups in tetra(hydrocarbon)ammonium 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 includes tetraalkylammonium fluoride. Specific examples of tetraalkylammonium fluoride include, but are not limited to, tetramethylammonium fluoride, tetraethylammonium fluoride, tetrapropylammonium fluoride, and tetrabutylammonium fluoride (also called tetrabutylammonium fluoride). Among these, tetrabutylammonium fluoride is preferred.

[0125] Quaternary ammonium salts such as tetraammonium fluoride may be used in hydrate form. Furthermore, quaternary ammonium salts such as tetraammonium fluoride may be used alone or in combination of two or more types. The amount of quaternary ammonium salt is not particularly limited as long as it dissolves in the solvent contained in the detergent composition, but is usually 0.1 to 30% by mass relative to the detergent composition.

[0126] When a detergent composition contains a salt, the solvent used in combination is not particularly limited as long as it is used for this type of application and dissolves salts such as quaternary ammonium salts. However, from the viewpoint of obtaining a detergent composition with excellent cleaning properties with good reproducibility, and from the viewpoint of dissolving salts such as quaternary ammonium salts well and obtaining a detergent composition with excellent uniformity, the detergent composition preferably contains one or more amide-based solvents.

[0127] A suitable example of an amide solvent is an acid amide derivative represented by formula (Z).

[0128] In the formula, R ０ R represents an ethyl group, a propyl group, or an isopropyl group, with ethyl and isopropyl groups preferred, and ethyl group more preferred. Ａ and R Ｂ Each of these independently represents an alkyl group having 1 to 4 carbon atoms. The alkyl group having 1 to 4 carbon atoms may be linear, branched, or cyclic, and specific examples include methyl, ethyl, propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, s-butyl, t-butyl, and cyclobutyl groups. Of these, R Ａ and R Ｂ The groups are preferably methyl or ethyl, more preferably both are methyl or ethyl, and even more preferably both are methyl.

[0129] Examples of acid amide derivatives represented by formula (Z) include N,N-dimethylpropionamide, N,N-diethylpropionamide, N-ethyl-N-methylpropionamide, N,N-dimethylbutyrate amide, N,N-diethylbutyrate amide, N-ethyl-N-methylbutyrate amide, N,N-dimethylisobutyrate amide, N,N-diethylisobutyrate amide, and N-ethyl-N-methylisobutyrate amide. Of these, N,N-dimethylpropionamide and N,N-dimethylisobutylamide are particularly preferred, and N,N-dimethylpropionamide is more preferred.

[0130] The acid amide derivative represented by formula (Z) may be synthesized by substitution reaction between the corresponding carboxylic acid ester and amine, or a commercially available product may be used.

[0131] Another example of a preferred amide solvent is a lactam compound represented by formula (Y).

[0132] In equation (Y), R １０１ R represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. １０２ The symbol represents an alkylene group having 1 to 6 carbon atoms. Specific examples of alkyl groups having 1 to 6 carbon atoms include methyl, ethyl, n-propyl, and n-butyl groups, while specific examples of alkylene groups having 1 to 6 carbon atoms include, but are not limited to, methylene, ethylene, trimethylene, tetramethylene, pentamethylene, and hexamethylene groups.

[0133] Specific examples of lactam compounds represented by formula (Y) include α-lactam compounds, β-lactam compounds, γ-lactam compounds, δ-lactam compounds, etc., which can be used individually or in combination of two or more.

[0134] In one preferred embodiment, the lactam compound represented by formula (Y) comprises 1-alkyl-2-pyrrolidone (N-alkyl-γ-butyrolactam), in one more preferred embodiment, comprises N-methylpyrrolidone (NMP) or N-ethylpyrrolidone (NEP), and in one even more preferred embodiment, comprises N-methylpyrrolidone (NMP).

[0135] The cleaning agent composition used in this invention may contain water as a solvent, but from the viewpoint of avoiding corrosion of the substrate, etc., only organic solvents are usually intentionally used as solvents. In this case, however, it is not ruled out that trace amounts of water contained in the salt's hydrated water or in the organic solvent may be included in the cleaning agent composition. The water content of the cleaning agent composition used in this invention is usually 5% by mass or less.

[0136] The components and method elements relating to the above-described steps of the method for manufacturing a processed semiconductor substrate or electronic device substrate (semiconductor substrate, etc.) of the present invention may be modified in various ways as long as they do not depart from the spirit of the present invention. The method for manufacturing a processed semiconductor substrate or electronic device substrate (semiconductor substrate, etc.) of the present invention may include steps other than those described above.

[0137] 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.

[0138] (1) Agitator: Rotating and revolving mixer, manufactured by Thinky Co., Ltd., ARE-500 (2) Vacuum bonding device: manufactured by ZUS Microtech Co., Ltd., XBS-300 (3) Delamination device: manufactured by ZUS Microtech Co., Ltd., XBC-300

[0139] [1] Preparation of adhesive composition [Preparation example 1] In a 600 mL stirring container for a stirrer, 64.5 g of MQ resin (manufactured by Wacker Chem Co., Ltd.) containing polysiloxane and vinyl groups as polyorganosiloxane (a1), 10.94 g of vinyl group-containing linear polydimethylsiloxane (manufactured by Wacker Chem Co., Ltd.) with a viscosity of 100 mPa·s as polyorganosiloxane (a1), 6.82 g of SiH group-containing linear polydimethylsiloxane (manufactured by Wacker Chem Co., Ltd.) with a viscosity of 70 mPa·s as polyorganosiloxane (a2), 1.0 g of epoxy group-containing linear polydimethylsiloxane X-22-343 (manufactured by Shin-Etsu Chemical Co., Ltd.) with a viscosity of 25 mPa·s as release agent component (B), linear polydimethylsiloxane GENIOPLAST 5 g of GUM (manufactured by Wacker Chem Co., Ltd.), 0.09 g of 1-ethynyl-1-cyclohexanol (manufactured by Wacker Chem Co., Ltd.) as a polymerization inhibitor, 0.09 g of 1,1-diphenyl-2-propyne-1-ol (manufactured by Tokyo Chemical Industry Co., Ltd.) as a polymerization inhibitor, 0.01 g of platinum catalyst (manufactured by Wacker Chem Co., Ltd.) as a platinum group metal catalyst (A2), and 18.39 g of p-menthane (manufactured by Tokyo Chemical Industry Co., Ltd.) as a solvent were added and stirred with a stirrer for 5 minutes. Finally, the resulting mixture was filtered through a 300 mesh nylon filter to obtain adhesive composition 1.

[0140] [Preparation Example 2] 100 g of adhesive composition 1 obtained in Preparation Example 1 was taken out, 1 g of triethoxypropylsilane (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the mixture was stirred with a stirrer for 5 minutes to obtain adhesive composition 2.

[0141] [Preparation Example 3] 100 g of adhesive composition 1 obtained in Preparation Example 1 was taken out, 5 g of triethoxypropylsilane (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the mixture was stirred with a stirrer for 5 minutes to obtain adhesive composition 3.

[0142] [Preparation Example 4] 100 g of adhesive composition 1 obtained in Preparation Example 1 was taken out, 1 g of allyltriethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the mixture was stirred with a stirrer for 5 minutes to obtain adhesive composition 4.

[0143] [Preparation Example 5] 100 g of adhesive composition 1 obtained in Preparation Example 1 was taken out, 5 g of allyltriethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the mixture was stirred with a stirrer for 5 minutes to obtain adhesive composition 5.

[0144] [Preparation Example 6] 100 g of adhesive composition 1 obtained in Preparation Example 1 was taken out, 1 g of [bicyclo[2,2,1]hepta-5-en-2-yl]triethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the mixture was stirred with a stirrer for 5 minutes to obtain adhesive composition 6.

[0145] [Preparation Example 7] 100 g of adhesive composition 1 obtained in Preparation Example 1 was taken out, 5 g of [bicyclo[2,2,1]hepta-5-en-2-yl]triethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the mixture was stirred with a stirrer for 5 minutes to obtain adhesive composition 7.

[0146] [Preparation Example 8] 100 g of adhesive composition 1 obtained in Preparation Example 1 was taken out, 1 g of allyltrimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the mixture was stirred with a stirrer for 5 minutes to obtain adhesive composition 8.

[0147] [Preparation Example 9] 100 g of adhesive composition 1 obtained in Preparation Example 1 was taken out, 5 g of allyltrimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the mixture was stirred with a stirrer for 5 minutes to obtain adhesive composition 9.

[0148] [Preparation Example 10] 100 g of adhesive composition 1 obtained in Preparation Example 1 was taken out, 1 g of triethoxy(7-octen-1-yl)silane (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the mixture was stirred with a stirrer for 5 minutes to obtain adhesive composition 10.

[0149] [Preparation Example 11] 100 g of adhesive composition 1 obtained in Preparation Example 1 was taken out, 5 g of triethoxy(7-octen-1-yl)silane (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the mixture was stirred with a stirrer for 5 minutes to obtain adhesive composition 11.

[0150] [2] Manufacturing of Laminates and Confirmation of Peelability [Comparative Examples 1-3] The adhesive compositions obtained in Preparation Examples 1-3 were spin-coated onto a 300 mm silicon wafer (thickness 775 μm) as the device-side substrate, so that the final film thickness in the resulting laminate was 60 μm. The wafer was then heat-treated at 120°C for 1 minute to form an adhesive coating layer on the silicon wafer, which is the semiconductor substrate. A 300 mm silicon wafer (thickness 775 μm) was used as the carrier-side substrate. The device-side silicon wafer and the carrier-side silicon wafer were bonded together using a bonding device, sandwiching the adhesive coating layer between them. After this, a post-heat treatment was performed at 200°C for 10 minutes to produce a laminate in which the device substrate, adhesive layer, and support substrate were stacked in this order. The bonding was performed at a temperature of 23°C and a reduced pressure of 1,500 Pa. The required number of laminates were manufactured. Subsequently, peeling was performed using a peeling device to confirm peelability. After delamination, the delamination interface between the adhesive composition and the substrate was visually observed to determine whether delamination occurred from the device side or the carrier side. The results are shown in Table 1.

[0151] [Examples 1-8] The adhesive compositions obtained in Preparation Examples 4-11 were spin-coated onto a 300 mm silicon wafer (775 μm thick) as the device-side substrate, so that the final film thickness in the resulting laminate was 60 μm. The wafer was then heat-treated at 120°C for 1 minute to form an adhesive coating layer on the silicon wafer, which is the semiconductor substrate. A 300 mm silicon wafer (775 μm thick) was used as the carrier-side substrate. The device-side silicon wafer and the carrier-side silicon wafer were bonded together using a bonding apparatus, sandwiching the adhesive coating layer between them. A post-heat treatment was then performed at 200°C for 10 minutes to produce a laminate in which the device substrate, adhesive layer, and support substrate were stacked in this order. The bonding was performed at a temperature of 23°C and a reduced pressure of 1,500 Pa. The required number of laminates were manufactured. Subsequently, peeling was performed using a peeling apparatus to confirm peelability. After peeling, the peeling interface between the adhesive composition and the substrate was visually observed to confirm whether peeling occurred from the device side or the carrier side interface. These results are shown in Table 1.

[0152]

[0153] In Comparative Examples 1 to 3, which used adhesive compositions 1 to 3, delamination occurred at the interface between the carrier-side substrate and the adhesive composition. In Examples 1 to 8, which used adhesive compositions 4 to 11, delamination occurred at the interface between the device-side substrate and the adhesive composition. From the results in Table 1, it was found that including a silane coupling agent having an ethylenically unsaturated group in the adhesive composition is effective in obtaining a laminate that can be delaminated on the device side.

[0154] According to the present invention, a laminate that can be peeled (device peeled) at the interface between the semiconductor substrate and the adhesive layer can be provided, making it useful for manufacturing processed semiconductor substrates.

[0155] 1 Semiconductor substrate 2 Adhesive layer 2a Adhesive coating layer 3 Support substrate 21 Semiconductor chip substrate 22 Adhesive layer 22a Adhesive coating layer 23 Support substrate 25 Encapsulation resin 26 Electronic device substrate

Claims

1. An adhesive composition for forming an adhesive layer provided between a support substrate and a semiconductor substrate or an electronic device substrate, wherein the adhesive composition comprises an adhesive component (A) that hardens by a hydrosilylation reaction and a silane coupling agent having an ethylenically unsaturated group.

2. The adhesive composition according to claim 1, wherein the silane coupling agent having an ethylenically unsaturated group is a silane compound represented by the following formula (1). (In formula (1), R １ (where represents a methyl or ethyl group, Q represents a monovalent organic group having an ethylenically unsaturated group, and n represents an integer from 0 to 2.) 3. The adhesive composition according to claim 2, wherein the group represented by Q in formula (1) is a monovalent group represented by the following formula (i-1) or a monovalent group represented by the following formula (ii-1). (In equation (i-1) or equation (ii-1), R ２１ R represents an alkylene group with 1 to 10 carbon atoms. ２２ R represents a hydrogen atom or a methyl group. ２３ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and * represents a bond to the silicon atom in formula (1).

4. The adhesive composition according to claim 2, wherein the silane compound represented by formula (1) is the silane compound represented by the following formula (1a). (In formula (1a), R １ (where represents a methyl or ethyl group, and Q represents a monovalent organic group having an ethylenically unsaturated group.) 5. The adhesive composition according to claim 3, wherein the monovalent group represented by formula (ii-1) is a monovalent group represented by the following formula (ii-1a). (In formula (ii-1a), R ２１ represents an alkylene group with 1 to 10 carbon atoms. * represents a bond to the silicon atom in formula (1).

6. The adhesive composition according to claim 4, wherein the silane compound represented by formula (1a) is a silane compound represented by the following formula (11) or a silane compound represented by the following formula (12). (In equations (11) and (12), R １ R represents a methyl group or an ethyl group. ２１ (This represents an alkylene group with 1 to 10 carbon atoms.) 7. The adhesive composition according to claim 6, wherein the silane compound represented by formula (1a) is at least one silane compound selected from the following silane compounds.

8. The adhesive composition according to claim 1, further comprising a release agent component (B).

9. The adhesive component (A) cured by the hydrosilylation reaction contains a polysiloxane (A1) containing siloxane units (Q units) represented by SiO ２ , siloxane units (M units) represented by R １ R ２ R ３ SiO １／２ , siloxane units (D units) represented by R ４ R ５ SiO ２／２ , siloxane units (T units) represented by R ６ SiO ３／２ , and siloxane units selected from the group consisting of combinations of two or more of these (R １ to R ６ each independently represent a monovalent chemical group that is an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or a hydrogen atom, provided that R １ to R ６ are each bonded to a silicon atom by an Si-C bond or an Si-H bond).) and a platinum group metal-based catalyst (A2). The adhesive composition according to claim 1.

10. The adhesive composition according to claim 8, wherein the release agent component (B) comprises an epoxy group-containing polyorganosiloxane.

11. A laminate comprising a support substrate, a semiconductor substrate or an electronic device substrate, and an adhesive layer provided between the semiconductor substrate or the electronic device substrate and the support substrate, wherein the adhesive layer is formed from the adhesive composition described in any one of claims 1 to 10.

12. A method for manufacturing a laminate having a support substrate, a semiconductor substrate or an electronic device substrate, and an adhesive layer provided between the semiconductor substrate or the electronic device substrate and the support substrate, comprising the steps of: applying an adhesive composition according to any one of claims 1 to 10 to the semiconductor substrate or the electronic device substrate to form an adhesive coating layer on the semiconductor substrate or the electronic device substrate; arranging a support substrate so as to sandwich the adhesive coating layer formed on the semiconductor substrate or the electronic device substrate, and bonding the semiconductor substrate or the electronic device substrate and the support substrate; and heating the adhesive coating layer to form an adhesive layer, thereby bonding the semiconductor substrate or the electronic device substrate and the support substrate via the adhesive layer.

13. A method for manufacturing a processed semiconductor substrate or electronic device substrate, comprising: a fifth step of processing the semiconductor substrate or electronic device substrate of the laminate according to claim 11; and a sixth step of separating the semiconductor substrate or electronic device substrate processed in the fifth step from the support substrate.

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