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

Abstract

The present invention provides, for example, a laminate which has a support substrate, a semiconductor substrate or an electronic device substrate, and an adhesive layer that is disposed between the semiconductor substrate or the electronic device substrate and the support substrate, wherein when a semiconductor wafer is separated from the support substrate, the interface between the semiconductor wafer and the adhesive layer serves as the separation interface, thereby enabling the achievement of device separation.

Description

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

[0001] The present invention relates to adhesive compositions, laminates, methods for making laminates, and methods for making processed semiconductor or electronic device substrates.

[0002] Semiconductor wafers have traditionally been integrated in a two-dimensional plane, but for the purpose of further integration, semiconductor integration technology is required that integrates (stacks) the plane in a three-dimensional plane as well. This three-dimensional stacking is a technology that integrates multiple layers while connecting vias (TSVs). When integrating multiple layers, each wafer to be integrated is thinned by polishing the side opposite the circuit surface (i.e., the backside), and the thinned semiconductor wafers are stacked. The unthinned semiconductor wafer (herein simply referred to as wafer) is adhered to a support for polishing with a polishing device.

[0003] Semiconductor wafers (herein simply referred to as wafers) before thinning are bonded to a support in preparation for polishing with a polishing device. This bond must be easily peeled off after polishing, and is therefore called a temporary bond. This temporary bond must be easily removed from the support; applying a large force to remove it can cause the thinned semiconductor wafer to break or deform, so it must be easily removed to prevent this from happening. However, it is undesirable for the temporary bond to become dislodged or shifted due to the polishing stress during polishing of the backside of the semiconductor wafer. Therefore, the performance required of the temporary bond is to withstand the stress during polishing and 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 Pamphlet International Publication No. 2018 / 216732 Pamphlet

[0006] As described above, in the temporary bonding between a semiconductor wafer and a support, the adhesive layer formed from the temporary adhesive is difficult to peel off from the support or semiconductor wafer during temporary bonding, while the adhesive layer must be easily peeled off from the support or semiconductor wafer when the semiconductor wafer is peeled off from the support. When peeling the semiconductor wafer from the support, the peeling location may be the interface between the semiconductor wafer and the adhesive layer (also referred to as device peeling (device release)), or the interface between the support and the adhesive layer (also referred to as carrier peeling (carrier release)). For example, when the peeling is carrier peeling, the adhesive layer remains (adheres) on the device side of the semiconductor wafer, which increases the cleaning time after peeling compared to device peeling, raising concerns that the cleaning burden on the device substrate (semiconductor wafer) may be increased. Therefore, in order to avoid the above-mentioned concerns, device peeling is preferred. Therefore, when the semiconductor wafer is peeled off from the support, it is convenient that the peeling location (peeling interface) is the device release, which is the interface between the semiconductor wafer and the adhesive layer.

[0007] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a laminate including 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, in which, when the semiconductor wafer 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] As a result of extensive research conducted by the present inventors to solve the above-mentioned problems, they discovered that the above-mentioned problems can be solved by specifying the content ratios of a specific adhesive component constituting the adhesive composition and a specific release component constituting the adhesive composition within specific ranges in an adhesive composition for forming an adhesive layer, and thus completed the present invention, which has the following gist.

[0009] That is, the present invention includes 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, the adhesive composition comprising an adhesive component (A) that cures by a hydrosilylation reaction and a release agent component (B), the adhesive component (A) that cures by a hydrosilylation reaction containing SiO ２ Siloxane units (Q units) represented by R １ R ２ R ３ SiO １／２ Siloxane units (M units) represented by R ４ R ５ SiO ２／２ Siloxane units (D units) represented by the formula: and R ６ SiO ３／２ and a polysiloxane (A1) (R １ ~R ６ each independently represents 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 ~R ６ are bonded to silicon atoms by Si-C bonds or Si-H bonds), and the polysiloxane (A1) comprises a polyorganosiloxane (a1) (the polyorganosiloxane (a1) has an alkenyl group having 2 to 10 carbon atoms, and SiO ２ Siloxane units (Q′ units) represented by the formula: and R ６ 'SiO ３／２ and 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 Si—H groups and SiO ２ Siloxane units (Q″ units) represented by R １ "R ２ "R ３ "SiO １／２Siloxane units (M″ units) represented by R ４ "R ５ "SiO ２／２ Siloxane units (D″ units) represented by R ６ "SiO ３／２ and a siloxane unit selected from the group consisting of a siloxane unit (T″ unit) represented by the formula: １ “~R ６ " each independently represent an alkyl group having 1 to 10 carbon atoms or a hydrogen atom), and the release agent component (B) comprises an epoxy group-containing polyorganosiloxane, and when the content of the polyorganosiloxane (a1) in the total components excluding the solvent in the adhesive composition is y %, and the content of the epoxy group-containing polyorganosiloxane in the total components excluding the solvent in the adhesive composition is x %, the adhesive composition satisfies the following formula (I): y≦2.50In(x)+70.12 (I) [2] The polysiloxane (A1) further comprises a polyorganosiloxane (a3) ​​(the polyorganosiloxane (a3) ​​is a polyorganosiloxane represented by the formula １ 'R ２ 'R ３ 'SiO １／２ Siloxane units (M′ units) represented by the formula: ４ 'R ５ 'SiO ２／２ and R １ '~R ５each independently represent 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. [3] 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 [1] or [2]. [4] A method for producing 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 the adhesive composition according to [1] or [2] to either the semiconductor substrate or the electronic device substrate, or the support substrate, to form the adhesive layer. [5] A method for manufacturing a processed semiconductor substrate or electronic device substrate, comprising: a fifth step of processing the semiconductor substrate or the electronic device substrate of the laminate described in [3]; 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, it is possible 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, in which, when the semiconductor wafer is peeled off from the support substrate, the peeling interface becomes the interface between the semiconductor wafer and the adhesive layer, which is device peeling.

[0011] Fig. 1 is a schematic cross-sectional view of an example of a laminate. Fig. 2 is a schematic cross-sectional view of another example of a laminate. Fig. 3A is a schematic cross-sectional view (part 1) for explaining a method for manufacturing the laminate shown in Fig. 1. Fig. 3B is a schematic cross-sectional view (part 2) for explaining a method for manufacturing the laminate shown in Fig. 1. Fig. 4A is a schematic cross-sectional view (part 1) for explaining a method for manufacturing the laminate shown in Fig. 2. Fig. 4B is a schematic cross-sectional view (part 2) for explaining a method for manufacturing the laminate shown in Fig. 2. Fig. 4C is a schematic cross-sectional view (part 3) for explaining a method for manufacturing the laminate shown in Fig. 2. Fig. 5 shows the results of an example for determining formula (I).

[0012] (Laminate) The laminate of the present invention is 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 formed from a specific adhesive composition described below. The laminate is used in applications where the support substrate and the semiconductor substrate or the electronic device substrate are separated after processing of the semiconductor substrate or the electronic device substrate in the laminate.

[0013] The laminate of the present invention is used for temporary bonding when processing a semiconductor substrate or an electronic device substrate, and can be suitably used for processing such as thinning a semiconductor substrate or an electronic device substrate (hereinafter, "semiconductor substrate or electronic device substrate" will also be collectively referred to as "semiconductor substrate, 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, residue of the adhesive layer remaining on the semiconductor substrate or electronic device substrate can be removed, for example, with a cleaning composition for cleaning semiconductor substrates, etc.

[0014] Each of the constituent elements of the laminate will be described below.

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

[0016] The thickness of the adhesive layer provided 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 due to a thick film, it is preferably 200 μm or less, more preferably 150 μm or less, even more preferably 120 μm or less, and even more preferably 100 μm or less.

[0017] The method for forming the adhesive layer from the adhesive composition will be described in detail in the section explaining the method for producing the laminate.

[0018] <<Adhesive Composition>> The adhesive composition according to the present invention contains an adhesive component (A) that cures via a hydrosilylation reaction and a release agent component (B). Here, the release agent component (B) is a component that does not undergo a hydrosilylation reaction or a curing reaction. For example, polyorganosiloxane can be mentioned. In the present invention, "does not undergo a curing reaction" does not mean that any curing reaction does not occur, but rather that the curing reaction occurring in the curing adhesive component (A) does not occur. The adhesive composition according to the present invention may contain other components.

[0019] <<<Adhesive Component (A)>>> The adhesive component (A) is a component that cures by a hydrosilylation reaction. The adhesive component (A) may be a polyorganosiloxane component (A') ... ２ Siloxane units (Q units) represented by R １ R ２ R ３ SiO １／２ Siloxane units (M units) represented by R ４ R ５ SiO２／２ Siloxane units (D units) represented by the formula: and R ６ SiO ３／２ and a polysiloxane (A1) (R １ ~R ６ each independently represents 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 ~R ６ are each 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).

[0020] R １ ~R ６ are groups or atoms bonded to the silicon atom, and each independently represents an optionally substituted alkyl group, an optionally substituted alkenyl group, or a hydrogen atom. Examples of the substituent include a halogen atom, a nitro group, a cyano group, an amino group, a hydroxyl group, a carboxyl group, an aryl group, and a heteroaryl group.

[0021] <<<<<Polysiloxane Component (A1)>>>> The polysiloxane (A1) is a polyorganosiloxane (a1) (the polyorganosiloxane (a1) has an alkenyl group having 2 to 10 carbon atoms, and SiO ２ Siloxane units (Q′ units) represented by the formula: and R ６ 'SiO ３／２ and 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 Si—H groups and SiO ２ Siloxane units (Q″ units) represented by R １ "R ２ "R ３ "SiO １／２Siloxane units (M″ units) represented by R ４ "R ５ "SiO ２／２ Siloxane units (D″ units) represented by R ６ "SiO ３／２ and a siloxane unit selected from the group consisting of a siloxane unit (T″ unit) represented by the formula: １ “~R ６ " each independently represents an alkyl group having 1 to 10 carbon atoms or a hydrogen atom).

[0022] The polysiloxane (A1) further comprises a polyorganosiloxane (a3) ​​(the polyorganosiloxane (a3) ​​is represented by R １ 'R ２ 'R ３ 'SiO １／２ Siloxane units (M′ units) represented by the formula: ４ 'R ５ 'SiO ２／２ and R １ '~R ５ Each of the 's 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 the polyorganosiloxane (a3) ​​contains a polyorganosiloxane (a1) different from the polyorganosiloxane (a1).

[0023] The polyorganosiloxane (a1) has an alkenyl group having 2 to 10 carbon atoms, and SiO ２ Siloxane units (Q′ units) represented by the formula: ６ 'SiO ３／２ and further comprising at least one siloxane unit (T′ unit) represented by R １ 'R ２ 'R ３ 'SiO １／２ Siloxane units (M′ units) represented by R ４ 'R ５ 'SiO ２／２ and a siloxane unit selected from the group consisting of a siloxane unit (D′ unit) represented by the following formula:１ '~R ６ Preferably, the polyorganosiloxane is a polyorganosiloxane in which each of the groups 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.

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

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

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

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

[0028] Specific examples of the optionally substituted cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a 1-methylcyclopropyl group, a 2-methylcyclopropyl group, a cyclopentyl group, a 1-methylcyclobutyl group, a 2-methylcyclobutyl group, a 3-methylcyclobutyl group, a 1,2-dimethylcyclopropyl group, a 2,3-dimethylcyclopropyl group, a 1-ethylcyclopropyl group, a 2-ethylcyclopropyl group, a cyclohexyl group, a 1-methylcyclopentyl group, a 2-methylcyclopentyl group, a 3-methylcyclopentyl group, a 1-ethylcyclobutyl group, a 2-ethylcyclobutyl group, a 3-ethylcyclobutyl group, a 1,2-dimethylcyclobutyl group, a 1,3-dimethylcyclobutyl group, a 2,2-dimethylcyclobutyl group, a 2,3-dimethylcyclobutyl group, a 2,4-dimethylcyclobutyl group, a 3,3-dimethylcyclobutyl group, a cyclopropyl ... Examples of such cycloalkyl groups include cycloalkyl groups such as 1-n-propyl-cyclobutyl group, 1-n-propyl-cyclopropyl group, 2-n-propyl-cyclopropyl group, 1-i-propyl-cyclopropyl group, 2-i-propyl-cyclopropyl group, 1,2,2-trimethyl-cyclopropyl group, 1,2,3-trimethyl-cyclopropyl group, 2,2,3-trimethyl-cyclopropyl group, 1-ethyl-2-methyl-cyclopropyl group, 2-ethyl-1-methyl-cyclopropyl group, 2-ethyl-2-methyl-cyclopropyl group, and 2-ethyl-3-methyl-cyclopropyl group; and bicycloalkyl groups such as bicyclobutyl group, bicyclopentyl group, bicyclohexyl group, bicycloheptyl group, bicyclooctyl group, bicyclononyl group, and bicyclodecyl group, but are not limited to these. The number of carbon atoms in the cycloalkyl groups is usually 3 to 14, preferably 4 to 10, and more preferably 5 to 6.

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

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

[0031] As described above, the polysiloxane (A1) contains polyorganosiloxane (a1) and polyorganosiloxane (a2), and more preferably contains polyorganosiloxane (a1), polyorganosiloxane (a3), and polyorganosiloxane (a2). In this specification, polyorganosiloxane (a1) and polyorganosiloxane (a3) ​​are collectively referred to as "polyorganosiloxane (a1) and the like." The alkenyl groups contained in the polyorganosiloxane (a1) and the hydrogen atoms (Si—H groups) contained in the polyorganosiloxane (a2) form a crosslinked structure through a hydrosilylation reaction with a platinum group metal catalyst (A2), and the crosslinked structure is cured. As a result, a cured film is formed.

[0032] The polyorganosiloxane (a1) and the like are composed of siloxane units in which alkyl groups and / or alkenyl groups are bonded to the silicon atoms thereof, and R １ '~R ６ The proportion of alkenyl groups in all the substituents represented by R ′ is preferably 0.1 to 50.0 mol %, more preferably 0.5 to 30.0 mol %, and the remaining R １ '~R ６ ' can be an alkyl group.

[0033] The polyorganosiloxane (a2') is composed of siloxane units in which an alkyl group and / or a hydrogen atom is bonded to the silicon atom. １ "~R ６The proportion of hydrogen atoms in all the substituents and substituted atoms represented by R １ "~R ６ " can be an alkyl group.

[0034] In the polysiloxane (A1), the molar ratio of the polyorganosiloxane (a2) to the total amount of the polyorganosiloxane (a1) and the polyorganosiloxane (a3), for example, the alkenyl groups contained in the polyorganosiloxane (a1) and the hydrogen atoms constituting the Si—H bonds contained in the polyorganosiloxane (a2), is in the range of 1.0:0.5 to 1.0:0.66.

[0035] The weight average molecular weights of the polysiloxanes of polyorganosiloxane (a1), polyorganosiloxane (a3), and polyorganosiloxane (a2) are not particularly limited, but are usually 500 to 1,000,000, respectively. From the viewpoint of realizing the effects of the present invention with good reproducibility, it is preferably 5,000 to 50,000. In the present invention, the weight average molecular weight, number average molecular weight, and dispersity of the polyorganosiloxane can be measured using, for example, a GPC apparatus (EcoSEC, HLC-8320GPC manufactured by Tosoh Corporation) and a GPC column (TSKgel SuperMultiporeHZ-N, TSKgel SuperMultiporeHZ-H manufactured by Tosoh Corporation), a column temperature of 40 ° C., tetrahydrofuran as an eluent (elution solvent), a flow rate (flow rate) of 0.35 mL / min, and polystyrene (Shodex manufactured by Showa Denko K.K.) as a standard sample.

[0036] The viscosities of the polyorganosiloxane (a1), polyorganosiloxane (a3), and polyorganosiloxane (a2) are not particularly limited, but are usually 10 to 1,000,000 (mPa s), and from the viewpoint of reproducibly realizing the effects of the present invention, preferably 50 to 10,000 (mPa s). The viscosities of the polyorganosiloxane (a1), polyorganosiloxane (a3), and polyorganosiloxane (a2) are values ​​measured at 25 ° C. using an E-type rotational viscometer.

[0037] Polyorganosiloxane (a1), polyorganosiloxane (a3), and polyorganosiloxane (a2) react with each other via a hydrosilylation reaction, and therefore the curing mechanism is different from that via, for example, silanol groups, and therefore none of the siloxanes need contain silanol groups or functional groups that form silanol groups upon hydrolysis, such as alkyloxy groups.

[0038] <<<<<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.

[0039] Specific examples of platinum-based metal catalysts that can be used include known platinum-based compounds (platinum or compounds containing platinum). Specific examples include platinum fine powder, platinum black, chloroplatinic acid, alcohol-modified chloroplatinic acid, complexes of chloroplatinic acid and diolefins, platinum-olefin complexes, platinum-carbonyl complexes (platinum bis(acetoacetate), platinum bis(acetylacetonate), etc.), chloroplatinic acid-alkenylsiloxane complexes (chloroplatinic acid-divinyltetramethyldisiloxane complex, chloroplatinic acid-tetravinyltetramethylcyclotetrasiloxane complex, etc.), platinum-alkenylsiloxane complexes (platinum-divinyltetramethyldisiloxane complex, platinum-tetravinyltetramethylcyclotetrasiloxane complex, etc.), and complexes of chloroplatinic acid and acetylene alcohols. Among these, platinum-alkenylsiloxane complexes are particularly preferred due to their high hydrosilylation reaction-accelerating effect. These hydrosilylation reaction catalysts may be used either individually or in combination of two or more.

[0040] The alkenylsiloxane used in the platinum-alkenylsiloxane complex is not particularly limited, and examples thereof include 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, alkenylsiloxane oligomers in which some of the methyl groups of these alkenylsiloxanes have been substituted with ethyl groups, phenyl groups, etc., and alkenylsiloxane oligomers in which the vinyl groups of these alkenylsiloxanes have been substituted with allyl groups, hexenyl groups, etc. 1,3-divinyl-1,1,3,3-tetramethyldisiloxane is particularly preferred because the resulting platinum-alkenylsiloxane complex has good stability.

[0041] 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 the polyorganosiloxane (a1), the polyorganosiloxane (a3), and the polyorganosiloxane (a2).

[0042] <<<<<Polymerization Inhibitor>>>> The adhesive component may contain a polymerization inhibitor for the purpose of inhibiting the progress of the hydrosilylation reaction. The polymerization inhibitor is not particularly limited as long as it can inhibit the progress of the hydrosilylation reaction, and specific examples include alkynyl alcohols such as 1-ethynyl-1-cyclohexanol and 1,1-diphenyl-2-propyn-1-ol. The amount of the polymerization inhibitor is not particularly limited, but, for example, relative to the total amount of polyorganosiloxane (a1), polyorganosiloxane (a3), and polyorganosiloxane (a2), it is usually 1000.0 ppm or more from the viewpoint of obtaining the effect, and 10000.0 ppm or less from the viewpoint of preventing excessive inhibition of the hydrosilylation reaction.

[0043] <<<Release Agent Component>>> As the release agent component, from the viewpoint of more suitably obtaining the effects of the present invention, polyorganosiloxane is preferred, and epoxy group-containing polyorganosiloxane is preferred. The polyorganosiloxane as the release agent component usually does not react with the adhesive component. For example, the polyorganosiloxane as the release agent component is a component that does not undergo a hydrosilylation reaction.

[0044] The adhesive composition of the present invention may contain two or more release agent components.

[0045] <<<<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 undergo a hydrosilylation reaction.

[0046] Examples of epoxy group-containing polyorganosiloxanes include R １１ R １２ SiO ２／２ The siloxane unit (D １０ Examples include those containing units.

[0047] R １１ is a group bonded to a silicon atom and represents an alkyl group; R １２ is a group bonded to a silicon atom and represents an epoxy group or an organic group containing an epoxy group, and specific examples of the alkyl group include those listed above. The epoxy group in the organic group containing an epoxy group may be an independent epoxy group that is not condensed with another ring, or may be an epoxy group that forms a condensed ring with another ring, such as a 1,2-epoxycyclohexyl group. Specific examples of organic groups 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 is, but is not limited to, epoxy group-containing polydimethylsiloxane.

[0048] The epoxy group-containing polyorganosiloxane contains the above-mentioned siloxane unit (D １０units), but D １０ In addition to the units, the epoxy group-containing polyorganosiloxane may contain Q units, M units and / or T units. In a preferred embodiment of the present invention, specific examples of the epoxy group-containing polyorganosiloxane include D １０ Polyorganosiloxane consisting only of units, D １０ polyorganosiloxanes containing D units and Q units; １０ Polyorganosiloxanes containing D units and M units, １０ Polyorganosiloxanes containing D units and T units, １０ polyorganosiloxanes containing units, Q units and M units, １０ Polyorganosiloxanes containing units, M units and T units, D １０ Examples of suitable organosiloxanes include polyorganosiloxanes containing Q units, M units, and T units.

[0049] The epoxy group-containing polyorganosiloxane is preferably an epoxy group-containing polydimethylsiloxane having an epoxy value of 0.1 to 5. The weight average molecular weight thereof is not particularly limited, but is usually 1,500 to 500,000, and from the viewpoint of suppressing precipitation in the composition, it is preferably 100,000 or less.

[0050] Specific examples of epoxy group-containing polyorganosiloxanes include, but are not limited to, those represented by formulas (E1) to (E3).

[0051] (m １ and n １ indicates the number of each repeating unit and is a positive integer.)

[0052] (m ２ and n ２ indicates the number of each repeating unit and is a positive integer, and R is an alkylene group having 1 to 10 carbon atoms which may be interrupted by at least one of an oxygen atom and an unsaturated bond (e.g., a carbon-carbon double bond, a carbon-carbon triple bond, or -N=N-).

[0053] (m ３ , n ３ and ３indicates the number of each repeating unit and is a positive integer, and R is an alkylene group having 1 to 10 carbon atoms which may be interrupted by at least one of an oxygen atom and an unsaturated bond (e.g., a carbon-carbon double bond, a carbon-carbon triple bond, or -N=N-).

[0054] In the above general formula, m １ , m ２ , m ３ , and o ３ When the number of repeating units is two or more, the repeating units may be arranged adjacent to each other to form a block, or may be arranged randomly.

[0055] Since the polyorganosiloxane represented by formula (E3) has an epoxy group and a phenyl group, it is an epoxy group-containing polyorganosiloxane and also a phenyl group-containing polyorganosiloxane. The epoxy group-containing polyorganosiloxane may or may not have a phenyl group.

[0056] The weight-average molecular weight of the epoxy group-containing polyorganosiloxane is not particularly limited, but is typically 100,000 to 2,000,000. From the viewpoint of reproducibly achieving the effects of the present invention, it is preferably 200,000 to 1,200,000, more preferably 300,000 to 900,000. Furthermore, its dispersity is not particularly limited, but is typically 1.0 to 10.0. From the viewpoint of reproducibly achieving suitable release, it is preferably 1.5 to 5.0, more preferably 2.0 to 3.0. The weight-average molecular weight and dispersity can be measured using the method described above for polyorganosiloxanes as adhesive components. The viscosity of the epoxy group-containing polyorganosiloxane is not particularly limited, but is typically 1,000 to 2,000,000 mm ２ The viscosity value of the epoxy group-containing polyorganosiloxane is expressed as a kinematic viscosity, and is expressed as centistokes (cSt) = mm ２ Viscosity (mPa s) is converted to density (g / cm ３ That is, the value can be calculated from the viscosity and density measured with an E-type rotational viscometer at 25°C, and the kinematic viscosity (mm２ / s)=viscosity (mPa・s) / density (g / cm ３ ) can be calculated using the formula:

[0057] <<<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 specific examples include, but are not limited to, hexane, heptane, octane, nonane, decane, undecane, dodecane, isododecane, menthane, limonene, toluene, xylene, methylene, cumene, MIBK (methyl isobutyl ketone), butyl acetate, diisobutyl ketone, 2-octanone, 2-nonanone, and 5-nonanone. Such solvents may be used alone or in combination of two or more.

[0058] When the adhesive composition contains a solvent, the content of the solvent is appropriately set taking into consideration the desired viscosity of the composition, the coating method to be used, the thickness of the thin film to be produced, and the like, but is, for example, in the range of about 10 to 90 mass % relative to the entire composition.

[0059] The viscosity of the adhesive composition used in the present invention is not particularly limited, but is usually 500 to 20,000 mPa·s, and preferably 1,000 to 1,0000 mPa·s at 25°C.

[0060] <<<Content Ratio of Adhesive Component (a1) and Release Agent Component (B)>>> The present invention specifies the content ratio of polyorganosiloxane (a1) in adhesive component (A) and epoxy group-containing polyorganosiloxane in release agent component (B) in the adhesive composition. The adhesive composition of the present invention is prepared so that the contents of polyorganosiloxane (a1) and epoxy group-containing polyorganosiloxane satisfy the following formula (I): y≦2.50In(x)+70.12 (I) Here, x represents the proportion (x %) of the epoxy group-containing polyorganosiloxane in the total components excluding the solvent in the adhesive composition, and y represents the proportion (y %) of the polyorganosiloxane (a1) in the total components excluding the solvent in the adhesive composition. As will be shown in the examples described later, a laminate having an adhesive layer formed from an adhesive composition that satisfies formula (I) above can cause peeling (device peeling) at the interface between the semiconductor wafer and the adhesive layer when the semiconductor wafer is peeled from the support substrate.

[0061] <<<Preparation of Adhesive Composition>>> An example of the adhesive composition used in the present invention can be produced by mixing the adhesive component (A), the release agent component (B), and a solvent. The mixing order is not particularly limited, and examples of methods that can easily and reproducibly produce an adhesive composition include, but are not limited to, a method of dissolving the adhesive component (A) and the release agent component (B) in a solvent, or a method of dissolving a portion of the adhesive component (A) and the remainder of the release agent component (B) in a solvent and mixing the resulting solutions. When preparing the adhesive composition, heating may be performed as appropriate within a range that does not cause decomposition or deterioration of the components. In the present invention, the solvent, solution, etc. used may be filtered using a filter or the like during the production of the adhesive composition or after all of the components have been mixed in order to remove foreign matter.

[0062] <Support Substrate> The support substrate is not particularly limited as long as it is a member that can support a semiconductor substrate when the semiconductor substrate is processed, and examples thereof include a glass support substrate and a silicon support substrate.

[0063] The shape of the support substrate is not particularly limited, but may be, for example, a disk shape. The disk-shaped support substrate does not need to have a perfectly circular surface; for example, the outer periphery of the support substrate may have a straight line portion called an orientation flat, or a notch. The thickness of the disk-shaped support substrate may be determined appropriately depending on the size of the semiconductor substrate, and is not particularly limited, but is, for example, 500 to 1,000 μm. The diameter of the disk-shaped support substrate may be determined appropriately depending on the size of the semiconductor substrate, and is not particularly limited, but is, for example, 100 to 1,000 mm.

[0064] An example of the support substrate is a glass wafer or a silicon wafer having a diameter of about 300 mm and a thickness of about 700 μmm.

[0065] When the peeling of the laminate is performed by light irradiation, for example, a substrate that is optically transparent to the light used is used as the support substrate.

[0066] <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 suitable for this type of application, and examples thereof include silicon, silicon carbide, compound semiconductors, and glass substrates with organic resins. The shape of the semiconductor substrate is not particularly limited, and may be, for example, a disk. Note that the surface of a disk-shaped semiconductor substrate does not need to be perfectly circular; for example, the outer periphery of the semiconductor substrate may have a linear portion called an orientation flat or a notch. The thickness of the disk-shaped semiconductor substrate may be determined appropriately depending on the intended use of the semiconductor substrate, and is not particularly limited, and is, for example, 500 to 1,000 μm. The diameter of the disk-shaped semiconductor substrate may be determined appropriately depending on the intended use of the semiconductor substrate, and is not particularly limited, and is, for example, 100 to 1,000 mm.

[0067] The semiconductor substrate may have bumps. Bumps are protruding terminals. In a laminate, when the semiconductor substrate has bumps, the bumps are located on the support substrate side. In a semiconductor substrate, the bumps are typically formed on the surface on which the circuit is formed. The circuit may be single-layered or multi-layered. The shape of the circuit is not particularly limited. In a semiconductor substrate, the surface opposite to the surface having the 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. The height, radius, and pitch of the bumps are typically determined appropriately based on the following conditions: a bump height of approximately 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 be composed of only a single component or multiple components. More specifically, examples include alloy platings mainly containing Sn, such as SnAg bumps, SnBi bumps, Sn bumps, and AuSn bumps. The bump may also have a laminate structure including a metal layer composed of at least one of these components.

[0068] An example of a semiconductor substrate is a silicon wafer with a diameter of about 300 mm and a thickness of about 770 μm.

[0069] <<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 multiple semiconductor chip substrates are embedded in a sealing resin, that is, a substrate consisting of multiple semiconductor chip substrates and a sealing resin disposed between the semiconductor chip substrates. Here, "electronic device" refers to a member that constitutes at least a part of an electronic component. The electronic device is not particularly limited and can be a semiconductor substrate having various mechanical structures or circuits formed on the surface thereof. The electronic device is preferably a composite of a member made of metal or semiconductor and a resin that seals or insulates the member. The electronic device may have a rewiring layer (described later) and / or a semiconductor element or other element sealed or insulated with a sealing material or insulating material, and may have a single-layer or multi-layer structure.

[0070] <Layer structure of laminate> An example of the structure of the laminate will be described below with reference to the drawings. Fig. 1 shows a schematic cross-sectional view of an example of the laminate. The laminate of Fig. 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.

[0071] Fig. 2 shows a schematic cross-sectional view of another example of a laminate. The laminate in Fig. 2 includes, in this order, a support substrate 23, an adhesive layer 22, and an electronic device substrate 26. The electronic device substrate 26 includes a plurality of semiconductor chip substrates 21 and sealing resin 25, which serves as 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.

[0072] (Method for manufacturing a laminate) The method for manufacturing a laminate of the present invention is 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, characterized in that it comprises a step of applying the above-mentioned adhesive composition of the present invention to either the semiconductor substrate or the electronic device substrate, or the support substrate, in order to form the adhesive layer.

[0073] A method for producing a laminate 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 produced, for example, by a method including the following first to third steps. First step: A step of applying an adhesive composition to a semiconductor substrate to form an adhesive coating layer (and, if necessary, further heating to form an adhesive layer). Second step: A step of placing a support substrate on the adhesive coating layer or adhesive layer, and bonding the support substrate and semiconductor substrate via the adhesive coating layer or adhesive layer while performing at least one of a heat treatment and a decompression treatment. Third step: A step of curing the adhesive coating layer by post-heat treatment to form an adhesive layer.

[0074] The method for applying the adhesive composition is not particularly limited, but is typically spin coating. Alternatively, a method can be employed in which a coating film is formed separately by spin coating or the like, a sheet-like coating film is formed, and the sheet-like coating film is then applied as an adhesive coating layer. The heating temperature of the applied adhesive composition cannot be generally specified because it varies depending on the type and amount of adhesive components contained in the adhesive composition, whether or not a solvent is contained, the boiling point of the solvent used, the desired thickness of the adhesive layer, and other factors. However, it is typically 80 to 150°C, and the heating time is typically 30 seconds to 5 minutes. When the adhesive composition contains a solvent, the applied adhesive composition is typically heated. The thickness of the adhesive coating layer obtained by applying the adhesive composition and, if necessary, heating it is typically about 5 to 500 μm, and is appropriately determined so as to ultimately achieve the above-mentioned range of adhesive layer thickness.

[0075] In the present invention, the laminate of the present invention can be obtained by applying a load in the thickness direction of the semiconductor substrate and the support substrate while performing a heat treatment, a decompression treatment, or both, and then performing a post-heat treatment. The treatment conditions to be adopted, whether heat treatment, decompression treatment, or a combination of both, are appropriately determined taking into consideration various factors such as the type of adhesive composition, the film thickness, and the desired adhesive strength.

[0076] The heat treatment temperature is determined appropriately from the viewpoint of removing the solvent from the composition, etc., usually within the range of 20 to 160° C. In particular, from the viewpoint of suppressing or avoiding excessive curing or unnecessary deterioration of the adhesive component (A), the heat treatment temperature is preferably 150° C. or lower, more preferably 130° C. or lower, and the heating time is determined appropriately depending on the heating temperature and the type of adhesive, but is usually 30 seconds or longer, preferably 1 minute or longer, from the viewpoint of reliably achieving suitable adhesion, and is usually 10 minutes or shorter, preferably 5 minutes or shorter, from the viewpoint of suppressing deterioration of the adhesive layer and other components.

[0077] The reduced pressure treatment can be carried out by exposing the adhesive coated layers in contact with each other to an atmospheric pressure of 10 to 10,000 Pa. The reduced pressure treatment time is usually 1 to 30 minutes.

[0078] 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 therebetween and can firmly adhere them to each other, but is usually within the range of 10 to 50,000 N.

[0079] The post-heating temperature 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 longer, preferably 5 minutes or longer, from the viewpoint of achieving suitable bonding of the substrate and layers constituting the laminate, and usually 180 minutes or shorter, preferably 120 minutes or shorter, from the viewpoint of suppressing or avoiding adverse effects on each layer due to excessive heating. Heating can be performed using a hot plate, oven, or the like. When post-heating is performed using a hot plate, either the semiconductor substrate or the support substrate of the laminate may be heated facing down, but from the viewpoint of achieving suitable peeling with good reproducibility, post-heating with the semiconductor substrate facing down is preferred. Note that one purpose of the post-heating treatment is to achieve an adhesive layer that is a more suitable free-standing film, and in particular to achieve suitable curing by a hydrosilylation reaction.

[0080] 3A and 3B are diagrams illustrating one embodiment of the manufacturing method for the laminate shown in FIG. 1 . First, a laminate is prepared in which an adhesive coating layer 2a is formed on a semiconductor substrate 1 ( FIG. 3A ). This laminate can be obtained, for example, by applying an adhesive composition to the semiconductor substrate 1 and then heating the applied composition. Next, a support substrate 3 shown in FIG. 3B and a laminate consisting of the semiconductor substrate 1 having the adhesive coating layer 2a shown in FIG. 3A are bonded together via the adhesive coating layer 2a. 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 surface of the semiconductor substrate 1 opposite the surface where the adhesive coating layer 2a contacts. The adhesive coating layer 2a is heated and cured by the heating device, converting it into the adhesive layer 2 ( FIG. 3B ). The laminate shown in FIG. 1 is obtained by the steps shown in FIGS. 3A and 3B .

[0081] 2 as an example, a method for producing a laminate will be described below. An example of the laminate of the present invention can be produced by a method including the following steps 1 (D) to 4 (D). Step 1 (D): A step of applying an adhesive composition to a semiconductor chip substrate to form an adhesive coating layer (and, if necessary, further heating to form an adhesive layer). Step 2 (D): A step of placing a support substrate on the adhesive coating layer or adhesive layer, and bonding the support substrate and semiconductor chip substrate via the adhesive coating layer or adhesive layer while performing at least one of a heat treatment and a decompression treatment. Step 3 (D): A step of curing the adhesive coating layer by post-heat treatment to form an adhesive layer. Step 4 (D): A step of sealing the semiconductor chip substrate fixed on the adhesive layer with a sealing resin.

[0082] 4A to 4C are diagrams illustrating one embodiment of manufacturing the laminate shown in FIG. 2 . First, a laminate is prepared in which an adhesive coating layer 22a is formed on a semiconductor chip substrate 21 ( FIG. 4A ). This laminate can be obtained, for example, by applying an adhesive composition to the semiconductor chip substrate 21 and heating it. The adhesive coating layer 22a may then be heated to form the adhesive layer 22. Next, a support substrate 23 shown in FIG. 4B and a laminate consisting of the semiconductor chip substrate 21 having the adhesive coating layer 22a shown in FIG. 4A are bonded together via the adhesive coating layer 22a. 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 surface of the semiconductor chip substrate 21 opposite the surface where the adhesive coating layer 22a contacts. The adhesive coating layer 22a is heated and cured by the heating device, converting it into the adhesive layer 22 ( FIG. 4B ). Next, as shown in Fig. 4C, the semiconductor chip substrates 21 fixed on the adhesive layer 22 are sealed with sealing resin 25. In Fig. 4C, multiple semiconductor chip substrates 21 temporarily bonded to a support substrate 24 via the adhesive layer 22 are sealed with sealing resin 25. An electronic device substrate 26 having semiconductor chip substrates 21 and sealing resin 25 disposed between the semiconductor chip substrates 21 is formed on the adhesive layer 22. In this manner, the electronic device substrate 26 is a base layer in which multiple semiconductor chip substrates are embedded in sealing resin. The laminate shown in Fig. 2 is obtained by the steps shown in Figs. 4A to 4C.

[0083] <Encapsulating Step> The semiconductor chip substrate 21 is encapsulated using an encapsulant. The encapsulant used for encapsulating the semiconductor chip substrate 21 is a material capable of insulating or encapsulating components made of metal or semiconductor. In the present invention, for example, a resin composition (encapsulating resin) is used as the encapsulant. The type of encapsulating resin is not particularly limited as long as it is capable of encapsulating and / or insulating metal or semiconductor, but it is preferable to use, for example, an epoxy-based resin or a silicone-based resin. The encapsulating material may contain other components such as a filler in addition to the resin component. Examples of fillers include spherical silica particles. In the encapsulating step, the encapsulating resin, heated to, for example, 130 to 170°C, is supplied onto the adhesive layer 22 while maintaining a high viscosity, so as to cover the semiconductor chip substrate 21, and is compression-molded to form a layer made of the encapsulating resin 25 on the adhesive layer 22. The temperature conditions during this process are, for example, 130 to 170°C. The pressure applied to the semiconductor chip substrate 21 is, for example, 50 to 500 N / cm. ２ is.

[0084] (Method for manufacturing a processed semiconductor substrate or electronic device substrate) Using the laminate of the present invention, it is possible to provide a method for manufacturing a processed semiconductor substrate or a method for manufacturing a processed electronic device substrate. The method for manufacturing a processed semiconductor substrate or electronic device substrate of the present invention is characterized by comprising: a fifth step in which a 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 of the present invention comprises the following fifth step and sixth step. The method for manufacturing a processed electronic device substrate may further comprise the following seventh step. Fifth step: a step of processing a 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; and Seventh step: a step of cleaning the processed semiconductor substrate or electronic device substrate after the sixth step.

[0085] The processing performed on the semiconductor substrate or electronic device substrate (semiconductor substrate, etc.) in the fifth step is, for example, processing of the side opposite the circuit surface of the wafer, such as thinning the wafer by polishing the back surface of the wafer. Thereafter, for example, through-silicon vias (TSVs) are formed, and then the thinned wafer is peeled off from the support substrate to form a wafer stack, which is then three-dimensionally mounted. Also, for example, before or after this, formation of wafer backside electrodes, etc. is also performed. During the wafer thinning and TSV process, a heat load of approximately 250 to 350°C is applied while the wafer is adhered to the support substrate. The laminate of the present invention, including the adhesive layer, typically has heat resistance to this load. The processing is not limited to the above-described processing, and also includes, for example, the implementation of a semiconductor component mounting process when the wafer is temporarily adhered to a support substrate to support the substrate for mounting the semiconductor component.

[0086] In particular, when the laminate has an electronic device substrate, examples of the processing performed on the electronic device substrate in the fifth step include the grinding step and wiring layer formation step described below.

[0087] <Grinding Step> The grinding step is a step of grinding away the resin portion of the sealing resin 25 layer on the electronic device substrate 26 so that a part of the semiconductor chip substrate 21 is exposed.

[0088] <Wiring Layer Forming Process> The wiring layer forming process is a process of forming a wiring layer on the exposed semiconductor chip substrate 21 after the grinding process. The wiring layer is also called an RDL (Redistribution Layer), and is a thin-film wiring body that constitutes wiring connected to the substrate, and can have a single-layer or multi-layer structure. The wiring layer is made of a dielectric (silicon oxide (SiO ｘ The wiring layer may be formed by a conductor (for example, a metal such as aluminum, copper, titanium, nickel, gold, or silver, or an alloy such as a silver-tin alloy) between a layer of a sealing resin 25 (e.g., a photosensitive resin such as a photosensitive epoxy, photosensitive resin, etc.), but is not limited to this. Examples of methods for forming the wiring layer include the following methods. First, silicon oxide (SiO ｘ), a dielectric layer made of a photosensitive resin or the like is formed. The dielectric layer made of silicon oxide can be formed by, for example, sputtering, vacuum deposition, or the like. The dielectric layer made of a photosensitive resin can be formed by applying the photosensitive resin onto the layer of sealing resin 25 by, for example, spin coating, dipping, roller blade, spray coating, slit coating, or the like. Next, wiring is formed on the dielectric layer using a conductor such as metal. Methods for forming the wiring include, for example, known semiconductor process techniques such as lithography processes such as photolithography (resist lithography), etching, and the like. Examples of such lithography processes include lithography processes using a positive resist material and lithography processes using a negative resist material.

[0089] In the sixth step, the method for separating (peeling) the semiconductor substrate or electronic device substrate from the support substrate (e.g., semiconductor substrate) is not particularly limited. For example, a method of mechanically peeling them using a tool with a sharp part (a so-called debonder) can be used. Specifically, for example, a sharp part is inserted between the semiconductor substrate or electronic device substrate (e.g., semiconductor substrate) and the support substrate, and then the semiconductor substrate or electronic device substrate (e.g., semiconductor substrate) and the support substrate are separated.

[0090] The substrates can be cleaned by spraying the cleaning composition onto the surface of at least one of the separated semiconductor substrate or electronic device substrate (semiconductor substrate, etc.) and the supporting substrate, or by immersing the separated semiconductor substrate or electronic device substrate (semiconductor substrate, etc.) or the supporting substrate in the cleaning composition. The surface of the processed semiconductor substrate, etc. may also be cleaned using a removal tape or the like. As an example of cleaning the substrate, a seventh step of cleaning the processed semiconductor substrate, etc. may be performed after the sixth step. Examples of cleaning compositions used for cleaning include the following.

[0091] The cleaning agent composition usually contains a solvent. Examples of the solvent include lactones, ketones, polyhydric alcohols, compounds having an ester bond, derivatives of polyhydric alcohols, cyclic ethers, esters, and aromatic organic solvents. Examples of the lactones include γ-butyrolactone. Examples of the ketones include acetone, methyl ethyl ketone, cyclohexanone, methyl-n-pentyl ketone, methyl isopentyl ketone, and 2-heptanone. Examples of the polyhydric alcohols include ethylene glycol, diethylene glycol, propylene glycol, and dipropylene glycol. Examples of compounds having an ester bond include ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, and dipropylene glycol monoacetate. Examples of derivatives of polyhydric alcohols include compounds having an ether bond, such as monoalkyl ethers or monophenyl ethers of the above polyhydric alcohols or compounds having an ester bond, such as monomethyl ether, monoethyl ether, monopropyl ether, and monobutyl ether. 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, phenetole, butylphenyl ether, ethylbenzene, diethylbenzene, pentylbenzene, isopropylbenzene, toluene, xylene, cymene, mesitylene, etc. These can be used alone 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.

[0092] Also preferred are mixed solvents containing PGMEA and a polar solvent. The blending ratio (mass ratio) can be determined appropriately taking into account the compatibility of the PGMEA and the polar solvent, but is preferably within the range of 1:9 to 9:1, and more preferably 2:8 to 8:2. For example, when EL is blended as the polar solvent, the mass ratio of PGMEA:EL is preferably 1:9 to 9:1, and more preferably 2:8 to 8:2. When PGME is blended 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 blended as the polar solvents, 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.

[0093] The cleaning composition may or may not contain a salt; however, the absence of a salt is preferred in terms of increasing versatility in processing semiconductor substrates using the laminate and reducing costs.

[0094] 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. A typical example of such a quaternary ammonium cation is a tetra(hydrocarbon)ammonium cation. On the other hand, the anion paired with the quaternary ammonium cation is a hydroxide ion (OH － ) ; fluorine ion (F － ), chloride ions (Cl － ), bromine ion (Br － ), iodine ion (I － ) and other halogen ions; tetrafluoroborate ion (BF４ － ) ; hexafluorophosphate ion (PF ６ － ) and the like, but are not limited to these.

[0095] The quaternary ammonium salt is preferably a halogen-containing quaternary ammonium salt, more preferably a fluorine-containing quaternary ammonium salt. In the quaternary ammonium salt, the halogen atom may be contained in either the cation or the anion, but is preferably contained in the anion.

[0096] In a preferred embodiment, the fluorine-containing quaternary ammonium salt is tetra(hydrocarbon)ammonium fluoride. Specific examples of the hydrocarbon group 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, the tetra(hydrocarbon)ammonium fluoride includes tetraalkylammonium fluoride. Specific examples of tetraalkylammonium fluorides include, but are not limited to, tetramethylammonium fluoride, tetraethylammonium fluoride, tetrapropylammonium fluoride, and tetrabutylammonium fluoride (also known as tetrabutylammonium fluoride). Of these, tetrabutylammonium fluoride is preferred.

[0097] The quaternary ammonium salts such as tetra(hydrocarbon)ammonium fluoride may be used in the form of a hydrate. The quaternary ammonium salts such as tetra(hydrocarbon)ammonium fluoride may be used singly or in combination of two or more. The amount of the quaternary ammonium salt is not particularly limited as long as it dissolves in the solvent contained in the cleaning composition, but is usually 0.1 to 30 mass% based on the cleaning composition.

[0098] When the cleaning composition contains a salt, the solvent to be used in combination with the salt is not particularly limited as long as it is used for this type of application and dissolves the salt such as a quaternary ammonium salt. However, from the viewpoint of reproducibly obtaining a cleaning composition having excellent cleaning properties and from the viewpoint of satisfactorily dissolving the salt such as a quaternary ammonium salt to obtain a cleaning composition having excellent uniformity, the cleaning composition preferably contains one or two or more amide solvents.

[0099] A suitable example of the amide solvent is an acid amide derivative represented by formula (Z).

[0100] In the formula, R ０ represents an ethyl group, a propyl group, or an isopropyl group, preferably an ethyl group or an isopropyl group, and more preferably an ethyl group. Ａ and R Ｂ each 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 a methyl group, an ethyl group, a propyl group, an isopropyl group, a cyclopropyl group, an n-butyl group, an isobutyl group, an s-butyl group, a t-butyl group, and a cyclobutyl group. Of these, R Ａ and R Ｂ As the alkyl group, a methyl group or an ethyl group is preferred, and both of them are more preferably methyl groups or ethyl groups, and both of them are even more preferably methyl groups.

[0101] Examples of the acid amide derivative represented by formula (Z) include N,N-dimethylpropionamide, N,N-diethylpropionamide, N-ethyl-N-methylpropionamide, N,N-dimethylbutyric acid amide, N,N-diethylbutyric acid amide, N-ethyl-N-methylbutyric acid amide, N,N-dimethylisobutyric acid amide, N,N-diethylisobutyric acid amide, N-ethyl-N-methylisobutyric acid amide, etc. Among these, N,N-dimethylpropionamide and N,N-dimethylisobutyric acid amide are particularly preferred, and N,N-dimethylpropionamide is more preferred.

[0102] The acid amide derivative represented by formula (Z) may be synthesized by a substitution reaction between a corresponding carboxylic acid ester and an amine, or a commercially available product may be used.

[0103] Another example of a preferred amide solvent is a lactam compound represented by formula (Y).

[0104] In formula (Y), R １０１ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R １０２ represents an alkylene group having 1 to 6 carbon atoms. Specific examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, an n-propyl group, and an n-butyl group, and specific examples of the alkylene group having 1 to 6 carbon atoms include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group, but are not limited to these.

[0105] Specific examples of the lactam compound represented by formula (Y) include α-lactam compounds, β-lactam compounds, γ-lactam compounds, and δ-lactam compounds, and these can be used alone or in combination of two or more.

[0106] In a preferred embodiment, the lactam compound represented by formula (Y) includes 1-alkyl-2-pyrrolidone (N-alkyl-γ-butyrolactam), in a more preferred embodiment, it includes N-methylpyrrolidone (NMP) or N-ethylpyrrolidone (NEP), and in an even more preferred embodiment, it includes N-methylpyrrolidone (NMP).

[0107] The cleaning composition used in the present invention may contain water as a solvent, but usually only an organic solvent is used as the solvent from the viewpoint of avoiding corrosion of the substrate, etc. In this case, it is not excluded that the cleaning composition may contain water of hydration of salts or trace amounts of water contained in the organic solvent. The water content of the cleaning composition used in the present invention is usually 5 mass% or less.

[0108] The constituent elements and methodological elements of 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 without departing 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.

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

[0110] (1) Mixer A: ARE-500 planetary centrifugal mixer manufactured by Thinky Corporation (2) Measurement of complex viscosity: MCR-302 rheometer manufactured by Anton Paar (3) Vacuum bonding device X: Manual bonder manufactured by SUSS MicroTec (4) Vacuum bonding device Y: Auto bonder manufactured by SUSS MicroTec (5) Peeling device X: Auto debonder manufactured by SUSS MicroTec

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

[0112]

[0113] [Measurement of Molecular Weight] The weight-average molecular weight, number-average molecular weight, and dispersity of polydimethylsiloxane were measured using a GPC apparatus (EcoSEC HLC-8320GPC manufactured by Tosoh Corporation) and a GPC column (TSKgel SuperMultipore HZ-N, TSKgel SuperMultipore HZ-H manufactured by Tosoh Corporation) at a column temperature of 40°C, using tetrahydrofuran as an eluent (elution solvent) at a flow rate (flow rate) of 0.35 mL / min, and using polystyrene (Showdex manufactured by Showa Denko K.K.) as a standard sample.

[0114] [1-1] Preparation of Adhesive Composition [Example 1] In a 600 mL stirring vessel dedicated to the stirrer, 70.0 g of MQ resin (manufactured by Wacker Chemie) containing polysiloxane and vinyl groups as polyorganosiloxane (a1), 16.0 g of SiH group-containing linear polydimethylsiloxane (manufactured by Wacker Chemie) having a viscosity of 100 mPa s as polyorganosiloxane (a2), 2.48 g of vinyl group-containing linear polydimethylsiloxane (manufactured by Wacker Chemie) having a viscosity of 200 mPa s as polyorganosiloxane (a3), and 2.48 g of vinyl group-containing linear polydimethylsiloxane (manufactured by Wacker Chemie) having a viscosity of 1000 mPa s represented by formula (W) were mixed. 10.0 g of dimethylsiloxane (manufactured by Wacker Chemical Co.), 0.25 g of 1-ethynylcyclohexanol (manufactured by Wacker Chemical Co.) as a polymerization inhibitor (a4), 0.25 g of 1,1-diphenyl-2-propyn-1-ol (manufactured by Tokyo Chemical Industry Co.) as a polymerization inhibitor (a5), 0.04 g of a platinum catalyst (manufactured by Wacker Chemical Co.) as a platinum group metal catalyst (a6), 14.9 g of p-menthane (manufactured by Tokyo Chemical Industry Co., Ltd.) as a solvent, and 1.00 g of X-22-343 (manufactured by Shin-Etsu Chemical Co., Ltd.) (component (B-1)) as a release agent component (B) were added and stirred for 5 minutes with a stirrer. Finally, the resulting mixture was filtered through a 300 mesh nylon filter to obtain adhesive composition 1.

[0115] [Examples 2 to 6 and Comparative Examples 1 to 3] Adhesive compositions 2 to 6 and comparative adhesive compositions 1 to 3 were prepared in the same manner as in Example 1, except that the content ratios were changed to those shown in Table 1 below, using the same procedures as in Example 1. The constituent ratios of each adhesive composition are shown in Table 1. Note that Example 6 and Comparative Example 3 are examples in which the release agent component (B) was changed from X-22-343 (manufactured by Shin-Etsu Chemical Co., Ltd.) (component (B-1)) to KF-1001 (manufactured by Shin-Etsu Chemical Co., Ltd.) (component (B-2)).

[0116] Details of component (B-1) and component (B-2) in Table 1 are as follows: X-22-343: Epoxy group-containing polyorganosiloxane manufactured by Shin-Etsu Chemical Co., Ltd. KF-1001: Epoxy group-containing polyorganosiloxane manufactured by Shin-Etsu Chemical Co., Ltd.

[0117] [2] Laminate Production and Confirmation of Peel Interface Each of the obtained adhesive compositions was spin-coated to a 60 μm thickness on a 300 mm silicon wafer (thickness: 770 μm) serving as the device-side wafer, and then heated at 90°C for 90 seconds to form an adhesive coating layer on the silicon wafer serving as the semiconductor substrate. Heating was performed using a heating device placed on the side of the device-side silicon wafer opposite the side contacting the adhesive coating layer (i.e., with the device-side wafer facing down). The silicon wafer bearing the adhesive coating layer was then bonded to a 300 mm silicon wafer (thickness: 770 μm) serving as the carrier-side wafer (support) in a vacuum bonding apparatus Y, sandwiching the adhesive coating layer between them. A laminate was then produced by heating the device-side wafer facing down on a hot plate at 200°C for 10 minutes (post-heat treatment). The bonding was performed at a temperature of 23°C, a vacuum of 1,000 Pa, and a load of 30 N. Peeling was then performed using a peeling apparatus to confirm peelability. After peeling, the peeled interface was visually inspected, and peeling on the device side was marked with ◯, and peeling on the carrier side was marked with ×.

[0118] The results are shown in Table 2 below.

[0119]

[0120] From the results in Table 2, it was found that in order to obtain a laminate that can be peeled off from the device side, it is effective to specify the composition of the adhesive resin (component (a1)) of the adhesive component (A) and the release agent component (B) in the adhesive composition. The boundary between device peeling and carrier peeling (see Table 3 below) was expressed as a relational equation of the content ratio of the resin component (a1) of the adhesive component (A) and the release agent component (B), and the following formula (I) was obtained (see the results in Figure 5). y ≤ 2.50In(x) + 70.12 (I) In formula (I), x represents the proportion x% of the content of the epoxy group-containing polyorganosiloxane in the total components excluding the solvent in the adhesive composition, and y represents the proportion y% of the content of the polyorganosiloxane (a1) in the total components excluding the solvent in the adhesive composition. The coefficient of determination R, which indicates the goodness (degree) of fit of the estimated regression equation in Figure 5, ２is 0.99.

[0121]

[0122] 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, and is therefore useful for producing processed semiconductor substrates.

[0123] REFERENCE SIGNS LIST 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 Sealing 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, the adhesive composition comprising an adhesive component (A) that cures by a hydrosilylation reaction and a release agent component (B), the adhesive component (A) that cures by a hydrosilylation reaction containing SiO ２ Siloxane units (Q units) represented by R １ R ２ R ３ SiO １／２ Siloxane units (M units) represented by R ４ R ５ SiO ２／２ Siloxane units (D units) represented by the formula: ６ SiO ３／２ and a polysiloxane (A1) (R １ ~R ６ each independently represents 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 ~R ６ are bonded to silicon atoms by Si-C bonds or Si-H bonds), and the polysiloxane (A1) comprises a polyorganosiloxane (a1) (the polyorganosiloxane (a1) has an alkenyl group having 2 to 10 carbon atoms, and SiO ２ Siloxane units (Q′ units) represented by the formula: ６ 'SiO ３／２ and 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 Si—H groups and SiO ２ Siloxane units (Q″ units) represented by R １ "R ２ "R ３ "SiO １／２ Siloxane units (M″ units) represented by R ４ "R ５ "SiO ２／２ Siloxane units (D″ units) represented by R ６ "SiO ３／２ and a siloxane unit selected from the group consisting of a siloxane unit (T″ unit) represented by the formula: １ “~R ６ " each independently represents an alkyl group having 1 to 10 carbon atoms or a hydrogen atom), and the release agent component (B) comprises an epoxy group-containing polyorganosiloxane, and when the content of the polyorganosiloxane (a1) in the total amount of components excluding the solvent in the adhesive composition is y %, and the content of the epoxy group-containing polyorganosiloxane in the total amount of components excluding the solvent in the adhesive composition is x %, the adhesive composition satisfies the following formula (I): y≦2.50In(x)+70.12 (I) 2. The polysiloxane (A1) further comprises a polyorganosiloxane (a3) ​​(the polyorganosiloxane (a3) ​​is R １ 'R ２ 'R ３ 'SiO １／２ Siloxane units (M′ units) represented by the formula: ４ 'R ５ 'SiO ２／２ and R １ '~R ５ 10 ' each independently represent 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.

3. 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 claim 1 or 2.

4. A method for producing 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, the method comprising the step of applying the adhesive composition according to claim 1 or 2 to either the semiconductor substrate or the electronic device substrate, or the support substrate, in order to form the adhesive layer.

5. A method for manufacturing a processed semiconductor substrate or electronic device substrate, comprising: a fifth step in which the semiconductor substrate or electronic device substrate of the laminate described in claim 3 is processed; and a sixth step in which the semiconductor substrate or electronic device substrate processed in the fifth step is separated from the support substrate.

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