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

Abstract

Provided is an adhesive composition for forming an adhesive layer between a support substrate and a semiconductor substrate or an electronic device substrate. The adhesive composition includes an adhesive component (A) that hardens by a hydrosilylation reaction, and the etching rate of the adhesive layer measured by a specific measurement method is 10 μm / min. or more.

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, semiconductor wafers are bonded to a support in preparation for polishing 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; applying too much force during removal can cause the thinned semiconductor wafer to cut or deform, so it must be easily removed to prevent such damage. 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 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] Incidentally, when a temporary adhesive (adhesive composition) is used to bond a support (support substrate) and a semiconductor wafer (semiconductor substrate or electronic device substrate), and after polishing the semiconductor wafer, the adhesive composition is required to be easily removed from the support and semiconductor wafer by washing.

[0007] The present invention has been made in view of the above circumstances, and aims to provide an adhesive composition that can be easily removed by cleaning after bonding a support substrate and a semiconductor substrate or an electronic device substrate, a laminate using the adhesive composition and a method for manufacturing the same, and a method for manufacturing a processed semiconductor substrate or an electronic device substrate using the laminate.

[0008] The inventors of the present invention conducted diligent studies to solve the aforementioned problems and found that the aforementioned problems can be solved by specifying the etching rate of the adhesive layer formed from the adhesive composition to a specific range, and have 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 the etching rate of the adhesive layer, as measured by the etching rate measurement method described below, is 10 μm / min or more. <Method for measuring etching rate> After measuring the thickness of the adhesive layer, which is approximately 100 μm thick, the adhesive layer, together with the semiconductor substrate or the electronic device substrate, is immersed in 7 mL of a cleaning agent composition prepared by mixing 5 g of tetrabutylammonium fluoride trihydrate with 95 g of N,N-dimethylpropionamide, while stirring for 5 minutes at 23°C, and the thickness after immersion is measured, and the etching rate is taken as x obtained by the following formula (1). x (μm / min) = [Thickness of the adhesive layer before immersion (μm) - Thickness of the adhesive layer after immersion (μm)] / 5 min ... (1) [2] The adhesive component (A) is SiO ２ Siloxane units (Q units) represented by R １ R ２ R ３ SiO１／２ The siloxane unit (M unit) represented by, R ４ R ５ SiO ２／２ The siloxane unit (D unit) represented by, and R ６ SiO ３／２ The 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 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 a Si-C bond or a Si-H bond.) is included, and the polysiloxane (A1) is a polyorganosiloxane (a1) (the polyorganosiloxane (a1) has an alkenyl group having 2 to 10 carbon atoms and is represented by SiO ２ The siloxane unit (Q' unit) represented by, and at least one of the siloxane units of R ６ 'SiO ３／２ The siloxane unit (T' unit) represented by, R ６ ' 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.) and a polyorganosiloxane (a2) (the polyorganosiloxane (a2) has a Si-H group and is represented by SiO ２ The siloxane unit (Q'' unit) represented by, R １ ”R ２ ”R ３ ”SiO １／２ The siloxane unit (M'' unit) represented by, R ４ ”R ５ ”SiO ２／２ [[ID=X]]”The siloxane unit (D'' unit) represented by, R ６ ”SiO ３／２ The siloxane unit (T'' unit) represented by, and a siloxane unit selected from the group consisting of two or more combinations thereof, R<X000029>” to R ６The adhesive composition according to [1], comprising (wherein each of these terms independently represents an alkyl group having 1 to 10 carbon atoms or a hydrogen atom), wherein the content of the polyorganosiloxane (a1) is 45 to 95% by mass relative to the total mass of the polysiloxane (A1). [3] The polysiloxane (A1) is further comprising polyorganosiloxane (a3) ​​(the polyorganosiloxane (a3) ​​is R １ 'R ２ 'R ３ 'SiO １／２ Siloxane units (M' units) represented by R ４ 'R ５ 'SiO ２／２ It contains at least one of the siloxane units (D' units) represented by R １ '~R ５[2] The adhesive composition according to [2], wherein each of the ' 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. [4] The adhesive composition according to any one of [1] to [3], wherein the adhesive component (A) further comprises a platinum group metal catalyst (A2). [5] The adhesive composition according to any one of [1] to [4], wherein the adhesive component (A) further comprises a polymerization inhibitor. [6] 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 [5]. [7] 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 step of applying an adhesive composition according to any one of [1] to [5] to any of the substrates of the semiconductor substrate or the electronic device substrate and the support substrate in order to form the adhesive layer. [8] 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 [6], 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 an adhesive composition that can be easily removed by cleaning after bonding a support substrate and a semiconductor substrate or electronic device substrate, a laminate using the adhesive composition and a method for manufacturing the same, and a method for manufacturing a processed semiconductor substrate or electronic device substrate using the laminate.

[0011] Figure 1 is a schematic cross-sectional view of an example of a laminate in the first embodiment. Figure 2 is a schematic cross-sectional view of another example of a laminate in the first embodiment. Figure 3A is a schematic cross-sectional view illustrating a method for manufacturing a laminate in an example of the first embodiment (part 1). Figure 3B is a schematic cross-sectional view illustrating a method for manufacturing a laminate in an example of the first embodiment (part 2). Figure 4 is a schematic cross-sectional view of another example of a laminate in the second embodiment. Figure 5 is a schematic cross-sectional view of another example of a laminate in the second embodiment. Figure 6A is a schematic cross-sectional view illustrating a method for manufacturing a laminate in an example of the second embodiment (part 1). Figure 6B is a schematic cross-sectional view illustrating a method for manufacturing a laminate in an example of the second embodiment (part 2). Figure 6C is a schematic cross-sectional view illustrating a method for manufacturing a laminate in an example of the second embodiment (part 3).

[0012] (Adhesive Composition) The adhesive composition of the present invention is an adhesive composition for forming an adhesive layer used for temporary bonding of a support substrate and a semiconductor substrate or an electronic device substrate. The adhesive composition contains an adhesive component (A) that hardens by a hydrosilylation reaction. The adhesive composition may contain other components.

[0013] In the adhesive layer formed from the adhesive composition of the present invention, the etching rate measured by the etching rate measurement method described below is 10 μm / min or more, preferably 12 μm / min or more, and more preferably 15 μm / min or more. If the etching rate is above the lower limit, the adhesive layer can be easily removed from the support substrate, semiconductor substrate, or electronic device substrate by cleaning. The upper limit of the etching rate is not particularly limited, but for example, 50 μm / min or less is preferred. <Method for measuring etching rate> The adhesive composition is applied to a semiconductor substrate or electronic device substrate to a thickness of approximately 100 μm, and the thickness of the adhesive layer obtained by heating it at 200°C for 10 minutes using a hot plate is measured. Then, the adhesive layer, together with the semiconductor substrate or electronic device substrate, is immersed in 7 mL of a cleaning agent composition prepared by mixing 5 g of tetrabutylammonium fluoride trihydrate with 95 g of N-methyl-2-pyrrolidone at 23°C for 5 minutes while stirring, and the thickness after immersion is measured. The value of x obtained by the following formula (1) is taken as the etching rate. x (μm / min) = [Film thickness of the adhesive layer before immersion (μm) - Film thickness of the adhesive layer after immersion (μm)] / 5 min ... (1)

[0014] The etching rate of the adhesive layer can be controlled by the type and content of the polyorganosiloxane (a1) in the adhesive component (A), the type and content of the platinum group metal catalyst (A2), and combinations thereof, as described later.

[0015] <Adhesive component (A)> Adhesive component (A) is a component that hardens by a hydrosilylation reaction. Adhesive component (A) contains polysiloxane (A1). Polysiloxane (A1) 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 ３／２It includes siloxane units (T units) represented by and siloxane units selected from the group consisting of two or more combinations thereof. Here, R １ ~R ６ Each of these independently represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or a monovalent chemical group consisting of a hydrogen atom. However, R １ ~R ６ These are each bonded to a silicon atom by either a Si-C bond or a Si-H bond.

[0016] R １ ~R ６ This group or atom is bonded to a silicon atom and independently represents an optionally substituted alkyl group, an optionally substituted alkenyl group, or a hydrogen atom. Examples of substituents include halogen atoms, nitro groups, cyano groups, amino groups, hydroxyl groups, carboxyl groups, aryl groups, heteroaryl groups, and the like.

[0017] <<Polysiloxane (A1)>> Polysiloxane (A1) contains polyorganosiloxane (a1) and polyorganosiloxane (a2). 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 siloxane unit of the siloxane unit (T' unit) represented by , where 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. 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 ３／２It includes siloxane units (T'' units) represented by and siloxane units selected from the group consisting of two or more combinations thereof. Here, R １ “~R ６ Each of these independently represents an alkyl group or hydrogen atom having 1 to 10 carbon atoms.

[0018] The content of polyorganosiloxane (a1) is preferably 45 to 95% by mass, more preferably 50 to 90% by mass, and even more preferably 60 to 85% by mass, relative to the total mass of polysiloxane (A1). If the content of polyorganosiloxane (a1) is above the lower limit, the etching rate of the adhesive layer formed from the adhesive composition can be further increased. If the content of polyorganosiloxane (a1) is below the upper limit, the viscosity of the adhesive composition can be reduced, and the applicability to semiconductor substrates or electronic device substrates can be further improved.

[0019] The polysiloxane (A1) preferably further contains polyorganosiloxane (a3). Polyorganosiloxane (a3) ​​is R １ 'R ２ 'R ３ 'SiO １／２ Siloxane units (M' units) represented by R ４ 'R ５ 'SiO ２／２ It contains at least one siloxane unit of the siloxane unit (D' unit) represented by . Here, R １ '~R ５ Each of the symbols ' 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. Note that polyorganosiloxane (a3) ​​is different from polyorganosiloxane (a1).

[0020] 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) represented by, R ４ 'R ５ 'SiO ２／２ siloxane units (D' units) represented by, and siloxane units selected from the group consisting of combinations of two or more of these, and R １ ' to R ６ ' 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, and is preferably a polyorganosiloxane.

[0021] R １ ' to R ６ ' are groups bonded to silicon atoms, and each independently represents an optionally substituted alkyl group or an optionally substituted alkenyl group, but at least one of R １ ' to R ６ ' is an optionally substituted alkenyl group. Examples of the substituent include a halogen atom, a nitro group, a cyano group, an amino group, a hydroxy group, a carboxy group, an aryl group, a heteroaryl group, and the like.

[0022] R １ ” to R ６ ” are groups or atoms bonded to silicon atoms, and each independently represents an optionally substituted alkyl group or a hydrogen atom, but at least one of R １ ” to R ６ ” 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 carboxy group, an aryl group, a heteroaryl group, and the like.

[0023] The alkyl group may be linear, branched, or cyclic, but a linear or branched alkyl group is preferred, and the number of carbon atoms thereof 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.

[0024] 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.

[0025] 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.

[0026] 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.

[0027] Specific examples of substituted linear or branched alkenyl groups include, but are not limited to, vinyl groups, allyl groups, buttenyl groups, and pentenyl groups. The number of carbon atoms is usually 2 to 14, preferably 2 to 10, and more preferably 1 to 6. Among these, ethenyl groups and 2-propenyl groups are particularly preferred. Specific examples of substituted cyclic alkenyl groups include, but are not limited to, cyclopentenyl and cyclohexenyl groups. The number of carbon atoms is usually 4 to 14, preferably 5 to 10, and more preferably 5 to 6.

[0028] As described above, polysiloxane (A1) comprises polyorganosiloxane (a1) and polyorganosiloxane (a2), and more preferably comprises polyorganosiloxane (a1), polyorganosiloxane (a3), and polyorganosiloxane (a2). In this specification, polyorganosiloxane (a1) and polyorganosiloxane (a3) ​​are collectively referred to as "polyorganosiloxane (a1), etc." The alkenyl groups contained in polyorganosiloxane (a1), etc. and the hydrogen atoms (Si-H groups) contained in polyorganosiloxane (a2) form a crosslinked structure through a hydrosilylation reaction by a platinum group metal catalyst (A2), and then harden. As a result, a hardened film is formed.

[0029] Polyorganosiloxanes (a1), etc., are composed of siloxane units in which an alkyl group and / or an alkenyl group is bonded to the silicon atom, R １ '~R ６ The proportion of alkenyl groups in the total substituents represented by ' is preferably 0.1 to 50.0 mol%, more preferably 0.5 to 30.0 mol%, and the remaining R １ '~R ６ ' can be an alkyl group.

[0030] Polyorganosiloxane (a2) is composed of siloxane units in which an alkyl group and / or a hydrogen atom is bonded to the silicon atom, R １ "~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.

[0031] When polysiloxane (A1) includes polyorganosiloxane (a1), polyorganosiloxane (a3), and polyorganosiloxane (a2), in a preferred embodiment of the present invention, the molar ratio of alkenyl groups contained in polyorganosiloxane (a1), etc., to hydrogen atoms constituting the Si-H bond contained in polyorganosiloxane (a2) is in the range of 1.0:0.5 to 1.0:0.66.

[0032] 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.

[0033] 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.

[0034] 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.

[0035] <<Platinum Group Metal Catalyst (A2)>> The adhesive component (A) of the present invention preferably contains a platinum group metal catalyst (A2) together with polysiloxane (A1). 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.

[0036] 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 and diolefins, platinum-olefin complexes, platinum-carbonyl complexes (e.g., platinum-bis(acetate), 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 and 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.

[0037] 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.

[0038] The content of the platinum group metal catalyst (A2) in the adhesive component (A) is preferably 0.1 to 100 ppm by mass, more preferably 0.1 to 50 ppm by mass, and even more preferably 0.1 to 10 ppm by mass, relative to the total mass of the polysiloxane (A1), in terms of metal. If the content of the platinum group metal catalyst (A2) is above the lower limit, the effect of promoting the hydrosilylation reaction can be further enhanced. If the content of the platinum group metal catalyst (A2) is below the upper limit, the viscosity of the adhesive composition can be reduced, and the coatability on semiconductor substrates can be further enhanced.

[0039] <<Polymerization Inhibitor>> The adhesive component (A) may contain a polymerization inhibitor for the purpose of suppressing the progress of the hydrosilylation reaction. The polymerization inhibitor is not particularly limited as long as it suppresses the progress of the hydrosilylation reaction, and specific examples include alkynyl alcohols such as 1-ethynyl-1-cyclohexanol and 1,1-diphenyl-2-propyne-1-ol. The amount of polymerization inhibitor is not particularly limited, but for example, it is usually 1000.0 ppm or more relative to the total amount of polyorganosiloxane (a1), polyorganosiloxane (a3), and polyorganosiloxane (a2), from the viewpoint of obtaining its effect, and 10000.0 ppm or less from the viewpoint of preventing excessive suppression of the hydrosilylation reaction.

[0040] <Release Agent Component> After processing of semiconductor substrates, etc., the semiconductor substrate or electronic device substrate (hereinafter also referred to as "semiconductor substrate, etc.") and the support substrate are separated. The adhesive composition of the present invention preferably contains a release agent component from the viewpoint of more easily separating the semiconductor substrate, etc. and the support substrate. Here, the release agent component is a component that does not undergo a hydrosilylation reaction and does not undergo a curing reaction. For example, polyorganosiloxane is an example. In this invention, "does not undergo a curing reaction" does not mean that no curing reaction occurs at all, but rather that it does not undergo the curing reaction that occurs in the curing adhesive component (A).

[0041] While there are no particular limitations on the release agent component, polyorganosiloxanes are preferred from the viewpoint of more favorably obtaining the effects of the present invention. Polyorganosiloxanes as release agent components do not usually react with adhesive component (A). For example, polyorganosiloxanes as release agent components are components that do not undergo hydrosilylation reactions.

[0042] The polyorganosiloxane is not particularly limited and examples include polydimethylsiloxane, epoxy group-containing polyorganosiloxane, phenyl group-containing polyorganosiloxane, and carbinol-modified polyorganosiloxane.

[0043] <<Polydimethylsiloxane>> Unlike epoxy group-containing polydimethylsiloxane, phenyl group-containing polydimethylsiloxane, carbinol-modified polyorganosiloxane, etc., the "polydimethylsiloxane" in this invention is an unmodified polyorganosiloxane having a methyl group as an organic group bonded to a silicon atom.

[0044] Specific examples of polydimethylsiloxanes include those represented by formula (M1), but are not limited to these.

[0045] (n ４ (This indicates the number of repeating units and is a positive integer.)

[0046] The weight-average molecular weight of polydimethylsiloxane is not particularly limited, but is usually 100,000 to 2,000,000, and 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. The degree of dispersion is not particularly limited, but is usually 1.0 to 10.0, and from the viewpoint of reproducibly achieving suitable peeling, it is preferably 1.5 to 5.0, more preferably 2.0 to 3.0. The weight-average molecular weight and degree of dispersion can be measured by the method described above for polyorganosiloxane. The viscosity of polydimethylsiloxane is not particularly limited, but is usually 1,000 to 2,000,000 mm². ２ The viscosity is given by / s. Note that the viscosity of polydimethylsiloxane is expressed as kinematic viscosity, centistokes (cSt) = mm². ２ It is / s. Viscosity (mPa·s) is compared to density (g / cm³). ３ It can also be obtained by dividing by ). In other words, the value can be obtained from the viscosity and density measured with an E-type rotational viscometer at 25°C, and the kinematic viscosity (mm²) ２ / s)=viscosity (mPa・s) / density (g / cm ３ It can be calculated using the formula:

[0047] <<Epoxy group-containing polyorganosiloxanes>> Examples of epoxy group-containing polyorganosiloxanes include R １１ R １２ SiO ２／２ Siloxane units (D) are represented by these units. １０ Examples include those containing units.

[0048] R １１ R is a group that bonds to a silicon atom and represents an alkyl group. １２The group is a group that bonds to a silicon atom and represents an epoxy group or an organic group containing an epoxy group. Specific examples of alkyl groups include those mentioned above. The epoxy group in an organic group containing an epoxy group may be an independent epoxy group that does not condense with other rings, or it may be an epoxy group that forms a fused ring with other rings, such as a 1,2-epoxycyclohexyl group. Specific examples of organic groups containing 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 an epoxy group-containing polyorganosiloxane is, but is not limited to, an epoxy group-containing polydimethylsiloxane.

[0049] Epoxy group-containing polyorganosiloxanes are the siloxane units (D) described above. １０ It includes units, but D １０ In addition to units, Q units, M units and / or T units may also be included. In a preferred embodiment of the present invention, a specific example of the epoxy group-containing polyorganosiloxane is D １０ Polyorganosiloxanes consisting only of units, D １０ Polyorganosiloxane containing units and Q units, D １０ Polyorganosiloxane containing units and M units, D １０ Polyorganosiloxanes containing units and T units, D １０ Polyorganosiloxane containing units, Q units, and M units, D １０ Polyorganosiloxane containing units, M units, and T units, D １０ Examples include polyorganosiloxanes containing units, Q units, M units, and T units.

[0050] The epoxy group-containing polyorganosiloxane may have epoxy groups in its side chains, or at one end, or at both ends.

[0051] 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.

[0052] Specific examples of epoxy group-containing polyorganosiloxanes include, but are not limited to, those represented by formulas (E1) to (E3).

[0053] (m １ and n １ (This indicates the number of each repeating unit and is a positive integer.)

[0054] (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-).

[0055] (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-).

[0056] 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.

[0057] 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.

[0058] The weight-average molecular weight of the epoxy group-containing polyorganosiloxane 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. 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 peeling. The weight-average molecular weight and degree of dispersion can be measured by the method described above for polyorganosiloxane. The viscosity of the epoxy group-containing polyorganosiloxane is not particularly limited, but is usually 1,000 to 2,000,000 mm². ２ The viscosity is given by / s. Note that the viscosity of epoxy group-containing polyorganosiloxanes is expressed as kinematic viscosity, centistokes (cSt) = mm². ２ It is / s. Viscosity (mPa·s) is compared to density (g / cm³). ３ It can also be obtained by dividing by ). In other words, the value can be obtained from the viscosity and density measured with an E-type rotational viscometer at 25°C, and the kinematic viscosity (mm²) ２ / s)=viscosity (mPa・s) / density (g / cm ３ It can be calculated using the formula:

[0059] <<Phenyl group-containing polyorganosiloxanes>> Examples of phenyl group-containing polyorganosiloxanes include R ３１ R ３２ SiO ２／２ Siloxane units (D) are represented by these units. ３０ Examples include those containing units.

[0060] 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.

[0061] 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.

[0062] In a preferred embodiment, 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.

[0063] Specific examples of phenyl group-containing polyorganosiloxanes include, but are not limited to, those represented by formula (P1) or (P2).

[0064] (m5 and n5 represent the number of repeating units and are positive integers.)

[0065] (m6 and n6 are positive integers, representing the number of each repeating unit.)

[0066] In the above general formula, m ５ , and m ６ 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.

[0067] <<Carbinol-Modified Polyorganosiloxane>> There are no particular restrictions on the carbinol-modified polyorganosiloxane. A carbinol-modified polyorganosiloxane is a polyorganosiloxane having a hydroxyl group directly bonded to a carbon atom. Thus, the carbinol in "carbinol-modified polyorganosiloxane" is not limited to methanol in the narrow sense, but includes methanol derivatives.

[0068] Carbinol-modified polyorganosiloxanes are, for example, carbinol-modified polydimethylsiloxanes.

[0069] The number of hydroxyl groups directly bonded to carbon atoms in a carbinol-modified polyorganosiloxane is not particularly limited and may be one or two or more.

[0070] Carbinol-modified polyorganosiloxane may have hydroxyl groups directly bonded to carbon atoms in its side chains, or at one end, or at both ends. It is preferable that the carbinol-modified polyorganosiloxane has hydroxyl groups directly bonded to carbon atoms in its side chains. In this case, even a small amount of carbinol-modified polyorganosiloxane can impart good release properties to the adhesive layer formed from the adhesive composition.

[0071] Carbinol-modified polyorganosiloxanes, for example, have a group represented by the following formula (Cg) as a group directly bonded to a silicon atom.

[0072] (In formula (Cg), R １ The symbol (*) represents a group with one or more carbon atoms. The asterisk (*) represents a bond to a silicon atom. However, the hydroxyl group in formula (Cg) is directly bonded to a carbon atom.

[0073] The number of hydroxyl groups directly bonded to the carbon atom in the group represented by formula (Cg) may be one or more. Examples of two or more include two, three, four, etc.

[0074] R １ The number of carbon atoms is not particularly limited; for example, it may be 1 to 30, 1 to 20, or 1 to 10.

[0075] Examples of groups represented by formula (Cg) include those represented by the following formulas (Cg-1) to (Cg-4). (In formula (Cg-1), R １１ R represents an alkylene group having 1 to 6 carbon atoms, which may be substituted with an alkoxy group having 1 to 3 carbon atoms. In formula (Cg-2), R １２ R represents an alkylene group with 1 to 6 carbon atoms. １３ R represents an alkylene group having 1 to 6 carbon atoms, which may be substituted with an alkoxy group having 1 to 3 carbon atoms or a hydroxyl group. In formula (Cg-3), R １４ R represents an alkylene group with 1 to 6 carbon atoms. １５ R represents an alkylene group with 1 to 3 carbon atoms. m represents an integer from 1 to 10. In formula (Cg-4), R １６ ~R １８ Each of these independently represents an alkylene group with 1 to 6 carbon atoms. In formulas (Cg-1) to (Cg-4), * represents a bond to a silicon atom.

[0076] R １１ ~R １８ The alkylene group may be linear, branched, or cyclic.

[0077] Examples of groups represented by formula (Cg) include the following: (In the formula, m1 represents an integer between 2 and 10. * represents a bond connecting to a silicon atom.)

[0078] Carbinol-modified polyorganosiloxanes are represented, for example, by the following formula (CPS-1) or formula (CPS-2). (In formula (CPS-1), R ５１ Each of these independently represents a hydrocarbon group. １ R represents the base represented by the above formula (Cg). n1 represents an integer greater than or equal to 0. n2 represents an integer greater than or equal to 1. In formula (CPS-2), R５２ Each of these independently represents a hydrocarbon group. ２ X represents the group represented by the above formula (Cg). ３ (where n3 represents a hydrocarbon group or a group represented by the above formula (Cg). n3 represents an integer of 0 or greater.)

[0079] R ５１ , R ５２ , and X ３ Examples of hydrocarbon groups in this include alkyl groups having 1 to 8 carbon atoms. A methyl group is preferred among the alkyl groups having 1 to 8 carbon atoms. That is, the carbinol-modified polyorganosiloxane is preferably a polydimethylsiloxane represented by the following formula (CPS-1a) or formula (CPS-2a). (In formula (CPS-1a), X １ represents the base represented by the above formula (Cg). n1 represents an integer greater than or equal to 0. n2 represents an integer greater than or equal to 1. In formula (CPS-2a), X ２ X represents the group represented by the above formula (Cg). ３ (where n3 represents a methyl group or a group represented by the above formula (Cg). n3 represents an integer of 0 or greater.)

[0080] Furthermore, the carbinol-modified polyorganosiloxane represented by formula (CPS-1) and the carbinol-modified polydimethylsiloxane represented by formula (CPS-1a) have hydroxyl groups directly bonded to carbon atoms in their side chains. The carbinol-modified polyorganosiloxane represented by formula (CPS-2) and the carbinol-modified polydimethylsiloxane represented by formula (CPS-2a) have hydroxyl groups directly bonded to carbon atoms at one or both ends.

[0081] Furthermore, in the carbinol-modified polyorganosiloxane represented by formula (CPS-1), if n2 is 2 or more, -Si(R ５１ ) (X １ The siloxane units represented by formula (CPS-1a) -O- may be arranged adjacently to form blocks, or they may be arranged randomly. In addition, in the carbinol-modified polydimethylsiloxane represented by formula (CPS-1a), when n2 is 2 or more, -Si(CH ３ ) (X１ The siloxane units represented by )-O- may be arranged adjacent to each other to form blocks, or they may be arranged randomly.

[0082] The weight-average molecular weight of the carbinol-modified polyorganosiloxane is not particularly limited, but is usually 500 to 1,000,000, and is preferably 5,000 to 50,000 from the viewpoint of reproducibly 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 peeling. The viscosity of the carbinol-modified polyorganosiloxane is not particularly limited, but is usually 100 to 200,000 mm². ２ The viscosity is given by / s. Note that the viscosity of polydimethylsiloxane is expressed as kinematic viscosity, centistokes (cSt) = mm². ２ It is / s. Viscosity (mPa·s) is compared to density (g / cm³). ３ It can also be obtained by dividing by ). In other words, the value can be obtained from the viscosity and density measured with an E-type rotational viscometer at 25°C, and the kinematic viscosity (mm²) ２ / s)=viscosity (mPa・s) / density (g / cm ３ It can be calculated using the formula:

[0083] Polyorganosiloxanes can be used as a release agent component either individually or in combination of two or more types. Here, "two or more polyorganosiloxanes" refers to, for example, a combination of polydimethylsiloxane and an epoxy group-containing polyorganosiloxane, or a combination of polydimethylsiloxane and a phenyl group-containing polyorganosiloxane, and does not refer to a combination of two epoxy group-containing polyorganosiloxanes that differ in molecular weight, viscosity, type of epoxy group, etc.

[0084] The polyorganosiloxane, which is the release agent component, may be a commercially available product or a synthesized product. Examples of commercially available polyorganosiloxanes include the WACKERSILICONE FLUID AK series (AK50, AK350, AK1000, AK10000, AK1000000) and GENIOPLAST, both manufactured by Wacker Chemistry. GUM, dimethyl silicone oil (KF-96L, KF-96A, KF-96, KF-96H, KF-69, KF-965, KF-968) and cyclic dimethyl silicone oil (KF-995) manufactured by Shin-Etsu Chemical Co., Ltd.; epoxy group-containing polyorganosiloxane (product names CMS-227, ECMS-327, EMS-622) manufactured by Gellest; epoxy group-containing polyorganosiloxane (KF-101, KF-1001, KF-1005, X-22-343) manufactured by Shin-Etsu Chemical Co., Ltd.; epoxy group-containing polyorganosiloxane (DOWSIL) manufactured by Dow-Toray. Examples include, but are not limited to, BY16-839, DOWSIL8413, DOWSIL8411; phenyl group-containing polyorganosiloxanes from Gellest (PMM-1043, PMM-1025, PDM-0421, PDM-0821); phenyl group-containing polyorganosiloxanes from Shin-Etsu Chemical Co., Ltd. (KF50-3000CS); and phenyl group-containing polyorganosiloxanes from Momentive (TSF431, TSF433).

[0085] Furthermore, commercially available carbinol-modified polyorganosiloxanes include, for example, KF6000, KF6001, KF6002, KF6003, X-22-4039, X-22-4015 from Shin-Etsu Silicone Co., Ltd.; DMS-C15, DMS-C16, DMS-C21, DMS-C23, DBE-C25, DBE-C22, DMS-CA21, DMS-CS26, CMS-221, CMS-222, CMS-832, CMS-626, MCR-C12, MCR-C18, MCR-C22, MCS-C11, MCS-C13, MCR-C61, MCR-C62, MCR-C63 from Dow Toray Corporation. Examples include 16-201, DOWSIL SF 8427 Fluid, DOWSIL SF 8428 Fluid, etc.

[0086] The content of the release agent component in the adhesive composition is not particularly limited, but from the viewpoint of suitably obtaining the effects of the present invention, it is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and particularly preferably 0.10% by mass or more, relative to the nonvolatile content of the adhesive composition. The upper limit is not particularly limited, but for example, it is preferably 30% by mass or less, more preferably 25% by mass or less, and particularly preferably 20% by mass or less. The nonvolatile content of the adhesive composition refers to components other than the solvent in the adhesive composition.

[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, 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 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] An example of an adhesive composition used in the present invention can be produced by mixing an adhesive component (A), a platinum group metal catalyst (A2), and a solvent. The mixing order is not particularly limited, but examples of methods that can easily and reproducibly produce an adhesive composition include, for example, dissolving the adhesive component (A) and the platinum group metal catalyst (A2) in the solvent, or dissolving a portion of the adhesive component (A) in the solvent, dissolving the remainder of the adhesive component (A) and the platinum group metal catalyst (A2) in the solvent, and mixing the resulting solutions, but are not limited to these. When preparing the adhesive composition, heating may be appropriate, as long as the components do not decompose or deteriorate. In the present invention, for the purpose of removing foreign matter, the solvent or solution used may be filtered using a filter or the like during the production of the adhesive composition or after all components have been mixed.

[0091] (Laminate) The laminate according to the present invention comprises a support substrate, a semiconductor substrate or an electronic device substrate, and an adhesive layer. The laminate according to the present invention may further have a release agent layer, in which case it has a configuration comprising a support substrate, a semiconductor substrate or an electronic device substrate, a release agent layer, and an adhesive layer.

[0092] The adhesive layer is provided between the semiconductor substrate or electronic device substrate and the support substrate.

[0093] In the adhesive layer, the etching rate measured by the etching rate measurement method described below is 10 μm / min or more, preferably 12 μm / min or more, and more preferably 15 μm / min or more. If the etching rate is above the lower limit, the adhesive layer can be easily removed from the support substrate, semiconductor substrate, or electronic device substrate by cleaning. The upper limit of the etching rate is not particularly limited, but for example, 50 μm / min or less is preferred. <Method for measuring the etching rate> After measuring the thickness of the adhesive layer with a thickness of approximately 100 μm, the adhesive layer together with the semiconductor substrate or electronic device substrate is immersed in 7 mL of a cleaning agent composition prepared by mixing 5 g of tetrabutylammonium fluoride trihydrate with 95 g of N-methyl-2-pyrrolidone at 23°C for 5 minutes while stirring, and the thickness after immersion is measured, and the etching rate is taken as x obtained by the following formula (1). x (μm / min) = [Thickness of the adhesive layer before immersion (μm) - Thickness of the adhesive layer after immersion (μm)] / 5 min ... (1)

[0094] The etching rate of the adhesive layer can be controlled by the type and content of the polyorganosiloxane (a1) in the adhesive component (A), the type and content of the platinum group metal catalyst (A2), and combinations thereof.

[0095] 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. While the semiconductor substrate is being processed such as thinning, the semiconductor substrate is supported by a support substrate. On the other hand, after the semiconductor substrate has been processed, the support substrate and the semiconductor substrate are separated. Similarly, while the electronic device substrate is being processed such as thinning, the electronic device substrate is supported by a support substrate. On the other hand, after the electronic device substrate has been processed, the support substrate and the electronic device substrate are separated. After the semiconductor substrate or electronic device substrate is separated from the support substrate, any residue of the release agent layer or adhesive layer remaining on the semiconductor substrate, electronic device substrate, or support substrate can be removed, for example, by a cleaning agent composition for cleaning semiconductor substrates, etc.

[0096] The following will be a detailed explanation, divided into two cases: when the laminate has a semiconductor substrate and when it has an electronic device substrate. The case where the laminate has a semiconductor substrate will be described in <First Embodiment> below, and the case where the laminate has an electronic device substrate will be described in <Second Embodiment> below.

[0097] <First Embodiment> A laminate having a semiconductor substrate is used for processing the semiconductor substrate. While the semiconductor substrate is being processed, the semiconductor substrate is bonded to a support substrate. After processing the semiconductor substrate, the semiconductor substrate is separated from the support substrate.

[0098] <<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 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.

[0099] A semiconductor substrate may have bumps. A bump is a protruding terminal. For example, a bump may be an electrode. In a laminate, if the semiconductor substrate has bumps, the bumps are located on the side of the support substrate. In a semiconductor substrate, bumps are usually formed on the surface on which the circuit is formed. The circuit may be single-layer or multi-layer. The shape of the circuit 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 materials for the bumps include low-melting-point solder, high-melting-point solder, tin, indium, gold, silver, and copper. The bumps may be composed of a single component or multiple components. More specifically, examples include Sn-based alloy plating such as SnAg bumps, SnBi bumps, Sn bumps, and AuSn bumps. The bumps may also have a laminated structure including a metal layer made of at least one of these components.

[0100] An example of a semiconductor substrate is a silicon wafer with a diameter of approximately 300 mm and a thickness of approximately 770 μm.

[0101] <<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.

[0102] 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.

[0103] An example of a support substrate is a glass wafer with a diameter of approximately 300 mm and a thickness of approximately 700 μm.

[0104] Furthermore, when delamination in a laminate is performed by light irradiation, a substrate that is light-transmitting to the light used is used as the support substrate.

[0105] <<Adhesive Layer>> The adhesive layer is provided between the support substrate and the semiconductor substrate. The adhesive layer is in contact with the semiconductor substrate, for example. The adhesive layer may also be in contact with the support substrate, for example. The adhesive layer is an adhesive layer formed from an adhesive composition.

[0106] 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.

[0107] The method for forming an adhesive layer from the adhesive composition will be described in detail below in the section titled "<>".

[0108] <<Release Agent Layer>> The laminate may have a release agent layer. In a laminate having a release agent layer, separation of the semiconductor substrate and the support substrate is performed, for example, by light irradiation of the release agent layer. The release agent layer is formed, for example, from a release agent composition.

[0109] <<<Release Agent Composition>>> The release agent composition contains, for example, at least an organic resin or a polynuclear phenol derivative, and optionally other components. The organic resin is preferably one that can exhibit suitable release ability, and when the semiconductor substrate and the support substrate are separated by light irradiation of the release agent layer, the organic resin preferably absorbs light and undergoes a change, such as decomposition, necessary to improve the release ability.

[0110] A laminate having a release agent layer formed from a release agent composition can be peeled off without applying excessive load for peeling by, for example, irradiating the release agent layer with a laser. The release agent layer of the laminate has a reduced adhesive strength compared to before irradiation, for example, when irradiated with a laser. That is, in the laminate, for example, while a semiconductor substrate is being processed such as thinning, the semiconductor substrate is suitably supported on a laser-transmitting support substrate via an adhesive layer and a release agent layer. After processing is complete, by irradiating a laser from the support substrate side, the laser that has passed through the support substrate is absorbed by the release agent layer, causing alteration (e.g., separation) of the release agent layer at the interface between the release agent layer and the adhesive layer, at the interface between the release agent layer and the support substrate, or within the release agent layer itself. As a result, suitable peeling (separation) can be achieved without applying excessive load for peeling.

[0111] <<<<<Novolac resin>>>> Examples of organic resins include novolac resins. Novolac resins are resins obtained by condensing at least one of a phenolic compound, a carbazole compound, and an aromatic amine compound with at least one of an aldehyde compound, a ketone compound, and a divinyl compound under acid catalyst.

[0112] Examples of phenolic compounds include phenols, naphthols, antrols, and hydroxypyrenes. Examples of phenols include phenol, cresol, xylenol, resorcinol, bisphenol A, p-tert-butylphenol, p-octylphenol, 9,9-bis(4-hydroxyphenyl)fluorene, and 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane. Examples of naphthols include 1-naphthol, 2-naphthol, 1,5-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, and 9,9-bis(6-hydroxynaphthyl)fluorene. Examples of antrols include 9-antrol. Examples of hydroxypyrenes include 1-hydroxypyrene and 2-hydroxypyrene. Examples of carbazole compounds include carbazole, 1,3,6,8-tetranitrocarbazole, 3,6-diaminocarbazole, 3,6-dibromo-9-ethylcarbazole, 3,6-dibromo-9-phenylcarbazole, 3,6-dibromocarbazole, 3,6-dichlorocarbazole, 3-amino-9-ethylcarbazole, 3-bromo-9-ethylcarbazole, 4,4'bis(9H-carbazole-9-yl)biphenyl, 4-glycidylcarbazole, 4-hydroxycarbazole, and 9-(1H-benzotriazole-1-ylmethyl Examples include (9-ethylcarbazole-9H-carbazole, 9-acetyl-3,6-diiodocarbazole, 9-benzoylcarbazole, 9-benzoylcarbazole-6-dicarboxyaldehyde, 9-benzylcarbazole-3-carboxyaldehyde, 9-methylcarbazole, 9-phenylcarbazole, 9-vinylcarbazole, potassium carbazole, carbazole-N-carbonyl chloride, N-ethylcarbazole-3-carboxyaldehyde, and N-((9-ethylcarbazole-3-yl)methylene)-2-methyl-1-indolinylamine. Examples of aromatic amine compounds include diphenylamine and N-phenyl-1-naphthylamine. These can be used individually or in combination of two or more. They may also have substituents.For example, these may have substituents on the aromatic ring.

[0113] Examples of aldehyde compounds include formaldehyde, paraformaldehyde, acetaldehyde, propylaldehyde, butyraldehyde, isobutyraldehyde, valeraldehyde, caproaldehyde, 2-methylbutyraldehyde, hexylaldehyde, undecanealdehyde, 7-methoxy-3,7-dimethyloctylaldehyde, cyclohexanealdehyde, 3-methyl-2-butyraldehyde, glyoxal, malonaldehyde, succinaldehyde, glutaraldehyde, and azipi Examples of suitable aldehydes include saturated aliphatic aldehydes such as ammonium aldehydes, unsaturated aliphatic aldehydes such as acrolein and methacrolein, heterocyclic aldehydes such as furfural and pyridine aldehyde, and aromatic aldehydes such as benzaldehyde, naphthyl aldehyde, anthryl aldehyde, phenanthryl aldehyde, salicyl aldehyde, phenylacetaldehyde, 3-phenylpropionaldehyde, tolyl aldehyde, (N,N-dimethylamino)benzaldehyde, and acetoxybenzaldehyde. Among these, aromatic aldehydes are preferred. Examples of suitable ketone compounds include diaryl ketone compounds such as diphenyl ketone, phenylnaphthyl ketone, dinaphthyl ketone, phenyltolyl ketone, and ditolyl ketone. Examples of divinyl compounds include divinylbenzene, dicyclopentadiene, tetrahydroindene, 4-vinylcyclohexene, 5-vinylnoborna-2-ene, divinylpyrene, limonene, and 5-vinylnorbornadiene. These can be used individually or in combination of two or more.

[0114] The organic resin contained in the above-mentioned release agent composition is preferably novolac resin. Therefore, the above-mentioned release agent composition preferably contains novolac resin alone as the organic resin. However, other polymers may be included together with the novolac resin for purposes such as adjusting the film properties. Examples of such other polymers include polyacrylic acid ester compounds, polymethacrylic acid ester compounds, polyacrylamide compounds, polymethacrylamide compounds, polyvinyl compounds, polystyrene compounds, polymaleimide compounds, polymaleic anhydride, and polyacrylonitrile compounds.

[0115] The content of novolac resin in the release agent composition is not particularly limited, but it is preferably 70% by mass or more relative to the total amount of polymer contained in the release agent composition. The content of novolac resin in the release agent composition is not particularly limited, but it is preferably 50 to 100% by mass relative to the film constituent components. In this invention, film constituent components refer to components other than the solvent contained in the composition.

[0116] <<<<<Polynuclear phenol derivatives>>>> A polynuclear phenol derivative is represented, for example, by the following formula (P).

[0117] In formula (P), Ar represents an arylene group, and the number of carbon atoms is not particularly limited, but is usually 6 to 60. From the viewpoint of preparing a release agent composition with excellent uniformity and obtaining a release agent layer with higher flatness with good reproducibility, the number of carbon atoms is preferably 30 or less, more preferably 20 or less, even more preferably 18 or less, and still more preferably 12 or less.

[0118] Specific examples of such arylene groups include 1,2-phenylene, 1,3-phenylene, 1,4-phenylene; 1,5-naphthalenediyl, 1,8-naphthalenediyl, 2,6-naphthalenediyl, 2,7-naphthalenediyl, 1,2-anthracenediyl, 1,3-anthracenediyl, 1,4-anthracenediyl, 1,5-anthracenediyl, 1,6-anthracenediyl, 1,7-anthracenediyl, 1,8-anthracenediyl, and 2,3-anthracenediyl. Examples include, but are not limited to, groups derived by removing two hydrogen atoms from the aromatic ring of fused ring aromatic hydrocarbon compounds such as diyl, 2,6-anthracenediyl, 2,7-anthracenediyl, 2,9-anthracenediyl, 2,10-anthracenediyl, and 9,10-anthracenediyl groups; and groups derived by removing two hydrogen atoms from the aromatic ring of ring-linked ring aromatic hydrocarbon compounds such as biphenyl-4,4'-diyl group and paraterphenyl-4,4''-diyl group.

[0119] From the viewpoint of obtaining a laminate that exhibits good peelability as a release agent layer and allows for good separation of the support substrate with good reproducibility, the polynuclear phenol derivative represented by formula (P) is preferably a polynuclear phenol derivative represented by formula (P-1), more preferably a polynuclear phenol derivative represented by formula (P-1-1), and even more preferably a polynuclear phenol derivative represented by formula (P1).

[0120]

[0121] The content of the polynuclear phenol derivative in the release agent composition is not particularly limited, but it is preferably 50 to 100% by mass relative to the film components.

[0122] <<

[0123] In a preferred embodiment, the release agent composition contains at least a novolac resin and optionally other components such as a crosslinking agent, an acid generator, an acid, a surfactant, or a solvent. In another preferred embodiment, the release agent composition contains at least a polynuclear phenol derivative and a crosslinking agent, and optionally other components such as an acid generator, an acid, a surfactant, or a solvent. In yet another preferred embodiment, the release agent composition contains at least an organic resin and a branched polysilane, and optionally other components such as a crosslinking agent, an acid generator, an acid, a surfactant, or a solvent.

[0124] <<<<Solvent>>>> The release agent composition preferably contains a solvent. As such a solvent, for example, a highly polar solvent that can well dissolve the aforementioned organic resins, polynuclear phenol derivatives, branched polysilanes, and other film components can be used, and if necessary, a low-polarity solvent may be used for the purpose of adjusting viscosity, surface tension, etc. In this invention, a low-polarity solvent is defined as one with a relative permittivity of less than 7 at a frequency of 100 kHz, and a highly polar solvent is defined as one with a relative permittivity of 7 or more at a frequency of 100 kHz. The solvent can be used alone or in combination of two or more types.

[0125] Examples of highly polar solvents include amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylisobutylamide, N-methylpyrrolidone, and 1,3-dimethyl-2-imidazolidinone; ketone solvents such as ethyl methyl ketone, isophorone, and cyclohexanone; cyano solvents such as acetonitrile and 3-methoxypropionitrile; polyhydric alcohol solvents such as ethylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, 1,3-butanediol, and 2,3-butanediol; monohydric alcohol solvents other than aliphatic alcohols such as propylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monophenyl ether, triethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, benzyl alcohol, 2-phenoxyethanol, 2-benzyloxyethanol, 3-phenoxybenzyl alcohol, and tetrahydrofurfuryl alcohol; and sulfoxide solvents such as dimethyl sulfoxide.

[0126] Examples of low-polarity solvents include chlorine-based solvents such as chloroform and chlorobenzene; aromatic hydrocarbon solvents such as alkylbenzenes such as toluene, xylene, tetralin, cyclohexylbenzene, and decylbenzene; aliphatic alcohol solvents such as 1-octanol, 1-nonanol, and 1-decanol; ether-based solvents such as tetrahydrofuran, dioxane, anisole, 4-methoxytoluene, 3-phenoxytoluene, dibenzyl ether, diethylene glycol dimethyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, and triethylene glycol butyl methyl ether; and ester-based solvents such as methyl benzoate, ethyl benzoate, butyl benzoate, isoamyl benzoate, bis(2-ethylhexyl) phthalate, dibutyl maleate, dibutyl oxalate, hexyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, and diethylene glycol monobutyl ether acetate.

[0127] The solvent content is determined appropriately considering the viscosity of the desired composition, the coating method used, the thickness of the film to be produced, etc., but is 99% by mass or less of the total composition, preferably 70 to 99% by mass of the total composition, that is, the amount of film components in that case is 1 to 30% by mass of the total composition.

[0128] The viscosity and surface tension of the release agent composition are appropriately adjusted by changing the type of solvent used, their ratios, and the concentration of film components, taking into consideration various factors such as the application method used and the desired film thickness.

[0129] A release agent composition can be produced, for example, by mixing an organic resin or a polynuclear phenol derivative with a solvent and, if necessary, a crosslinking agent. The mixing order is not particularly limited, but examples of methods that can easily and reproducibly produce a release agent composition include, but are not limited to, a method in which the organic resin or polynuclear phenol derivative and the crosslinking agent are dissolved in the solvent at once, or a method in which a portion of the organic resin or polynuclear phenol derivative and the crosslinking agent are dissolved in the solvent, the remainder is dissolved separately in the solvent, and the resulting solutions are mixed. Furthermore, when preparing the release agent composition, heating may be appropriately applied, as long as the components do not decompose or deteriorate. In the present invention, for the purpose of removing foreign matter, the solvent or solution used may be filtered using a filter or the like during the production of the release agent composition or after all components have been mixed.

[0130] The thickness of the release agent layer is not particularly limited, but is usually 5 nm to 100 μm, 10 nm to 10 μm in one embodiment, 50 nm to 1 μm in another embodiment, and 100 nm to 700 nm in yet another embodiment.

[0131] There are no particular limitations on the method for forming a release agent layer from a release agent composition, but one example is a method of forming a release agent layer by coating the release agent composition. There are no particular limitations on the method of coating the release agent composition, but it is usually a spin coating method. The heating temperature of the coated release agent composition cannot be specified in general terms as it varies depending on the type and amount of release agent components contained in the release agent composition, the desired thickness of the release agent layer, etc. However, from the viewpoint of reproducibly achieving a suitable release agent layer, it is 80°C to 300°C, and the heating time is usually appropriately determined in the range of 10 seconds to 10 minutes depending on the heating temperature. The heating temperature is preferably 100°C to 280°C, and more preferably 150°C to 250°C. The heating time is preferably 30 seconds to 8 minutes, and more preferably 1 minute to 5 minutes. Heating can be carried out using a hot plate, oven, etc.

[0132] The following describes an example of the configuration of the laminate according to the first embodiment, using the figures. Figure 1 shows a schematic cross-sectional view of an example of the laminate according to the first embodiment. The laminate in Figure 1 has a semiconductor substrate 1, an adhesive layer 2, and a support substrate 4 in this order. That is, the adhesive layer 2 is provided between the semiconductor substrate 1 and the support substrate 4. The adhesive layer 2 is in contact with the semiconductor substrate 1 and the support substrate 4.

[0133] The following describes another example of the configuration of the laminate according to the first embodiment, using the figures. Figure 2 shows a schematic cross-sectional view of another example of the laminate according to the first embodiment. The laminate in Figure 2 has a semiconductor substrate 1, an adhesive layer 2, a release agent layer 3, and a support substrate 4 in this order. The adhesive layer 2 and the release agent layer 3 are provided between the semiconductor substrate 1 and the support substrate 4. The adhesive layer 2 is in contact with the semiconductor substrate 1. The release agent layer 3 is in contact with the adhesive layer 2 and the support substrate 4.

[0134] <<Example of Manufacturing Method for a Laminate in the First Embodiment>> The manufacturing method for a laminate will be described below, using the laminate shown in Figure 1 as an example from the laminates in the first embodiment. An example of the laminate of the present invention can be manufactured by a method including the following first and second steps. First step: A step of applying an adhesive composition onto a semiconductor substrate to form an adhesive coating layer. Second step: A step of heating the adhesive coating layer to form an adhesive layer.

[0135] 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.

[0136] In this invention, the laminate can be obtained by applying a load in the thickness direction of the semiconductor substrate and the support substrate while performing heat treatment, vacuum treatment, or both, and then performing 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.

[0137] The heat treatment is usually determined appropriately from a range of 20 to 160°C, from the viewpoint of removing the solvent 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.

[0138] 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.

[0139] 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.

[0140] 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 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 it is preferable to post-heat with the semiconductor substrate facing downwards from the viewpoint of achieving suitable peeling with good reproducibility. 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.

[0141] Figures 3A to 3C illustrate one method of manufacturing a laminate. 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 heating it. Next, the laminate shown in Figure 3A and the support substrate 4 are bonded together so that the adhesive coating layer 2a and the support substrate 4 are in contact. Then, after applying a load in the thickness direction of the semiconductor substrate 1 and the support substrate 4 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 heated and cured by the heating device to convert it into an adhesive layer 2 (Figure 3B). The laminate shown in Figure 1 is obtained by the process shown in Figures 3A to 3B.

[0142] <Second Embodiment> A laminate having an electronic device substrate is used for processing the electronic device substrate. While the electronic device substrate is being processed, the electronic device substrate is bonded to a support substrate. After processing the electronic device substrate, the electronic device substrate is separated from the support substrate.

[0143] <<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.

[0144] <<Support Substrate>> An example of a support substrate is the same as the one described in the <<Support Substrate>> section of the <<First Embodiment>> above.

[0145] <<Release Agent Layer>> The release agent layer is formed using the release agent composition described above. A detailed explanation of the release agent layer is as described in the <<Release Agent Layer>> section of the <<First Embodiment>> above.

[0146] <<Adhesive Layer>> The adhesive layer is formed using the adhesive composition described above. A detailed description of the adhesive layer is as described in the <<Adhesive Layer>> section of the <<First Embodiment>> above.

[0147] The following describes an example of the configuration of the laminate according to the second embodiment with reference to the figures. The laminate in Figure 4 has a support substrate 24, 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 24. The adhesive layer 22 is in contact with the electronic device substrate 26 and the support substrate 24.

[0148] Figure 5 shows a schematic cross-sectional view of another example of the laminate of the second embodiment. The laminate of Figure 5 has a support substrate 24, a release agent layer 23, an adhesive layer 22, and an electronic device substrate 26 in this 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 and the release agent layer 23 are provided between the electronic device substrate 26 and the support substrate 24. The adhesive layer 22 is in contact with the electronic device substrate 26. The release agent layer 23 is in contact with the adhesive layer 22 and the support substrate 24.

[0149] <<Example of a manufacturing method for a laminate in the second embodiment>> The manufacturing method for a laminate will be described below using the laminate shown in Figure 4 as an example from the laminates in the second embodiment. The laminate of the present invention can be manufactured by a method including the following first to fourth steps. First step: Apply an adhesive composition to the surface of the support substrate to form an adhesive coating layer (and if necessary, further heat to form an adhesive layer) Second step: Place a semiconductor chip substrate on the adhesive coating layer or adhesive layer and bond the semiconductor chip substrate to the adhesive coating layer or adhesive layer while performing at least one of a heat treatment and a vacuum treatment Third step: Harden the adhesive coating layer by post-heat treatment to form an adhesive layer Fourth step: Seal the semiconductor chip substrate fixed on the adhesive layer using a sealing resin A more detailed explanation of the second step is, for example, the step of the embodiment in (i) below. (i) A semiconductor chip substrate is placed on the adhesive coating layer or adhesive layer, and while performing at least one of a heat treatment and a reduced pressure treatment, a load is applied in the thickness direction to the semiconductor chip substrate and the support substrate to bring them into close contact, thereby bonding the semiconductor chip substrate to the adhesive coating layer or adhesive layer.

[0150] Furthermore, the third step may be performed after the semiconductor chip substrate has been bonded to the adhesive coating layer in the second step, or it may be performed in conjunction with the second step. For example, the semiconductor chip substrate may be placed on the adhesive coating layer, and while applying a load in the thickness direction of the semiconductor chip substrate and the support substrate, the adhesive coating layer may be heated and cured to simultaneously achieve adhesion between the semiconductor chip substrate and the adhesive coating layer and curing from the adhesive coating layer to the adhesive layer, thereby bonding the adhesive layer to the semiconductor chip substrate. Alternatively, the third step may be performed before the second step, in which case the semiconductor chip substrate may be placed on the adhesive layer, and while applying a load in the thickness direction of the semiconductor chip substrate and the support substrate, the adhesive layer and the semiconductor chip substrate may be bonded together.

[0151] The application method, the heating temperature of the applied adhesive composition, the heating means, etc., are as described in the section "<<Example of manufacturing method of laminate in the first embodiment>>" in the first embodiment above.

[0152] The method for manufacturing the laminate according to the second embodiment will be described in more detail below with reference to the figures. In this manufacturing method, the laminate shown in Figure 4 is manufactured. As shown in Figure 6A, an adhesive coating layer 22' made of an adhesive composition is formed on the support substrate 24. At this time, the adhesive coating layer 22' may be heated to form the adhesive layer 22. Next, as shown in Figure 6B, a semiconductor chip substrate 21 is placed on the adhesive layer 22 or adhesive coating layer 22', and while performing at least one of a heat treatment and a vacuum treatment, a load in the thickness direction is applied to the semiconductor chip substrate 21 and the support substrate 24 to bring them into close contact, thereby bonding the semiconductor chip substrate 21 to the adhesive layer 22 or adhesive coating layer 22'. If the semiconductor chip substrate 21 is bonded to the adhesive coating layer 22', the adhesive coating layer 22' is cured by post-heat treatment to become an adhesive layer 22, and the semiconductor chip substrate 21 is fixed to the adhesive layer 22. Next, as shown in Figure 6C, the semiconductor chip substrate 21 fixed on the adhesive layer 22 is sealed using a sealing resin 25. In Figure 6C, multiple semiconductor chip substrates 21, temporarily bonded to a support substrate 24 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.

[0153] <<<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 is compression molded to form a layer made of sealing resin 25 on the adhesive layer 22. 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.

[0154] (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.

[0155] 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.

[0156] 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.

[0157] <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.

[0158] <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.

[0159] 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, a method of mechanical peeling using equipment 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 (semiconductor substrate, etc.) and the support substrate, and then the semiconductor substrate or electronic device substrate (semiconductor substrate, etc.) and the support substrate are separated. If the laminate has a release agent layer, the release agent layer can be irradiated with light, and the release agent layer that absorbs the light undergoes a change in quality (e.g., separation or decomposition), making it easier to separate the semiconductor substrate or electronic device substrate from the support substrate.

[0160] 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.

[0161] 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.

[0162] 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.

[0163] 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.

[0164] 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.

[0165] 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.

[0166] 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.

[0167] 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.

[0168] 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.

[0169] A suitable example of an amide solvent is an acid amide derivative represented by formula (Z).

[0170] In the formula, R ０ R represents an ethyl group, a propyl group, or an isopropyl group, with ethyl and isopropyl groups being preferred, and ethyl group being 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.

[0171] 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.

[0172] The acid amide derivative represented by formula (Z) may be synthesized by substitution reaction of the corresponding carboxylic acid ester with an amine, or a commercially available product may be used.

[0173] Another example of a preferred amide solvent is a lactam compound represented by formula (Y).

[0174] 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.

[0175] 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.

[0176] 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-methyl-2-pyrrolidone (NMP) or N-ethyl-2-pyrrolidone (NEP), and in one even more preferred embodiment, comprises N-methyl-2-pyrrolidone (NMP).

[0177] 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.

[0178] 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.

[0179] 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.

[0180] (1) Mixing rotor: Mixing rotor VMR-5R manufactured by AS ONE Corporation (2) Stirrer: Rotating and revolving mixer ARE-500 manufactured by Sinky Co., Ltd.

[0181] [1] Preparation of adhesive composition [Preparation example 1] In a 600 mL stirring container for use with a stirrer, 80 g of MQ resin (manufactured by Wacker Chem Ltd.) containing polysiloxane and vinyl groups as polyorganosiloxane (a1), 2.52 g of linear polydimethylsiloxane containing SiH groups with a viscosity of 100 mPa·s (manufactured by Wacker Chem Ltd.) as polyorganosiloxane (a2), 5.89 g of linear polydimethylsiloxane containing SiH groups with a viscosity of 70 mPa·s (manufactured by Wacker Chem Ltd.) as polyorganosiloxane (a2), and 0.22 g of 1-ethynyl-1-cyclohexanol (manufactured by Wacker Chem Ltd.) as a polymerization inhibitor were added and stirred with a stirrer for 5 minutes to obtain mixture (I). Mixture (II) was obtained by stirring for 5 minutes with 0.147 g of platinum catalyst (manufactured by Wacker Chem Co., Ltd.) as a platinum group metal catalyst (A2) (10 ppm by mass in terms of metal relative to the total mass of polysiloxane (A1)) and 5.81 g of vinyl group-containing linear polydimethylsiloxane (manufactured by Wacker Chem Co., Ltd.) with a viscosity of 1000 mPa·s as polyorganosiloxane (a3). 3.96 g of mixture (II) was added to mixture (I) and stirred for 5 minutes with a stirrer to obtain adhesive composition (1). The ratio of components was adjusted so that the mass ratio of vinyl group-containing MQ resin / total polymer components was 49 / 100.

[0182] [Preparation Example 2] 1.0 g of 1,1-diphenyl-2-propyne-1-ol (manufactured by Tokyo Chemical Industry Co., Ltd.) as a polymerization inhibitor and 1.0 g of 1-ethynyl-1-cyclohexanol (manufactured by Wacker Chem Co., Ltd.) as a polymerization inhibitor were added to a 50 ml screw tube, and the mixture was stirred for 10 minutes with a mix rotor to obtain mixture (I). 232.3 g of vinyl group-containing MQ resin (manufactured by Wacker Chem Co., Ltd.), dissolved in paramentane to a solid content of 81.7%, was added as polyorganosiloxane (a1), and 0.02 g of platinum catalyst (manufactured by Wacker Chem Co., Ltd.) as a platinum group metal catalyst (A2) (0.5 ppm by mass in terms of metal relative to the total mass of polysiloxane (A1)) was added, and the mixture was stirred for 5 minutes with a stirrer to obtain mixture (II). Next, 1.0 g of mixture (I) was added to mixture (II), and the mixture was stirred with a stirrer for 5 minutes to obtain mixture (III). Next, a mixture (IV) was prepared by premixing the following polyorganosiloxanes in a mass ratio of 54:36:10: MQ resin containing polysiloxane and vinyl groups (manufactured by Wacker Chem Co., Ltd.) as polyorganosiloxane (a1), linear polydimethylsiloxane containing vinyl groups with a viscosity of 200 mPa·s (manufactured by Wacker Chem Co., Ltd.) as polyorganosiloxane (a3), and linear polydimethylsiloxane containing SiH groups with a viscosity of 100 mPa·s (manufactured by Wacker Chem Co., Ltd.) as polyorganosiloxane (a2). To mixture (III), 28.4 g of SiH group-containing linear polydimethylsiloxane (manufactured by Wacker Chem Co., Ltd.) with a viscosity of 100 mPa·s as polyorganosiloxane (a2) and 189.2 g of mixture (IV) were added, and the mixture was stirred with a stirrer for 5 minutes to obtain adhesive composition (2). The ratio of the components was adjusted so that the mass ratio of vinyl group-containing MQ resin / total polymer components was 70 / 100.

[0183] [Preparation Example 3] 2.3 g of 1,1-diphenyl-2-propyne-1-ol (manufactured by Tokyo Chemical Industry Co., Ltd.) as a polymerization inhibitor and 2.3 g of 1-ethynyl-1-cyclohexanol (manufactured by Wacker Chem Co., Ltd.) as a polymerization inhibitor were added to a 50 ml screw tube, and the mixture was stirred with a mixing rotor for 10 minutes to obtain mixture (I). In a 600 mL stirring container specifically for the rotation-orbit mixer, 401.9 g of vinyl group-containing MQ resin (manufactured by Wacker Chem Co., Ltd.), dissolved in paramentane to a solid content of 81.7%, was added as polyorganosiloxane (a1). 0.50 g of platinum catalyst (manufactured by Wacker Chem Co., Ltd.) was added as platinum group metal catalyst (A2) (10 ppm by mass in terms of metal relative to the total mass of polysiloxane (A1)). 46.7 g of vinyl group-containing linear polydimethylsiloxane (manufactured by Wacker Chem Co., Ltd.), with a viscosity of 100,000 mPa·s, was added as polyorganosiloxane (a3). The mixture was stirred with a stirrer for 5 minutes to obtain mixture (II). Next, 2.33 g of mixture (I) was added to mixture (II), and the mixture was stirred with a stirrer for 5 minutes to obtain mixture (III). Next, a mixture (IV) was prepared by premixing three polyorganosiloxanes in a mass ratio of 54:36:10: MQ resin (manufactured by Wacker Chem Co., Ltd.) containing polysiloxane and vinyl groups as polyorganosiloxane (a1), linear polydimethylsiloxane containing vinyl groups with a viscosity of 200 mPa·s (manufactured by Wacker Chem Co., Ltd.) as polyorganosiloxane (a3), and linear polydimethylsiloxane containing SiH groups with a viscosity of 100 mPa·s (manufactured by Wacker Chem Co., Ltd.) as polyorganosiloxane (a2). To mixture (III), 49.7 g of linear polydimethylsiloxane containing SiH groups with a viscosity of 100 mPa·s (manufactured by Wacker Chem Co., Ltd.) and 42.0 g of mixture (IV) were added, and the mixture was stirred with a stirrer for 5 minutes to obtain adhesive composition (3). The ratio of components was adjusted so that the mass ratio of vinyl group-containing MQ resin to total polymer components was 75 / 100.

[0184] [Preparation Example 4] 2.24 g of 1,1-diphenyl-2-propyne-1-ol (manufactured by Tokyo Chemical Industry Co., Ltd.) as a polymerization inhibitor and 2.24 g of 1-ethynyl-1-cyclohexanol (manufactured by Wacker Chem Co., Ltd.) as a polymerization inhibitor were added to a 50 ml screw tube, and the mixture was stirred with a mixing rotor for 10 minutes to obtain mixture (I). In a 600 mL stirring container specifically for the rotation-orbit mixer, 117.1 g of vinyl group-containing MQ resin (manufactured by Wacker Chem Co., Ltd.), dissolved in paramentane to a solid content of 81.7%, was added as polyorganosiloxane (a1). 0.02 g of platinum catalyst (manufactured by Wacker Chem Co., Ltd.) was added as platinum group metal catalyst (A2) (0.5 ppm by mass in terms of metal relative to the total mass of polysiloxane (A1)). 31.4 g of vinyl group-containing linear polydimethylsiloxane (manufactured by Wacker Chem Co., Ltd.), with a viscosity of 100,000 mPa·s, was added as polyorganosiloxane (a3). The mixture was stirred for 5 minutes using a stirrer to obtain mixture (II). Next, 2.24 g of mixture (I) was added to mixture (II), and the mixture was stirred for 5 minutes using a stirrer to obtain mixture (III). Next, a mixture (IV) was prepared by premixing polyorganosiloxane (a1) with MQ resin containing polysiloxane and vinyl groups (manufactured by Wacker Chem), polyorganosiloxane (a3) ​​with a viscosity of 200 mPa·s containing vinyl groups (manufactured by Wacker Chem), and polyorganosiloxane (a2) with a viscosity of 100 mPa·s containing SiH groups (manufactured by Wacker Chem) in a mass ratio of 54:36:10. To mixture (III), 47.8 g of polyorganosiloxane (a2) with a viscosity of 100 mPa·s containing SiH groups (manufactured by Wacker Chem) and 40.4 g of mixture (IV) were added, and the mixture was stirred with a stirrer for 5 minutes to obtain adhesive composition (4). The ratio of components was adjusted so that the mass ratio of vinyl group-containing MQ resin to total polymer components was 78 / 100.

[0185] [Preparation Example 5] 0.6 g of 1,1-diphenyl-2-propyne-1-ol (manufactured by Tokyo Chemical Industry Co., Ltd.) as a polymerization inhibitor and 0.6 g of 1-ethynyl-1-cyclohexanol (manufactured by Wacker Chem Co., Ltd.) as a polymerization inhibitor were added to a 50 ml screw tube, and the mixture was stirred with a mixing rotor for 10 minutes to obtain mixture (I). In a 600 mL stirring container specifically for the rotation-orbit mixer, 114.2 g of vinyl group-containing MQ resin (manufactured by Wacker Chem Co., Ltd.), dissolved in paramentane to a solid content of 81.7%, was added as polyorganosiloxane (a1). 0.13 g of platinum catalyst (manufactured by Wacker Chem Co., Ltd.), as a platinum group metal catalyst (A2), was added (10 ppm by mass in terms of metal relative to the total mass of polysiloxane (A1)). 9.0 g of vinyl group-containing linear polydimethylsiloxane (manufactured by Wacker Chem Co., Ltd.), with a viscosity of 100,000 mPa·s, was added as polyorganosiloxane (a3). The mixture was stirred with a stirrer for 5 minutes to obtain mixture (II). Next, 0.6 g of mixture (I) was added to mixture (II), and the mixture was stirred with a stirrer for 5 minutes to obtain mixture (III). Next, a mixture (IV) was prepared by premixing the following polyorganosiloxanes in a mass ratio of 54:36:10: MQ resin (manufactured by Wacker Chem Co., Ltd.) containing polysiloxane and vinyl groups as polyorganosiloxane (a1), vinyl group-containing linear polydimethylsiloxane (manufactured by Wacker Chem Co., Ltd.) with a viscosity of 200 mPa·s as polyorganosiloxane (a3), and SiH group-containing linear polydimethylsiloxane (manufactured by Wacker Chem Co., Ltd.) with a viscosity of 100 mPa·s as polyorganosiloxane (a2). To mixture (III), 13.6 g of SiH group-containing linear polydimethylsiloxane (manufactured by Wacker Chem Co., Ltd.) with a viscosity of 100 mPa·s and 12.4 g of mixture (IV) were added, and the mixture was stirred with a stirrer for 5 minutes to obtain adhesive composition (5). The ratio of components was adjusted so that the mass ratio of vinyl group-containing MQ resin to total polymer components was 78 / 100.

[0186] [Preparation Example 6] 0.3 g of 1,1-diphenyl-2-propyne-1-ol (manufactured by Tokyo Chemical Industry Co., Ltd.) as a polymerization inhibitor and 0.3 g of 1-ethynyl-1-cyclohexanol (manufactured by Wacker Chem Co., Ltd.) as a polymerization inhibitor were added to a 50 ml screw tube, and the mixture was stirred with a mixing rotor for 10 minutes to obtain mixture (I). Next, a mixture (II) was prepared by premixing polyorganosiloxane (a1) with MQ resin containing polysiloxane and vinyl groups (manufactured by Wacker Chem Co., Ltd.), polyorganosiloxane (a3) ​​with vinyl groups containing linear polydimethylsiloxane with a viscosity of 200 mPa·s (manufactured by Wacker Chem Co., Ltd.), and polyorganosiloxane (a2) with SiH groups containing linear polydimethylsiloxane with a viscosity of 100 mPa·s (manufactured by Wacker Chem Co., Ltd.) in a mass ratio of 54:36:10. As polyorganosiloxane (a2), 13.6 g of SiH group-containing linear polydimethylsiloxane (manufactured by Wacker Chem Ltd.) with a viscosity of 100 mPa·s, 12.7 g of mixture (II), 13.9 g of SiH group-containing linear polydimethylsiloxane (manufactured by Wacker Chem Ltd.) with a viscosity of 100 mPa·s as polyorganosiloxane (a2), and 13.5 g of polydimethylsiloxane with a viscosity of 6000 Pa·s as a release agent component were added, and the mixture was stirred with a stirrer for 5 minutes to obtain mixture (III). Mixture (I) 1.0 g was added to mixture (III), and the mixture was stirred with a stirrer for 5 minutes to obtain mixture (IV). In a 50 ml screw-cap tube, 13.5 g of vinyl group-containing linear polydimethylsiloxane (manufactured by Wacker Chem Co., Ltd.) with a viscosity of 1000 mPa·s was added as polyorganosiloxane (a3), 0.1 g of platinum catalyst (manufactured by Wacker Chem Co., Ltd.) as a platinum group metal catalyst (A2) (10 ppm by mass in terms of metal relative to the total mass of polysiloxane (A1)), and 1.15 g of p-menthane (manufactured by Tokyo Chemical Industry Co., Ltd.) was added. The mixture was stirred with a stirrer for 5 minutes to obtain mixture (V). 14.8 g of mixture (V) was added to mixture (IV), and the mixture was stirred with a stirrer for 5 minutes to obtain adhesive composition (6). The ratio of components was adjusted so that the mass ratio of vinyl group-containing MQ resin / total polymer components was 5 / 100.

[0187] [Preparation Example 7] 0.4 g of 1,1-diphenyl-2-propyne-1-ol (manufactured by Tokyo Chemical Industry Co., Ltd.) as a polymerization inhibitor and 0.4 g of 1-ethynyl-1-cyclohexanol (manufactured by Wacker Chem Co., Ltd.) as a polymerization inhibitor were added to a 50 ml screw tube, and the mixture was stirred with a mix rotor for 10 minutes to obtain mixture (I). 36.7 g of vinyl group-containing MQ resin (manufactured by Wacker Chem Co., Ltd.) as polyorganosiloxane (a1), 45.0 g of vinyl group-containing linear polydimethylsiloxane (manufactured by Wacker Chem Co., Ltd.) with a viscosity of 200 mPa·s as polyorganosiloxane (a3), and 0.1 g of platinum catalyst (manufactured by Wacker Chem Co., Ltd.) as platinum group metal catalyst (A2) (10 ppm by mass in terms of metal relative to the total mass of polysiloxane (A1)) were added, and the mixture was stirred with a stirrer for 5 minutes to obtain mixture (II). Mixture (II) was mixed with 0.4 g of mixture (I), and the mixture was stirred for 5 minutes to obtain mixture (III). To mixture (III), 10.7 g of SiH group-containing linear polydimethylsiloxane (manufactured by Wacker Chem Co., Ltd.) with a viscosity of 100 mPa·s was added as polyorganosiloxane (a2), and the mixture was stirred for 5 minutes to obtain adhesive composition (7). The ratio of components was adjusted so that the mass ratio of vinyl group-containing MQ resin / total polymer components was 35 / 100.

[0188] [2] Preparation of detergent composition [Preparation example 8] 5 g of tetrabutylammonium fluoride trihydrate (manufactured by Kanto Chemical Co., Ltd.) was mixed with 95 g of N,N-dimethylpropionamide and stirred well to obtain a detergent composition.

[0189] [3] Evaluation of film removeability [Example 1-1] As a semiconductor substrate, an adhesive composition (1) was formed on the circuit surface of a 4 × 4 cm bare silicon wafer by spin coating to form a temporary adhesive layer, with a film thickness of approximately 100 μm, to form the temporary adhesive layer (1). To cure the temporary adhesive layer (1), it was heated at 200°C for 10 minutes using a hot plate. Substrates with the film (adhesive layer (1)) formed on them were prepared in the number necessary for evaluation (the same applies below).

[0190] [Examples 1-2 to 1-5] Films (adhesive layers (2) to (5)) were formed on a bare silicon wafer in the same manner as in Example 1-1, except that adhesive compositions (2) to (5) obtained in Preparation Examples 2 to 5 were used instead of adhesive composition (1) obtained in Preparation Example 1.

[0191] [Comparative Examples 1-1 to 1-2] Films (adhesive layers (6) to (7)) were formed on a bare silicon wafer in the same manner as in Example 1-1, except that adhesive compositions (6) to (7) obtained in Preparation Examples 6 to 7 were used instead of adhesive composition (1) obtained in Preparation Example 1.

[0192] The film thickness of each film (adhesive layer (1) to (7)) obtained in Examples 1-1 to 1-5 and Comparative Examples 1-1 to 1-2 was measured (film thickness before immersion). Then, each film, along with the substrate, was immersed in 7 mL of the cleaning agent composition obtained in Preparation Example 8 at 23°C for 5 minutes while stirring, dried with an air gun, and the film thickness of each film was measured again (film thickness after immersion). The etching rate (x) due to immersion was calculated using the following formula (1). The etching rate (x) for each example was the arithmetic mean of two values. Etching rate (x) (μm / min) = [Film thickness before immersion (μm) - Film thickness after immersion (μm)] / 5 min ... (1) The results are shown in Table 1.

[0193]

[0194] As shown in Table 1, in Examples 1-1 to 1-5 to which the present invention was applied, the etching rate was 10 μm / min or more, and it was confirmed that the material could be easily removed by washing. In contrast, in Comparative Examples 1-1 to 1-2, the etching rate was less than 10 μm / min.

[0195] According to the present invention, an adhesive composition that can be easily removed by cleaning after bonding a support substrate and a semiconductor substrate or an electronic device substrate is provided, and a laminate using the adhesive composition is provided, making it useful for the manufacture of processed semiconductor substrates.

[0196] 1 Semiconductor substrate 2 Adhesive layer 2a Adhesive coating layer 3 Release agent layer 4 Support substrate 21 Semiconductor chip substrate 22 Adhesive layer 22' Adhesive coating layer 23 Release agent layer 24 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 contains an adhesive component (A) that hardens by a hydrosilylation reaction, and the etching rate of the adhesive layer, as measured by the etching rate measurement method described below, is 10 μm / min or more. <Method for measuring the etching rate> After measuring the thickness of the adhesive layer, which is approximately 100 μm thick, the adhesive layer, together with the semiconductor substrate or the electronic device substrate, is immersed in 7 mL of a cleaning agent composition prepared by mixing 5 g of tetrabutylammonium fluoride trihydrate with 95 g of N,N-dimethylpropionamide at 23°C for 5 minutes while stirring, and the thickness after immersion is measured, and the etching rate is taken as x obtained by the following formula (1). x (μm / min) = [Thickness of the adhesive layer before immersion (μm) - Thickness of the adhesive layer after immersion (μm)] / 5 min ... (1) 2. The adhesive component (A) contains polysiloxane (A1) including 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 , and siloxane units (T units) represented by R ６ SiO ３／２ , and being selected from the group consisting of combinations of two or more of these siloxane units (where 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). The polysiloxane (A1) includes: - polyorganosiloxane (a1) (the polyorganosiloxane (a1) has an alkenyl group having 2 to 10 carbon atoms and includes at least one of the siloxane units (Q' units) represented by SiO ２ and the siloxane units (T' units) represented by R ６ 'SiO ３／２ , and R ６ ' 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). - polyorganosiloxane (a2) (the polyorganosiloxane (a2) has an Si—H group and includes 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 , and siloxane units (T'' 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 The adhesive composition according to claim 1, comprising (wherein each of these independently represents an alkyl group or hydrogen atom having 1 to 10 carbon atoms), wherein the content of the polyorganosiloxane (a1) is 45 to 95% by mass relative to the total mass of the polysiloxane (A1).

3. The polysiloxane (A1) is further a polyorganosiloxane (a3) ​​(the polyorganosiloxane (a3) ​​is R １ 'R ２ 'R ３ 'SiO １／２ Siloxane units (M' units) represented by R ４ 'R ５ 'SiO ２／２ It contains at least one of the siloxane units (D' units) represented by R １ '~R ５ The adhesive composition according to claim 2, comprising ', each independently representing 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.

4. The adhesive composition according to claim 1, wherein the adhesive component (A) further comprises a platinum group metal catalyst (A2).

5. The adhesive composition according to claim 1, wherein the adhesive component (A) further comprises a polymerization inhibitor.

6. 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 5.

7. 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 step of applying an adhesive composition according to any one of claims 1 to 5 to form the adhesive layer on either the semiconductor substrate or the electronic device substrate or the support substrate.

8. 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 6; 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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