Release agent composition, laminate, and production method for processed semiconductor substrate

Abstract

A release agent composition for forming a release agent layer of a laminate that has a light-transmissive support substrate, a semiconductor substrate having a bump on the support substrate side thereof, the release agent layer interposed between the support substrate and the semiconductor substrate and in contact with the semiconductor substrate, and an adhesive agent layer interposed between the support substrate and the release agent layer and in contact with the release agent layer, and that is for use in separating the semiconductor substrate and the support substrate from each other after the release agent layer has absorbed light emitted from the support substrate side, the release agent composition comprising a polyphenol compound selected from tannins and flavonoids.

Description

Stripper composition, laminate, and method for producing processed semiconductor substrate

[0001] The present invention relates to a stripper composition, a laminate, and a method for producing a processed semiconductor substrate.

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

[0003] Semiconductor wafers (herein simply referred to as wafers) before thinning are bonded to a support in preparation for polishing with a polishing device. This bond must be easily peeled off after polishing, and is therefore called a temporary bond. This temporary bond must be easily removed from the support; applying a large force to remove it can cause the thinned semiconductor wafer to break or deform, so it must be easily removed to prevent this from happening. However, it is undesirable for the temporary bond to become dislodged or shifted due to the polishing stress during polishing of the backside of the semiconductor wafer. Therefore, the performance required of the temporary bond is to withstand the stress during polishing and be easily removed after polishing.

[0004] For example, high stress (strong adhesive strength) in the planar direction during polishing and low stress (weak adhesive strength) in the vertical direction during removal are required. For such adhesion and separation processes, methods using laser irradiation have been disclosed (see, for example, Patent Documents 1 and 2).

[0005] The present applicant has proposed a release agent composition capable of forming a release agent layer that can be applied to separation (peeling) by laser irradiation (see Patent Document 3).

[0006] Meanwhile, a temporary bonding and peeling process has been proposed (see Patent Document 4), which includes providing a stack including: a first substrate having a back surface and a front surface, the front surface having solder balls; a conformal layer of a composition on the front surface and the solder balls; a second substrate having a first surface; and a bonding layer on the first surface, the bonding layer being in contact with the conformal layer; and separating the first and second substrates.

[0007] Japanese Patent Application Laid-Open No. 2004-64040 Japanese Patent Application Laid-Open No. 2012-106486 International Publication No. 2023 / 074324 Pamphlet Japanese Patent Application Laid-Open No. 2024-507781

[0008] When an adhesive layer and a release agent layer are interposed between a semiconductor substrate and a support substrate in a laminate, there is an embodiment in which the semiconductor substrate, adhesive layer, release agent layer, and support substrate are laminated in this order, as shown in Figure 1 of Patent Document 3. In this case, cleaning is usually performed because the adhesive layer or its residue may remain on the semiconductor substrate during peeling. A salt-containing cleaning composition is generally used for cleaning, but if the semiconductor substrate has bumps such as solder balls on its surface, damage to the bumps due to salt may become a problem. On the other hand, there is also an embodiment in which the semiconductor substrate, release agent layer, adhesive layer, and support substrate are laminated in this order in a laminate. Even in this case, cleaning is usually performed because the release agent layer or its residue may remain on the semiconductor substrate during peeling. However, the release agent layer or its residue can be cleaned with a salt-free cleaning composition, so salt-induced damage to the bumps does not occur. Therefore, cleaning of the release agent layer or its residue on a semiconductor substrate has superior cleaning properties compared to cleaning of the adhesive layer or its residue on a semiconductor substrate. On the other hand, when a release agent layer is formed on a semiconductor substrate having bumps on its surface, the release agent layer is required to be able to cover the bumps, but since the release agent layer is thinner than the adhesive layer, it is not easy to cover the bumps.

[0009] An object of the present invention is to provide a release agent composition capable of forming a release agent layer that has excellent cleaning properties and excellent bump coverage, a laminate using the release agent composition, and a method for producing a processed semiconductor substrate using the release agent composition.

[0010] The present inventors have conducted extensive research to solve the above problems, and as a result have found that the above problems can be solved, and have completed the present invention having the following gist.

[0011] That is, the present invention includes the following: [1] A release agent composition for forming the release agent layer of a laminate having a light-transmitting support substrate, a semiconductor substrate having bumps on the support substrate side, a release agent layer interposed between the support substrate and the semiconductor substrate and in contact with the semiconductor substrate, and an adhesive layer interposed between the support substrate and the release agent layer and in contact with the release agent layer, the laminate being used to separate the semiconductor substrate from the support substrate after the release agent layer absorbs light irradiated from the support substrate side, the release agent composition containing a polyphenol compound selected from tannins and flavonoids. [2] The release agent composition according to [1], wherein the polyphenol compound is tannic acid. [3] The release agent composition according to [1] or [2], wherein the content of the polyphenol compound in the release agent composition is 90 mass% or more relative to the non-volatile content in the release agent composition. [4] A laminate comprising: a light-transmitting support substrate; a semiconductor substrate having bumps on the support substrate side; a release agent layer interposed between the support substrate and the semiconductor substrate and in contact with the semiconductor substrate; and an adhesive layer interposed between the support substrate and the release agent layer and in contact with the release agent layer, wherein the semiconductor substrate and the support substrate are separated after the release agent layer absorbs light irradiated from the support substrate side, wherein the release agent layer is formed from the release agent composition according to any one of [1] to [3]. [5] The laminate according to [4], wherein the adhesive layer is formed from an adhesive composition containing a compound having a siloxane structure. [6] The laminate according to [5], wherein the adhesive composition contains a curable component (A). [7] The laminate according to [6], wherein the component (A) is a component that cures by a hydrosilylation reaction. [8] The laminate according to [6], wherein the component (A) contains a polyorganosiloxane (a1) having an alkenyl group having 2 to 40 carbon atoms bonded to a silicon atom, a polyorganosiloxane (a2) having a Si—H group, and a catalyst (A2). [9] The laminate according to any one of [4] to [8], wherein the thickness of the release agent layer is 35% to 100% of the height of the bump.

[10] A method for manufacturing a processed semiconductor substrate, comprising: a first step of processing the semiconductor substrate of the laminate according to any one of [4] to [9]; and a second step of separating the semiconductor substrate processed in the first step from the support substrate.

[11] The method for manufacturing a processed semiconductor substrate according to

[10] , wherein the second step includes a step of irradiating the release agent layer with light.

[0012] According to the present invention, it is possible to provide a release agent composition capable of forming a release agent layer that has excellent cleaning properties and excellent bump coverage, a laminate using the release agent composition, and a method for producing a processed semiconductor substrate using the release agent composition.

[0013] Fig. 1 is a schematic cross-sectional view of an example of a laminate. Fig. 2A is a schematic cross-sectional view for explaining an example of a method for manufacturing a processed semiconductor substrate (part 1). Fig. 2B is a schematic cross-sectional view for explaining an example of a method for manufacturing a processed semiconductor substrate (part 2). Fig. 2C is a schematic cross-sectional view for explaining an example of a method for manufacturing a processed semiconductor substrate (part 3). Fig. 2D is a schematic cross-sectional view for explaining an example of a method for manufacturing a processed semiconductor substrate (part 4). Fig. 2E is a schematic cross-sectional view for explaining an example of a method for manufacturing a processed semiconductor substrate (part 5).

[0014] (Release Agent Composition) The release agent composition of the present invention is a composition for forming a release agent layer of a laminate. The laminate has a support substrate, a semiconductor substrate, a release agent layer, and an adhesive layer. The support substrate is light-transmitting. The semiconductor substrate has bumps on the support substrate side. The release agent layer is interposed between the support substrate and the semiconductor substrate and in contact with the semiconductor substrate. The adhesive layer is interposed between the support substrate and the release agent layer and in contact with the release agent layer. The laminate is used in such a way that the semiconductor substrate and the support substrate are separated after the release agent layer absorbs light irradiated from the support substrate side. The release agent composition contains a polyphenol compound selected from tannins and flavonoids. The release agent composition may contain other components such as a solvent and a surfactant.

[0015] The laminate is, for example, the laminate of the present invention described below.

[0016] The release agent composition contains a polyphenol compound selected from tannins and flavonoids, and thus the release agent layer formed from the release agent composition has excellent bump coverage. Here, "excellent bump coverage" means that the release agent layer is free from coating defects such as cracks and is able to cover bumps. Furthermore, when cleaning the release agent layer formed from the release agent composition or its residue, a salt-free cleaning composition can be used, resulting in excellent cleaning performance.

[0017] The present inventors attempted to prepare a laminate by laminating, in this order, a semiconductor substrate having bumps, a release agent layer, an adhesive layer, and a support substrate using a release agent composition containing a light-absorbing compound such as a polyphenol compound. They found that a release agent composition containing a polyphenol compound selected from tannin and flavonoid can form a release agent layer that is excellent in both cleaning properties and bump coverage. On the other hand, even with the light-absorbing compounds disclosed in Patent Document 3, the release agent layers formed from release agent compositions containing V886 and carminic acid exhibited insufficient bump coverage.

[0018] <Polyphenol Compound Selected from Tannins and Flavonoids> Tannins and flavonoids are types of polyphenol compounds. The polyphenol compound according to the present invention refers to a plant component having multiple phenolic hydroxy groups (hydroxy groups bonded to an aromatic ring such as a benzene ring or a naphthalene ring) in the molecule.

[0019] Tannins are water-soluble compounds derived from plants that react with proteins, alkaloids, and metal ions, forming weakly soluble salts. Tannins are ubiquitous in the plant kingdom and are aromatic compounds with multiple phenolic hydroxy groups. Examples of tannins include condensed tannins and hydrolyzable tannins.

[0020] Condensed tannins are compounds formed by polymerizing compounds having a flavanol skeleton represented by the following formula (p):

[0021] Hydrolyzable tannins are compounds formed by ester bonding between an aromatic compound such as gallic acid or ellagic acid and a sugar such as glucose, represented by the following formula (r):

[0022] A preferred embodiment of the hydrolyzable tannin is tannic acid represented by the following formula:

[0023] Flavonoids refer to compounds biosynthesized by various modifications of flavanone, a type of flavonoid, and refer to, for example, compounds derived from a compound having a flavanone skeleton structure represented by the following formula (s).

[0024] A preferred embodiment of the flavonoid is a flavonoid represented by the following formula:

[0025] The content of the polyphenol compound in the release agent composition is not particularly limited, but is preferably 90% by mass or more, and more preferably 95% by mass or more, of the non-volatile content in the release agent composition. The non-volatile content refers to components in the release agent composition other than the solvent.

[0026] The amount of the polyphenol compound contained in the release agent composition cannot be generally defined because it varies depending on the coating method used, the desired film thickness, etc., but is usually 0.1 to 80 mass %. From the viewpoint of reproducibly obtaining a laminate from which the semiconductor substrate and the support substrate can be easily separated, the amount is preferably 0.5 mass % or more, more preferably 1.0 mass % or more, even more preferably 5.0 mass % or more, and is preferably 70 mass % or less, more preferably 60 mass % or less, even more preferably 50 mass % or less, and even more preferably 40 mass % or less.

[0027] <Surfactant> The stripping composition may contain a surfactant for the purposes of adjusting the liquid properties of the composition itself and the film properties of the resulting film, and for the purpose of reproducibly preparing a highly uniform stripping composition. Examples of the surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether, polyoxyethylene alkylaryl ethers such as polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether, polyoxyethylene-polyoxypropylene block copolymers, sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, and sorbitan tristearate, polyoxyethylene sorbitan monolaurate, and polyoxyethylene sorbitan monopalmitate. nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters, such as polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate; fluorosurfactants such as Eftop EF301, EF303, and EF352 (trade names, manufactured by Tochem Products Co., Ltd.), Megafac F171, F173, R-30, and R-30N (trade names, manufactured by DIC Corporation), Fluorad FC430 and FC431 (trade names, manufactured by Sumitomo 3M Limited), Asahiguard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, and SC106 (trade names, manufactured by Asahi Glass Co., Ltd.); and organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.). The surfactant may be used alone or in combination of two or more. The amount of the surfactant is usually 2% by mass or less based on the nonvolatile content of the stripping composition.

[0028] <Solvent> The stripping agent composition preferably contains a solvent. As such a solvent, for example, a solvent capable of dissolving non-volatile components such as polyphenol compounds well can be used. If necessary, two or more solvents may be used in combination for the purpose of adjusting viscosity, surface tension, etc. An example of the use of two or more solvents in combination is a combination of a high-polarity solvent and a low-polarity solvent. In the present invention, a low-polarity solvent is defined as one having a relative dielectric constant of less than 7 at a frequency of 100 kHz, and a high-polarity solvent is defined as one having a relative dielectric constant of 7 or more at a frequency of 100 kHz. The solvents can be used alone or in combination of two or more.

[0029] Examples of highly polar solvents include amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylisobutyramide, 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.

[0030] Examples of low-polarity solvents include chlorine-based solvents such as chloroform and chlorobenzene; aromatic hydrocarbon-based solvents such as alkylbenzenes such as toluene, xylene, tetralin, cyclohexylbenzene and decylbenzene; aliphatic alcohol-based 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.

[0031] The content of the solvent is determined as appropriate taking into consideration the desired viscosity of the composition, the coating method to be used, the thickness of the film to be formed, and the like, but is, for example, 99% by mass or less of the entire composition, and preferably 70 to 99% by mass of the entire composition, i.e., the amount of nonvolatile components in this case is 1 to 30% by mass of the entire composition.

[0032] The viscosity and surface tension of the release agent composition are appropriately adjusted by changing the types of solvents used, their ratios, nonvolatile content concentration, etc., taking into consideration various factors such as the coating method used and the desired film thickness.

[0033] In one embodiment of the present invention, the stripper composition contains a glycol-based solvent from the viewpoint of reproducibly obtaining a highly uniform composition, reproducibly obtaining a composition with high storage stability, reproducibly obtaining a composition that gives a highly uniform film, etc. Note that the term "glycol-based solvent" used here is a general term for glycols, glycol monoethers, glycol diethers, glycol monoesters, glycol diesters, and glycol ester ethers.

[0034] An example of a preferred glycol-based solvent is represented by formula (G).

[0035] In formula (G), R Ｇ１ each independently represents a linear or branched alkylene group having 2 to 4 carbon atoms; R Ｇ２ and R Ｇ３ each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, or an alkylacyl group in which the alkyl moiety is a linear or branched alkyl group having 1 to 8 carbon atoms; n ｇ is an integer from 1 to 6.

[0036] Specific examples of the linear or branched alkylene group having 2 to 4 carbon atoms include, but are not limited to, an ethylene group, a trimethylene group, a 1-methylethylene group, a tetramethylene group, a 2-methylpropane-1,3-diyl group, a pentamethylene group, a hexamethylene group, etc. Among these, from the viewpoint of reproducibly obtaining a highly uniform composition, reproducibly obtaining a composition with high storage stability, and reproducibly obtaining a composition that gives a highly uniform film, linear or branched alkylene groups having 2 to 3 carbon atoms are preferred, and linear or branched alkylene groups having 3 carbon atoms are more preferred.

[0037] Specific examples of the linear or branched alkyl group having 1 to 8 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, an s-butyl group, a tertiary butyl group, an n-pentyl group, a 1-methyl-n-butyl group, a 2-methyl-n-butyl group, a 3-methyl-n-butyl group, a 1,1-dimethyl-n-propyl group, a 1,2-dimethyl-n-propyl group, a 2,2-dimethyl-n-propyl group, a 1-ethyl-n-propyl group, an n-hexyl group, a 1-methyl-n-pentyl group, a 2-methyl-n-pentyl group, a 3-methyl Examples of the alkyl group include, but are not limited to, a methyl group, a 4-methyl-n-pentyl group, a 1,1-dimethyl-n-butyl group, a 1,2-dimethyl-n-butyl group, a 1,3-dimethyl-n-butyl group, a 2,2-dimethyl-n-butyl group, a 2,3-dimethyl-n-butyl group, a 3,3-dimethyl-n-butyl group, a 1-ethyl-n-butyl group, a 2-ethyl-n-butyl group, a 1,1,2-trimethyl-n-propyl group, a 1,2,2-trimethyl-n-propyl group, a 1-ethyl-1-methyl-n-propyl group, and a 1-ethyl-2-methyl-n-propyl group. Among these, from the viewpoint of reproducibly obtaining a highly uniform composition, a highly storage stable composition, and a composition that gives a highly uniform film, a methyl group and an ethyl group are preferred, and a methyl group is more preferred.

[0038] Specific examples of the linear or branched alkyl group having 1 to 8 carbon atoms in the alkyl acyl group in which the alkyl moiety is a linear or branched alkyl group having 1 to 8 carbon atoms include the same as the specific examples described above. Among these, from the viewpoints of reproducibly obtaining a highly uniform composition, reproducibly obtaining a composition having high storage stability, and reproducibly obtaining a composition that gives a highly uniform film, a methylcarbonyl group and an ethylcarbonyl group are preferred, and a methylcarbonyl group is more preferred.

[0039] n ｇ is preferably 4 or less, more preferably 3 or less, even more preferably 2 or less, and most preferably 1, from the viewpoint of reproducibly obtaining a highly uniform composition, from the viewpoint of reproducibly obtaining a composition with high storage stability, from the viewpoint of reproducibly obtaining a composition that gives a highly uniform film, etc.

[0040] From the viewpoint of reproducibly obtaining a composition having high uniformity, a composition having high storage stability, and a composition that gives a film having high uniformity, it is preferable that R Ｇ２ and R Ｇ３ At least one of R is a linear or branched alkyl group having 1 to 8 carbon atoms, and more preferably R Ｇ２ and R Ｇ３ One of the groups is a linear or branched alkyl group having 1 to 8 carbon atoms, and the other is a hydrogen atom or an alkylacyl group in which the alkyl portion is a linear or branched alkyl group having 1 to 8 carbon atoms.

[0041]

[0033] From the viewpoint of reproducibly obtaining a highly uniform composition, a highly storage stable composition, and a composition that gives a highly uniform film, the content of the glycol-based solvent is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, still more preferably 90% by mass or more, and still more preferably 95% by mass or more, relative to the solvent contained in the stripper composition. From the viewpoint of reproducibly obtaining a highly uniform composition, a highly storage stable composition, and a composition that gives a highly uniform film, the non-volatile components in the stripper composition are uniformly dispersed or dissolved in the solvent, and preferably dissolved.

[0042] (Laminate) The laminate of the present invention has a support substrate, a semiconductor substrate, a release agent layer, and an adhesive layer. The support substrate is light-transmitting. The semiconductor substrate has bumps on the support substrate side. The release agent layer is interposed between the support substrate and the semiconductor substrate and in contact with the semiconductor substrate. The adhesive layer is interposed between the support substrate and the release agent layer and in contact with the release agent layer. The laminate is used in such a way that the semiconductor substrate and the support substrate are separated after the release agent layer absorbs light irradiated from the support substrate side. The release agent layer is a release agent layer formed from the release agent composition of the present invention.

[0043] The laminate of the present invention can be suitably used for processing such as thinning of a semiconductor substrate. In the laminate of the present invention, while the semiconductor substrate is being processed such as thinning, the semiconductor substrate is supported on the support substrate via the adhesive layer and the release agent layer. On the other hand, the polyphenol compound contained in the release agent composition absorbs light (e.g., laser light) in the release agent layer formed from the release agent composition, causing the release agent layer to change in quality (e.g., separate or decompose). As a result, after the release agent layer is irradiated with light, the semiconductor substrate and the support substrate are easily separated. Furthermore, the release agent layer or its residue remaining on the semiconductor substrate after the semiconductor substrate and the support substrate are separated can be easily removed with a cleaning composition for cleaning the semiconductor substrate.

[0044] The wavelength of the light used for peeling is, for example, preferably 250 to 600 nm, more preferably 250 to 370 nm. More preferred wavelengths are 308 nm, 343 nm, 355 nm, 365 nm, or 532 nm. The light irradiation amount required for peeling is an amount that can cause suitable alteration, for example, decomposition, of the polyphenol compound. The light used for peeling may be laser light or non-laser light emitted from a light source such as an ultraviolet lamp.

[0045] <Supporting Substrate> The supporting substrate is not particularly limited as long as it is a member that is optically transparent to the light irradiated onto the release agent layer and can support the semiconductor substrate when the semiconductor substrate is processed, and examples thereof include a glass supporting substrate.

[0046] The shape of the support substrate is not particularly limited, but may be, for example, a disk shape. The thickness of the disk-shaped support substrate may be determined appropriately depending on the size of the semiconductor substrate, etc., but is not particularly limited, and is, for example, 500 to 1,000 μm. The diameter of the disk-shaped support substrate may be determined appropriately depending on the size of the semiconductor substrate, etc., but is not particularly limited, and is, for example, 100 to 1,000 mm.

[0047] An example of the support substrate is a glass wafer having a diameter of about 300 mm and a thickness of about 700 μm.

[0048] <Semiconductor Substrate> The main material constituting the entire semiconductor substrate is not particularly limited as long as it is suitable for this type of application, and examples thereof include silicon, silicon carbide, and compound semiconductors. The shape of the semiconductor substrate is not particularly limited, and may be, for example, a disk. Note that the surface of a disk-shaped semiconductor substrate does not need to be perfectly circular; for example, the outer periphery of the semiconductor substrate may have a straight line portion called an orientation flat or a notch. The thickness of the disk-shaped semiconductor substrate may be determined appropriately depending on the intended use of the semiconductor substrate, and is not particularly limited, and is, for example, 500 to 1,000 μm. The diameter of the disk-shaped semiconductor substrate may be determined appropriately depending on the intended use of the semiconductor substrate, and is not particularly limited, and is, for example, 100 to 1,000 mm.

[0049] The semiconductor substrate has bumps. Bumps are protruding terminals. In a laminate, the semiconductor substrate has bumps on the support substrate side. In a semiconductor substrate, the bumps are usually formed on the surface on which a circuit is formed. The circuit may be single-layered or multi-layered. The shape of the circuit is not particularly limited. In a semiconductor substrate, the surface opposite to the surface having the bumps (the back surface) is the surface used for processing. The material, size, shape, structure, and density of the bumps on the semiconductor substrate are not particularly limited. Examples of bumps include ball bumps, printed bumps, stud bumps, and plated bumps. The height, diameter, and pitch of the bumps are usually determined appropriately based on the following conditions: a bump height of approximately 1 to 200 μm, a bump diameter of 1 to 200 μm, and a bump pitch of 1 to 500 μm. From the viewpoint of optimally obtaining the effects of the present invention, the bump height is preferably 1 to 50 μm, and more preferably 2 to 30 μm. From the viewpoint of optimally achieving the effects of the present invention, the bump diameter is preferably 1 to 50 μm, more preferably 2 to 30 μm. From the viewpoint of optimally achieving the effects of the present invention, the bump pitch is preferably 2 to 100 μm, more preferably 4 to 60 μm. The bump pitch is preferably 1.2 to 5 times the bump diameter, more preferably 1.5 to 3 times. The bump pitch is the distance between the centers of two adjacent bumps. Examples of bump materials 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 alloy platings mainly composed of Sn, such as SnAg bumps, SnBi bumps, Sn bumps, and AuSn bumps. The bumps may also have a layered structure including a metal layer composed of at least one of these components.

[0050] An example of a semiconductor substrate is a silicon wafer with a diameter of about 300 mm and a thickness of about 770 μm.

[0051] <Release Agent Layer> The release agent layer is a layer formed from the release agent composition of the present invention. The release agent layer is provided between the semiconductor substrate and the support substrate. The release agent layer is interposed between the support substrate and the semiconductor substrate and is in contact with the semiconductor substrate.

[0052] The method for forming the release agent layer from the release agent composition is not particularly limited, and examples thereof include the formation methods described below.

[0053] When forming a release agent layer from the release agent composition, the polyphenol compound may crosslink itself or react with other components to form a crosslinked structure, or may maintain its structure without crosslinking or reacting, as long as the effects of the present invention are obtained. In other words, in the release agent layer, the polyphenol compound may crosslink itself or react with other components to form a crosslinked structure, or may be present while maintaining its structure.

[0054] The thickness of the release agent layer provided in the laminate of the present invention is not particularly limited, but is usually 100 nm to 50 μm, in one embodiment 500 nm to 30 μm, in another embodiment 1,000 nm to 25 μm, and in still another embodiment 2,000 nm to 20 μm.

[0055] The thickness of the release agent layer is preferably 35% or more of the bump height. This allows the release agent layer to be appropriately thick, resulting in the formation of a release agent layer with better bump coverage. Here, the thickness of the release agent refers to the thickness of the release agent layer formed between the bumps on the semiconductor substrate. When the bump height is 10 μm and the thickness of the release agent layer formed between the bumps on the semiconductor substrate is 3.5 μm (3,500 nm), the thickness of the release agent layer is 35% of the bump height. While the upper limit of the thickness of the release agent layer is not particularly limited, the thickness of the release agent layer is preferably 100% or less of the bump height. This prevents the release agent layer from becoming too thick, thereby shortening the cleaning time with the cleaning composition.

[0056] <Adhesive Layer> The adhesive layer is provided between the support substrate and the semiconductor substrate. The adhesive layer is interposed between the support substrate and the release agent layer and is in contact with the release agent layer.

[0057] The adhesive layer is not particularly limited, but is preferably a layer formed from an adhesive composition.

[0058] <<Adhesive Composition>> Examples of adhesive compositions include, but are not limited to, polysiloxane-based adhesives, acrylic resin-based adhesives, epoxy resin-based adhesives, polyamide-based adhesives, polystyrene-based adhesives, polyimide adhesives, and phenolic resin-based adhesives. Among these, polysiloxane-based adhesives are preferred as adhesive compositions because they exhibit favorable adhesive properties during processing of semiconductor substrates and the like, are favorably releasable after processing, and further have excellent heat resistance and light transmittance. That is, the adhesive composition is preferably an adhesive composition containing a compound having a siloxane structure. Furthermore, the adhesive composition may be a thermosetting adhesive composition or a thermoplastic adhesive composition.

[0059] In a preferred embodiment, the adhesive composition contains a polyorganosiloxane. In another preferred embodiment, the adhesive composition contains a component that cures by a hydrosilylation reaction.

[0060] In a preferred embodiment, the adhesive composition used in the present invention contains a polyorganosiloxane. For example, the adhesive composition used in the present invention contains a curable component (A) that serves as an adhesive component. The adhesive composition used in the present invention may contain a curable component (A) that serves as an adhesive component and a component (B) that does not undergo a curing reaction. Here, an example of the component (B) that does not undergo a curing reaction is polyorganosiloxane. Note that, in the present invention, "does not undergo a curing reaction" does not mean that any curing reaction does not occur, but rather that the curing reaction occurring in the curable component (A) does not occur. In another preferred embodiment, component (A) may be a component that cures by a hydrosilylation reaction, or may be a polyorganosiloxane component (A') that cures by a hydrosilylation reaction. In another preferred embodiment, component (A) contains, for example, a polyorganosiloxane (a1) having an alkenyl group having 2 to 40 carbon atoms bonded to a silicon atom, as an example of component (A'), a polyorganosiloxane (a2) having a Si—H group, and a catalyst (A2). Here, the alkenyl group having 2 to 40 carbon atoms may be substituted. Examples of the substituent include a halogen atom, a nitro group, a cyano group, an amino group, a hydroxy group, a carboxyl group, an aryl group, and a heteroaryl group. In another preferred embodiment, the polyorganosiloxane component (A') that cures by a hydrosilylation reaction contains SiO ２ Siloxane units (Q units) represented by R １ R ２ R ３ SiO １／２ Siloxane units (M units) represented by R ４ R ５ SiO ２／２ Siloxane units (D units) represented by the formula: and R ６ SiO ３／２ and a catalyst (A2), wherein the polysiloxane (A1) contains one or more units selected from the group consisting of siloxane units (T units) represented by the following formula: ２ Siloxane units (Q′ units) represented by R １ 'R ２ 'R３ 'SiO １／２ Siloxane units (M′ units) represented by R ４ 'R ５ 'SiO ２／２ Siloxane units (D′ units) represented by the formula: ６ 'SiO ３／２ and a polyorganosiloxane (a1') containing at least one unit selected from the group consisting of M' units, D' units, and T' units, and SiO ２ Siloxane units (Q″ units) represented by R １ "R ２ "R ３ "SiO １／２ Siloxane units (M″ units) represented by R ４ "R ５ "SiO ２／２ Siloxane units (D″ units) represented by the formula: ６ "SiO ３／２ and a polyorganosiloxane (a2') containing one or more units selected from the group consisting of siloxane units (T" units) represented by the following formula: and containing at least one unit selected from the group consisting of M" units, D" units, and T" units. Note that (a1') is an example of (a1), and (a2') is an example of (a2).

[0061] R １ ~R ６ are groups or atoms bonded to the silicon atom, and each independently represents an optionally substituted alkyl group, an optionally substituted alkenyl group, or a hydrogen atom. Examples of the substituent include a halogen atom, a nitro group, a cyano group, an amino group, a hydroxyl group, a carboxyl group, an aryl group, and a heteroaryl group.

[0062] R １ '~R ６ R ′ is a group bonded to a silicon atom, and each independently represents an optionally substituted alkyl group or an optionally substituted alkenyl group. １ '~R ６At least one of the groups ' is an alkenyl group which may be substituted. Examples of the substituent include a halogen atom, a nitro group, a cyano group, an amino group, a hydroxy group, a carboxyl group, an aryl group, and a heteroaryl group.

[0063] R １ "~R ６ " are groups or atoms bonded to the silicon atom, and each independently represents an optionally substituted alkyl group or a hydrogen atom, but R １ "~R ６ At least one of " is a hydrogen atom. Examples of the substituent include a halogen atom, a nitro group, a cyano group, an amino group, a hydroxy group, a carboxyl group, an aryl group, and a heteroaryl group.

[0064] The alkyl group may be linear, branched, or cyclic, but is preferably a linear or branched alkyl group. The number of carbon atoms is not particularly limited, but is usually 1 to 40, preferably 30 or less, more preferably 20 or less, and even more preferably 10 or less.

[0065] Specific examples of the optionally substituted straight-chain or branched-chain alkyl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, an s-butyl group, a tertiary butyl group, an n-pentyl group, a 1-methyl-n-butyl group, a 2-methyl-n-butyl group, a 3-methyl-n-butyl group, a 1,1-dimethyl-n-propyl group, a 1,2-dimethyl-n-propyl group, a 2,2-dimethyl-n-propyl group, a 1-ethyl-n-propyl group, an n-hexyl group, a 1-methyl-n-pentyl group, a 2-methyl-n-pentyl group, a 3-methyl-n-pentyl group, a 4-methyl-n-pentyl group, a 5-methyl-n-pentyl group, a 6-methyl-n-pentyl group, a 7-methyl-n-pentyl group, a 8-methyl-n-pentyl group, a 9-methyl-n-pentyl group, a 10-methyl-n-pentyl group, a 11-methyl-n-pentyl group, a 12-methyl-n-pentyl group, a 13-methyl-n-pentyl group, a 14-methyl-n-pentyl group, a 15-methyl-n-pentyl group, a 16-methyl-n-pentyl group, a 17-methyl-n-pentyl group, a 18-methyl-n-pentyl group, a 19-methyl-n-pentyl group, a 20-methyl-n-pentyl group, a 21-methyl-n-pentyl group, a 22-methyl-n-pentyl group, a 23-methyl-n-pentyl group, a 24-methyl-n-pentyl group, a 25-methyl-n-pentyl group, a 26-methyl-n-pentyl group, a 27-methyl-n-pentyl group, a 2 Examples of such alkyl groups include, but are not limited to, 1,1-dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1,3-dimethyl-n-butyl, 2,2-dimethyl-n-butyl, 2,3-dimethyl-n-butyl, 3,3-dimethyl-n-butyl, 1-ethyl-n-butyl, 2-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl, 1,2,2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl, and 1-ethyl-2-methyl-n-propyl groups, and the number of carbon atoms is usually 1 to 14, preferably 1 to 10, and more preferably 1 to 6. Of these, a methyl group is particularly preferred.

[0066] Specific examples of the optionally substituted cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a 1-methylcyclopropyl group, a 2-methylcyclopropyl group, a cyclopentyl group, a 1-methylcyclobutyl group, a 2-methylcyclobutyl group, a 3-methylcyclobutyl group, a 1,2-dimethylcyclopropyl group, a 2,3-dimethylcyclopropyl group, a 1-ethylcyclopropyl group, a 2-ethylcyclopropyl group, a cyclohexyl group, a 1-methylcyclopentyl group, a 2-methylcyclopentyl group, a 3-methylcyclopentyl group, a 1-ethylcyclobutyl group, a 2-ethylcyclobutyl group, a 3-ethylcyclobutyl group, a 1,2-dimethylcyclobutyl group, a 1,3-dimethylcyclobutyl group, a 2,2-dimethylcyclobutyl group, a 2,3-dimethylcyclobutyl group, a 2,4-dimethylcyclobutyl group, a 3,3-dimethylcyclobutyl group, a cyclohexyl group, a cyclopent ...

[0044] Examples of cycloalkyl groups include cycloalkyl groups such as 1-n-ethyl-cyclobutyl group, 1-n-propyl-cyclopropyl group, 2-n-propyl-cyclopropyl group, 1-i-propyl-cyclopropyl group, 2-i-propyl-cyclopropyl group, 1,2,2-trimethyl-cyclopropyl group, 1,2,3-trimethyl-cyclopropyl group, 2,2,3-trimethyl-cyclopropyl group, 1-ethyl-2-methyl-cyclopropyl group, 2-ethyl-1-methyl-cyclopropyl group, 2-ethyl-2-methyl-cyclopropyl group, and 2-ethyl-3-methyl-cyclopropyl group; and bicycloalkyl groups such as bicyclobutyl group, bicyclopentyl group, bicyclohexyl group, bicycloheptyl group, bicyclooctyl group, bicyclononyl group, and bicyclodecyl group, but are not limited to these. The number of carbon atoms in the cycloalkyl groups is usually 3 to 14, preferably 4 to 10, and more preferably 5 to 6.

[0067] The alkenyl group may be either linear or branched, and the number of carbon atoms therein is not particularly limited, but is usually 2 to 40, preferably 30 or less, more preferably 20 or less, and even more preferably 10 or less.

[0068] Specific examples of optionally substituted linear or branched alkenyl groups include, but are not limited to, vinyl, allyl, butenyl, and pentenyl groups, and the number of carbon atoms is usually 2 to 14, preferably 2 to 10, and more preferably 1 to 6. Of these, ethenyl and 2-propenyl groups are particularly preferred. Specific examples of optionally substituted cyclic alkenyl groups include, but are not limited to, cyclopentenyl and cyclohexenyl, and the number of carbon atoms is usually 4 to 14, preferably 5 to 10, and more preferably 5 to 6.

[0069] As described above, polysiloxane (A1) contains polyorganosiloxane (a1') and polyorganosiloxane (a2'), and the alkenyl group contained in polyorganosiloxane (a1') and the hydrogen atom (Si-H group) contained in polyorganosiloxane (a2') form a crosslinked structure by a hydrosilylation reaction with catalyst (A2), and then the crosslinked structure is cured. As a result, a cured film is formed.

[0070] The polyorganosiloxane (a1') contains one or more units selected from the group consisting of Q' units, M' units, D' units and T' units, and also contains at least one unit selected from the group consisting of M' units, D' units and T' units. As the polyorganosiloxane (a1'), two or more polyorganosiloxanes satisfying these conditions may be used in combination.

[0071] Preferred combinations of two or more selected from the group consisting of Q' units, M' units, D' units and T' units include, but are not limited to, (Q' units and M' units), (D' units and M' units), (T' units and M' units), and (Q' units, T' units and M' units).

[0072] In addition, when two or more types of polyorganosiloxanes are included in the polyorganosiloxane (a1'), a combination of (Q' units and M' units) and (D' units and M' units), a combination of (T' units and M' units) and (D' units and M' units), a combination of (Q' units, T' units and M' units) and (T' units and M' units) is preferred, but is not limited to these.

[0073] The polyorganosiloxane (a2') contains one or more units selected from the group consisting of Q" units, M" units, D" units, and T" units, and also contains at least one unit selected from the group consisting of M" units, D" units, and T" units. As the polyorganosiloxane (a2'), two or more polyorganosiloxanes satisfying these conditions may be used in combination.

[0074] Preferred combinations of two or more selected from the group consisting of Q" units, M" units, D" units and T" units include, but are not limited to, (M" units and D" units), (Q" units and M" units), and (Q" units, T" units and M" units).

[0075] The polyorganosiloxane (a1') is composed of siloxane units in which alkyl groups and / or alkenyl groups are bonded to the silicon atoms thereof. １ '~R ６ The proportion of alkenyl groups in all the substituents represented by R ′ is preferably 0.1 to 50.0 mol %, more preferably 0.5 to 30.0 mol %, and the remaining R １ '~R ６ ' can be an alkyl group.

[0076] The polyorganosiloxane (a2') is composed of siloxane units in which an alkyl group and / or a hydrogen atom is bonded to the silicon atom. １ "~R ６ The proportion of hydrogen atoms in all the substituents and substituted atoms represented by R １ "~R ６ " can be an alkyl group.

[0077] When component (A) contains (a1) and (a2), in a preferred embodiment of the present invention, the molar ratio of the alkenyl groups contained in the polyorganosiloxane (a1) to the hydrogen atoms constituting the Si—H bonds contained in the polyorganosiloxane (a2) is in the range of 1.0:0.5 to 1.0:0.66.

[0078] The weight average molecular weight of polysiloxanes such as polyorganosiloxane (a1) and polyorganosiloxane (a2) is not particularly limited, but is usually 500 to 1,000,000, and from the viewpoint of realizing the effects of the present invention with good reproducibility, it is preferably 5,000 to 50,000. In the present invention, the weight average molecular weight, number average molecular weight, and dispersity of polyorganosiloxane (excluding the organosiloxane polymer) can be measured using, for example, a GPC apparatus (EcoSEC, HLC-8320GPC manufactured by Tosoh Corporation) and a GPC column (TSKgel SuperMultiporeHZ-N, TSKgel SuperMultiporeHZ-H manufactured by Tosoh Corporation), a column temperature of 40 ° C., tetrahydrofuran as an eluent (elution solvent), a flow rate (flow rate) of 0.35 mL / min, and polystyrene (Shodex manufactured by Showa Denko K.K.) as a standard sample.

[0079] The viscosities of the polyorganosiloxane (a1) and the polyorganosiloxane (a2) are not particularly limited, but are usually 10 to 1,000,000 (mPa s), and from the viewpoint of realizing the effects of the present invention with good reproducibility, are preferably 50 to 10,000 (mPa s). The viscosities of the polyorganosiloxane (a1) and the polyorganosiloxane (a2) are values ​​measured at 25 ° C. using an E-type rotational viscometer.

[0080] The polyorganosiloxane (a1) and the polyorganosiloxane (a2) react with each other to form a film by hydrosilylation, and therefore the curing mechanism is different from that via, for example, silanol groups, and therefore neither siloxane needs to contain a functional group that forms a silanol group upon hydrolysis, such as an alkyloxy group.

[0081] In a preferred embodiment of the present invention, the adhesive composition contains a catalyst (A2) in addition to the polyorganosiloxane component (A'). The catalyst (A2) is preferably a platinum group metal catalyst. Such a platinum metal catalyst promotes the hydrosilylation reaction between the alkenyl groups of the polyorganosiloxane (a1) and the Si—H groups of the polyorganosiloxane (a2).

[0082] Specific examples of platinum-based metal catalysts include, but are not limited to, platinum black, platinic chloride, chloroplatinic acid, reaction products of chloroplatinic acid with monohydric alcohols, complexes of chloroplatinic acid with olefins, platinum bisacetoacetate, etc. Examples of complexes of platinum with olefins include, but are not limited to, complexes of divinyltetramethyldisiloxane and platinum.

[0083] The amount of catalyst (A2) is not particularly limited, but is usually in the range of 1.0 to 50.0 ppm based on the total amount of polyorganosiloxane (a1) and polyorganosiloxane (a2).

[0084] The polyorganosiloxane component (A') may contain a polymerization inhibitor (A3) for the purpose of suppressing the progress of the hydrosilylation reaction. The polymerization inhibitor is not particularly limited as long as it can suppress the progress of the hydrosilylation reaction, and specific examples include alkynyl alcohols such as 1-ethynyl-1-cyclohexanol and 1,1-diphenyl-2-propyn-1-ol. The amount of the polymerization inhibitor is not particularly limited, but is usually 1000.0 ppm or more relative to the total amount of polyorganosiloxane (a1) and polyorganosiloxane (a2) from the viewpoint of obtaining the effect, and 10000.0 ppm or less from the viewpoint of preventing excessive suppression of the hydrosilylation reaction.

[0085] An example of the adhesive composition used in the present invention may contain a component (B) that does not undergo a curing reaction to become a release agent component along with the curable component (A). By including such a component (B) in the adhesive composition, the resulting adhesive layer can be reproducibly and suitably released. Typical examples of such component (B) include non-curable polyorganosiloxanes, and specific examples thereof include, but are not limited to, epoxy group-containing polyorganosiloxanes, methyl group-containing polyorganosiloxanes, and phenyl group-containing polyorganosiloxanes. Another example of component (B) is polydimethylsiloxane. The polydimethylsiloxane may be modified. Examples of optionally modified polydimethylsiloxanes include, but are not limited to, epoxy group-containing polydimethylsiloxanes, unmodified polydimethylsiloxanes, and phenyl group-containing polydimethylsiloxanes.

[0086] Preferred examples of the polyorganosiloxane of component (B) include, but are not limited to, epoxy group-containing polyorganosiloxanes, methyl group-containing polyorganosiloxanes, and phenyl group-containing polyorganosiloxanes.

[0087] The weight-average molecular weight of the polyorganosiloxane of component (B) is not particularly limited, but is typically 100,000 to 2,000,000. From the viewpoint of reproducibly achieving the effects of the present invention, it is preferably 200,000 to 1,200,000, more preferably 300,000 to 900,000. Furthermore, its dispersity is not particularly limited, but is typically 1.0 to 10.0. From the viewpoint of reproducibly achieving suitable release, it is preferably 1.5 to 5.0, more preferably 2.0 to 3.0. The weight-average molecular weight and dispersity can be measured using the method described above for polyorganosiloxane. The viscosity of the polyorganosiloxane of component (B) is not particularly limited, but is typically 1,000 to 2,000,000 mm ２ The viscosity value of the polyorganosiloxane, which is component (B), is expressed as a kinematic viscosity, and is expressed as centistokes (cSt) = mm ２Viscosity (mPa s) is converted to density (g / cm ３ That is, the value can be calculated from the viscosity and density measured with an E-type rotational viscometer at 25°C, and the kinematic viscosity (mm ２ / s)=viscosity (mPa・s) / density (g / cm ３ ) can be calculated using the formula:

[0088] Examples of epoxy group-containing polyorganosiloxanes include R １１ R １２ SiO ２／２ The siloxane unit (D １０ Examples include those containing units.

[0089] R １１ is a group bonded to a silicon atom and represents an alkyl group; R １２ is a group bonded to a silicon atom and represents an epoxy group or an organic group containing an epoxy group, and specific examples of the alkyl group include those listed above. The epoxy group in the organic group containing an epoxy group may be an independent epoxy group that is not condensed with another ring, or may be an epoxy group that forms a condensed ring with another ring, such as a 1,2-epoxycyclohexyl group. Specific examples of organic groups containing an epoxy group include, but are not limited to, 3-glycidoxypropyl and 2-(3,4-epoxycyclohexyl)ethyl. In the present invention, a preferred example of the epoxy group-containing polyorganosiloxane is, but is not limited to, epoxy group-containing polydimethylsiloxane.

[0090] The epoxy group-containing polyorganosiloxane contains the above-mentioned siloxane unit (D １０ units), but D １０ In addition to the units, the epoxy group-containing polyorganosiloxane may contain Q units, M units and / or T units. In a preferred embodiment of the present invention, specific examples of the epoxy group-containing polyorganosiloxane include D １０ Polyorganosiloxane consisting only of units, D １０ polyorganosiloxanes containing D units and Q units; １０ Polyorganosiloxanes containing D units and M units,１０ Polyorganosiloxanes containing D units and T units, １０ polyorganosiloxanes containing units, Q units and M units, １０ Polyorganosiloxanes containing units, M units and T units, D １０ Examples of suitable organosiloxanes include polyorganosiloxanes containing Q units, M units, and T units.

[0091] The epoxy group-containing polyorganosiloxane is preferably an epoxy group-containing polydimethylsiloxane having an epoxy value of 0.1 to 5. The weight average molecular weight thereof is not particularly limited, but is usually 1,500 to 500,000, and from the viewpoint of suppressing precipitation in the composition, it is preferably 100,000 or less.

[0092] Specific examples of epoxy group-containing polyorganosiloxanes include, but are not limited to, those represented by formulas (E1) to (E3).

[0093] (m １ and n １ indicates the number of each repeating unit and is a positive integer.)

[0094] (m ２ and n ２ indicates the number of each repeating unit and is a positive integer, and R is an alkylene group having 1 to 10 carbon atoms.

[0095] (m ３ , n ３ and ３ indicates the number of each repeating unit and is a positive integer, and R is an alkylene group having 1 to 10 carbon atoms.

[0096] Examples of the methyl group-containing polyorganosiloxane include R ２１０ R ２２０ SiO ２／２ The siloxane unit (D ２００ units), preferably R ２１ R ２１ SiO ２／２ The siloxane unit (D ２０ Examples include those containing units.

[0097] R ２１０ and R ２２０ are groups bonded to a silicon atom, and each independently represents an alkyl group, at least one of which is a methyl group. Specific examples of the alkyl group include those listed above. ２１ is a group bonded to a silicon atom, and represents an alkyl group, and specific examples of the alkyl group include those listed above. ２１ In the present invention, a preferred example of the methyl group-containing polyorganosiloxane is polydimethylsiloxane, but is not limited thereto.

[0098] The methyl group-containing polyorganosiloxane contains the above-mentioned siloxane unit (D ２００ Unit or D ２０ units), but D ２００ Units and D ２０ In addition to units, Q units, M units and / or T units may be included.

[0099] In one embodiment of the present invention, specific examples of the methyl group-containing polyorganosiloxane include D ２００ Polyorganosiloxane consisting only of units, D ２００ polyorganosiloxanes containing D units and Q units; ２００ Polyorganosiloxanes containing D units and M units, ２００ Polyorganosiloxanes containing D units and T units, ２００ polyorganosiloxanes containing units, Q units and M units, ２００ Polyorganosiloxanes containing units, M units and T units, D ２００ Examples of suitable polyorganosiloxanes include polyorganosiloxanes containing Q, M, and T units.

[0100] In a preferred embodiment of the present invention, specific examples of the methyl group-containing polyorganosiloxane include D ２０ Polyorganosiloxane consisting only of units, D ２０ polyorganosiloxanes containing D units and Q units; ２０ Polyorganosiloxanes containing D units and M units, ２０Polyorganosiloxanes containing D units and T units, ２０ polyorganosiloxanes containing units, Q units and M units, ２０ Polyorganosiloxanes containing units, M units and T units, D ２０ Examples of suitable polyorganosiloxanes include polyorganosiloxanes containing Q, M, and T units.

[0101] Specific examples of methyl group-containing polyorganosiloxanes include, but are not limited to, those represented by formula (M1).

[0102] (n ４ indicates the number of repeating units and is a positive integer.)

[0103] Examples of the phenyl group-containing polyorganosiloxane include R ３１ R ３２ SiO ２／２ The siloxane unit (D ３０ Examples include those containing units.

[0104] R ３１ is a group bonded to a silicon atom and represents a phenyl group or an alkyl group; R ３２ is a group bonded to a silicon atom, and represents a phenyl group. Specific examples of the alkyl group include those listed above, with a methyl group being preferred.

[0105] The phenyl group-containing polyorganosiloxane contains the above-mentioned siloxane unit (D ３０ units), but D ３０ In addition to units, Q units, M units and / or T units may be included.

[0106] In a preferred embodiment of the present invention, specific examples of the phenyl group-containing polyorganosiloxane include D ３０ Polyorganosiloxane consisting only of units, D ３０ polyorganosiloxanes containing D units and Q units; ３０ Polyorganosiloxanes containing D units and M units, ３０ Polyorganosiloxanes containing D units and T units, ３０ polyorganosiloxanes containing units, Q units and M units,３０ Polyorganosiloxanes containing units, M units and T units, D ３０ Examples of suitable polyorganosiloxanes include polyorganosiloxanes containing Q, M, and T units.

[0107] Specific examples of the phenyl group-containing polyorganosiloxane include, but are not limited to, those represented by formula (P1) or (P2).

[0108] (m ５ and n ５ indicates the number of each repeating unit and is a positive integer.)

[0109] (m ６ and n ６ indicates the number of each repeating unit and is a positive integer.)

[0110] The polyorganosiloxane of the release agent component (B) may be a commercially available product or may be synthesized. Commercially available polyorganosiloxanes include, for example, WACKERSILICONE FLUID AK series (AK50, AK 350, AK 1000, AK 10000, AK 1000000) and GENIOPLAST GUM, which are products manufactured by Wacker Chemie, dimethyl silicone oil (KF-96L, KF-96A, KF-96, KF-96H, KF-69, KF-965, KF-968), cyclic dimethyl silicone oil (KF-995) manufactured by Shin-Etsu Chemical Co., Ltd.; epoxy group-containing polyorganosiloxane (trade name CMS-227, ECMS-327) manufactured by Gelest, and Shin-Etsu Chemical Co., Ltd. Epoxy group-containing polyorganosiloxanes (KF-101, KF-1001, KF-1005, X-22-343), epoxy group-containing polyorganosiloxane (BY16-839) manufactured by Dow Corning; phenyl group-containing polyorganosiloxanes (PMM-1043, PMM-1025, PDM-0421, PDM-0821) manufactured by Gelest, phenyl group-containing polyorganosiloxane (KF50-3000CS) manufactured by Shin-Etsu Chemical Co., Ltd., and phenyl group-containing polyorganosiloxanes (TSF431, TSF433) manufactured by MOMENTIVE, but are not limited to these.

[0111] In one embodiment, the adhesive composition used in the present invention contains a component (A) that cures and a component (B) that does not undergo a curing reaction, and in another embodiment, component (B) contains a polyorganosiloxane.

[0112] An example of the adhesive composition used in the present invention can contain component (A) and component (B) in any ratio, but considering the balance between adhesion and peelability, the ratio of component (A) to component (B) is preferably 99.995:0.005 to 30:70, more preferably 99.9:0.1 to 75:25, in mass ratio [(A):(B)]. That is, when a polyorganosiloxane component (A') that cures by a hydrosilylation reaction is included, the ratio of component (A') to component (B) is preferably 99.995:0.005 to 30:70, more preferably 99.9:0.1 to 75:25, in mass ratio [(A'):(B)].

[0113] The viscosity of the adhesive composition used in the present invention is not particularly limited, but is usually 500 to 20,000 mPa·s, and preferably 1,000 to 1,0000 mPa·s at 25°C.

[0114] The adhesive composition used in the present invention may contain a solvent for the purpose of adjusting the viscosity, etc., and specific examples of the solvent include, but are not limited to, aliphatic hydrocarbons, aromatic hydrocarbons, and ketones.

[0115] More specifically, examples of the solvent include, but are not limited to, hexane, heptane, octane, nonane, isononane, decane, undecane, dodecane, isododecane, menthane, limonene, toluene, xylene, mesitylene, cumene, MIBK (methyl isobutyl ketone), butyl acetate, diisobutyl ketone, 2-octanone, 2-nonanone, 5-nonanone, cyclohexanone, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, etc. These solvents may be used alone or in combination of two or more.

[0116] When the adhesive composition used in the present invention contains a solvent, the content of the solvent is determined appropriately taking into consideration the desired viscosity of the composition, the coating method to be used, the thickness of the film to be produced, etc., but is generally in the range of about 10 to 90 mass % based on the total mass of the composition.

[0117] The viscosity of the adhesive composition used in the present invention is not particularly limited, but is usually 500 to 20,000 mPa·s, and preferably 1,000 to 5,000 mPa·s at 25° C. The viscosity of the adhesive composition used in the present invention can be adjusted by changing the types of solvents used, their ratios, the concentrations of the film constituent components, etc., taking into consideration various factors such as the coating method used and the desired film thickness.

[0118] An example of the adhesive composition used in the present invention can be produced by mixing component (A), component (B), if used, and a solvent. The order of mixing is not particularly limited, and examples of methods that can easily and reproducibly produce an adhesive composition include, but are not limited to, a method of dissolving component (A) and component (B) in a solvent, or a method of dissolving a portion of component (A) and a portion of component (B) in a solvent and the remaining portions in a solvent, and then mixing the resulting solutions. When preparing the adhesive composition, heating may be performed as appropriate within a range that does not cause decomposition or deterioration of the components. In the present invention, the solvent, solution, etc. used may be filtered using a filter or the like during the production of the adhesive composition or after all components have been mixed in order to remove foreign matter.

[0119] The thickness of the adhesive layer provided in the laminate of the present invention is not particularly limited, but is usually 5 to 500 μm. From the viewpoint of maintaining film strength, it is preferably 10 μm or more, more preferably 20 μm or more, and even more preferably 30 μm or more. From the viewpoint of avoiding non-uniformity due to a thick film, it is preferably 200 μm or less, more preferably 150 μm or less, even more preferably 120 μm or less, and even more preferably 70 μm or less.

[0120] An example of a laminate will be described below with reference to the drawings. FIG. 1 is a schematic cross-sectional view of an example of a laminate. The laminate of FIG. 1 includes, in this order, a semiconductor substrate 1 having bumps 1a, a release agent layer 2, an adhesive layer 3, and a support substrate 4. The bumps 1a of the semiconductor substrate 1 are disposed on the support substrate 4 side. The release agent layer 2 is interposed between the semiconductor substrate 1 and the support substrate 4. The release agent layer 2 is in contact with the semiconductor substrate 1. The release agent layer 2 covers the bumps 1a. The adhesive layer 3 is interposed between the release agent layer 2 and the support substrate 4. The adhesive layer 3 is in contact with the release agent layer 2 and the support substrate 4.

[0121] The laminate of the present invention is preferably produced, for example, by the following laminate production method.

[0122] <Method for producing laminate> The laminate of the present invention can be produced, for example, by a method including: a first step of applying a release agent composition to the surface of a semiconductor substrate and, if necessary, heating the composition to form a release agent coated layer; a second step of applying an adhesive composition to the surface of the release agent coated layer and, if necessary, heating the composition to form an adhesive coated layer; and a third step of applying a load in the thickness direction of the semiconductor substrate and the support substrate to bring the semiconductor substrate, on which the adhesive coated layer and the release agent coated layer have been formed, into close contact with a support substrate while performing at least one of a heat treatment and a decompression treatment, and then performing a post-heat treatment to form a laminate.

[0123] The method for applying the adhesive composition and the release agent composition is not particularly limited, but is usually a spin coating method. Alternatively, a method may be employed in which a coating film is separately formed by a spin coating method or the like, and the sheet-like coating film is attached as an adhesive coating layer or a release agent coating layer.

[0124] The heating temperature of the applied adhesive composition cannot be generally specified because it differs depending on the type and amount of adhesive components contained in the adhesive composition, whether or not a solvent is contained, the boiling point of the solvent used, the desired thickness of the adhesive layer, etc., but is usually 80 to 150°C, and the heating time is usually 30 seconds to 5 minutes. When the adhesive composition contains a solvent, the applied adhesive composition is usually heated.

[0125] The heating temperature of the applied release agent composition cannot be generally specified because it differs depending on the type and amount of the acid generator, the boiling point of the solvent used, the desired thickness of the release agent layer, etc., but is 80°C or higher from the viewpoint of realizing a suitable release agent layer with good reproducibility, and is 300°C or lower from the viewpoint of suppressing decomposition of the acid generator, etc., and the heating time is appropriately determined usually within the range of 10 seconds to 10 minutes depending on the heating temperature. When the release agent composition contains a solvent, the applied release agent composition is usually heated.

[0126] Heating can be carried out using a hot plate, an oven, or the like.

[0127] The thickness of the adhesive coating layer obtained by applying the adhesive composition and, if necessary, heating it is usually about 5 to 500 μm, and is appropriately determined so that the final thickness of the adhesive layer falls within the above-mentioned range.

[0128] The film thickness of the release agent coating layer obtained by applying the release agent composition and, if necessary, heating it is usually about 100 nm to 50 μm, and is appropriately determined so that the final thickness of the release agent layer falls within the above-mentioned range.

[0129] In the present invention, the laminate of the present invention can be obtained by placing such coating layers in contact with each other, applying a load in the thickness direction of the semiconductor substrate and the support substrate while performing a heat treatment or a decompression treatment, or both, to adhere the two layers, and then performing a post-heat treatment. Note that the treatment conditions to be adopted, whether heat treatment, decompression treatment, or a combination of both, are appropriately determined taking into consideration various factors such as the type of adhesive composition, the specific composition of the release agent composition, the compatibility of the films obtained from the two compositions, the film thickness, and the desired adhesive strength.

[0130] The heat treatment temperature is generally determined appropriately from the range of 20 to 150° C. from the viewpoint of removing the solvent if the composition contains one, and from the viewpoint of softening the adhesive coating layer to realize suitable bonding with the release agent coating layer. In particular, from the viewpoint of suppressing or avoiding excessive curing or unnecessary deterioration of the adhesive component (A), the heat treatment temperature is preferably 130° C. or lower, more preferably 90° C. or lower. The heating time is determined appropriately depending on the heating temperature and the type of adhesive, but is generally 30 seconds or longer, preferably 1 minute or longer, from the viewpoint of reliably achieving suitable adhesion, and is generally 10 minutes or shorter, preferably 5 minutes or shorter, from the viewpoint of suppressing deterioration of the adhesive layer and other components.

[0131] The reduced pressure treatment can be carried out by exposing the adhesive coated layer and the release agent coated layer, which are in contact with each other, to an atmospheric pressure of 10 to 10,000 Pa. The reduced pressure treatment time is usually 1 to 30 minutes.

[0132] From the viewpoint of reproducibly obtaining a laminate from which the substrates can be easily separated, the two layers that contact each other are preferably bonded together by a reduced pressure treatment, more preferably by a combination of a heat treatment and a reduced pressure treatment.

[0133] 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 two layers therebetween and can firmly adhere them to each other, but is usually within the range of 10 to 1000 N.

[0134] The post-heating temperature is preferably 120°C or higher from the viewpoint of achieving a sufficient curing rate, and preferably 260°C or lower from the viewpoint of preventing deterioration of the substrate and each layer. The post-heating time is usually 1 minute or longer, preferably 5 minutes or longer, from the viewpoint of achieving suitable bonding of the substrate and layers constituting the laminate, and usually 180 minutes or shorter, preferably 120 minutes or shorter, from the viewpoint of suppressing or avoiding adverse effects on each layer due to excessive heating. Heating can be performed using a hot plate, oven, or the like. When post-heating is performed using a hot plate, either the semiconductor substrate or the support substrate of the laminate may be heated facing down, but from the viewpoint of achieving suitable and reproducible peeling, post-heating with the semiconductor substrate facing down is preferred. Note that one purpose of the post-heating treatment is to achieve a more suitable self-standing adhesive layer and release agent layer, particularly to achieve suitable curing by a hydrosilylation reaction.

[0135] (Method for manufacturing a processed semiconductor substrate) The method for manufacturing a processed semiconductor substrate of the present invention includes a first step and a second step. The method for manufacturing a processed semiconductor substrate of the present invention may further include a third step. The first step is a step in which the semiconductor substrate of the laminate of the present invention is processed. The second step is a step in which the semiconductor substrate processed in the first step is separated from the support substrate. The third step is a step in which the separated semiconductor substrate is cleaned with a cleaning composition.

[0136] <First Step> The processing performed on the semiconductor substrate in the first step is, for example, processing of the side opposite the circuit surface of the wafer, such as thinning the wafer by polishing the backside of the wafer. Subsequently, through-silicon vias (TSVs) and the like are formed, and then the thinned wafer is peeled off from the support substrate to form a wafer stack, which is then three-dimensionally mounted. Also, before and after this, wafer backside electrodes and the like are formed. During the wafer thinning and TSV process, the wafer is subjected to a heat load of approximately 250 to 350°C while adhered to the support substrate. The laminate of the present invention, including the adhesive layer and release agent layer, typically has heat resistance to this load. Note that the processing is not limited to the above-described processing, and also includes, for example, the implementation of a semiconductor component mounting process when the wafer is temporarily adhered to a support substrate to support the substrate on which the semiconductor component is mounted.

[0137] <Second Step> The second step is a step of separating the semiconductor substrate processed in the first step from the support substrate, and preferably includes a step of irradiating the release agent layer with light. In the second step, methods for separating (peeling) the semiconductor substrate from the support substrate include, but are not limited to, mechanical peeling using a tool with a sharp part after irradiating the release agent layer with light, peeling between the support and the wafer, etc. By irradiating the release agent layer with light from the support substrate side, the release agent layer is altered (for example, separated or decomposed) as described above, and then, for example, one of the substrates can be pulled up to easily separate the semiconductor substrate from the support substrate.

[0138] The light irradiation of the release agent layer does not necessarily have to be performed on the entire area of ​​the release agent layer. Even if there are regions irradiated with light and regions not irradiated with light, as long as the release ability of the release agent layer as a whole is sufficiently improved, the semiconductor substrate and the support substrate can be separated by a slight external force, such as by lifting up the support substrate. The ratio and positional relationship of the light-irradiated and non-irradiated regions will vary depending on the type and specific composition of the adhesive used, the thickness of the adhesive layer, the thickness of the release agent layer, the intensity of the irradiated light, etc., but those skilled in the art will be able to set appropriate conditions without the need for excessive testing. For these reasons, the method for producing a processed semiconductor substrate of the present invention makes it possible to shorten the light irradiation time when peeling is performed by light irradiation from the support substrate side, for example, when the support substrate of the laminate used is optically transparent. As a result, not only can throughput be improved, but physical stresses and the like required for peeling can be avoided, and the semiconductor substrate and the support substrate can be easily and efficiently separated by light irradiation alone. Typically, the light irradiation dose for peeling is 50 to 3,000 mJ / cm. ２ The irradiation time is appropriately determined depending on the wavelength and the irradiation amount. The light irradiation may be performed using laser light or non-laser light from a light source such as an ultraviolet lamp.

[0139] In the third step, the surface of the separated semiconductor substrate is cleaned by spraying the cleaning composition onto the surface or immersing the separated semiconductor substrate in the cleaning composition, and then the surface is usually rinsed with a solvent and dried. Examples of the cleaning composition include those described below.

[0140] In the method for producing a processed semiconductor substrate of the present invention, the processed semiconductor substrate produced through the third step is well cleaned with the cleaning composition. However, this does not prevent the surface of the processed semiconductor substrate from being further cleaned using a removal tape or the like, and the surface may be further cleaned using a removal tape or the like, if necessary.

[0141] <<Cleaning Composition>> After light irradiation, residue of the release agent layer remaining on the semiconductor substrate after separation of the semiconductor substrate and the support substrate can be suitably removed by a cleaning composition, and such a cleaning composition usually contains a solvent.

[0142] Examples of solvents include lactones, ketones, polyhydric alcohols, compounds having an ester bond, 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 an ester bond include ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, and dipropylene glycol monoacetate. Examples of derivatives of polyhydric alcohols include compounds having an ether bond, such as monoalkyl ethers (e.g., monomethyl ether, monoethyl ether, monopropyl ether, and monobutyl ether) or monophenyl ethers of the above polyhydric alcohols or compounds having an ester bond. Among these, propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) are preferred. Examples of cyclic ethers include dioxane. Examples of esters include methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, and ethyl ethoxypropionate. Examples of aromatic organic solvents include anisole, ethyl benzyl ether, cresyl methyl ether, diphenyl ether, dibenzyl ether, phenetole, butyl phenyl ether, ethylbenzene, diethylbenzene, pentylbenzene, isopropylbenzene, toluene, xylene, cymene, and mesitylene. These may be used alone or in combination of two or more.Among these, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), cyclohexanone, and ethyl lactate (EL) are preferred.

[0143] Also preferred are mixed solvents containing PGMEA and a polar solvent. The blending ratio (mass ratio) can be determined appropriately taking into account the compatibility of the PGMEA and the polar solvent, but is preferably within the range of 1:9 to 9:1, and more preferably 2:8 to 8:2. For example, when EL is blended as the polar solvent, the mass ratio of PGMEA:EL is preferably 1:9 to 9:1, and more preferably 2:8 to 8:2. When PGME is blended as the polar solvent, the mass ratio of PGMEA:PGME is preferably 1:9 to 9:1, more preferably 2:8 to 8:2, and even more preferably 3:7 to 7:3. When PGME and cyclohexanone are blended as the polar solvents, the mass ratio of PGMEA:(PGME + cyclohexanone) is preferably 1:9 to 9:1, more preferably 2:8 to 8:2, and even more preferably 3:7 to 7:3.

[0144] The cleaning composition may or may not contain a salt, but it is preferable that the cleaning composition does not contain a salt, since this can suppress damage to the bumps.

[0145] An example of a detergent composition containing a salt is a detergent composition containing a quaternary ammonium salt and a solvent. The quaternary ammonium salt is composed of a quaternary ammonium cation and an anion, and is not particularly limited as long as it is used for this type of application. A typical example of such a quaternary ammonium cation is a tetra(hydrocarbon)ammonium cation. On the other hand, the anion paired with the quaternary ammonium cation is a hydroxide ion (OH － ) ; fluorine ion (F － ), chloride ions (Cl － ), bromine ion (Br － ), iodine ion (I － ) and other halogen ions; tetrafluoroborate ion (BF ４ －) ; hexafluorophosphate ion (PF ６ － ) and the like, but are not limited to these.

[0146] The quaternary ammonium salt is preferably a halogen-containing quaternary ammonium salt, more preferably a fluorine-containing quaternary ammonium salt. In the quaternary ammonium salt, the halogen atom may be contained in either the cation or the anion, but is preferably contained in the anion.

[0147] In a preferred embodiment, the fluorine-containing quaternary ammonium salt is tetra(hydrocarbon)ammonium fluoride. Specific examples of the hydrocarbon group in tetra(hydrocarbon)ammonium fluoride include alkyl groups having 1 to 20 carbon atoms, alkenyl groups having 2 to 20 carbon atoms, alkynyl groups having 2 to 20 carbon atoms, and aryl groups having 6 to 20 carbon atoms. In a more preferred embodiment, the tetra(hydrocarbon)ammonium fluoride includes tetraalkylammonium fluoride. Specific examples of tetraalkylammonium fluorides include, but are not limited to, tetramethylammonium fluoride, tetraethylammonium fluoride, tetrapropylammonium fluoride, and tetrabutylammonium fluoride (also known as tetrabutylammonium fluoride). Of these, tetrabutylammonium fluoride is preferred.

[0148] The quaternary ammonium salts such as tetra(hydrocarbon)ammonium fluoride may be used in the form of a hydrate. The quaternary ammonium salts such as tetra(hydrocarbon)ammonium fluoride may be used singly or in combination of two or more. The amount of the quaternary ammonium salt is not particularly limited as long as it dissolves in the solvent contained in the cleaning composition, but is usually 0.1 to 30 mass% based on the cleaning composition.

[0149] When the cleaning composition contains a salt, the solvent to be used in combination with the salt is not particularly limited as long as it is used for this type of application and dissolves the salt such as a quaternary ammonium salt. However, from the viewpoint of reproducibly obtaining a cleaning composition having excellent cleaning properties and from the viewpoint of satisfactorily dissolving the salt such as a quaternary ammonium salt to obtain a cleaning composition having excellent uniformity, the cleaning composition preferably contains one or two or more amide solvents.

[0150] A suitable example of the amide solvent is an acid amide derivative represented by formula (Z).

[0151] In the formula, R ０ represents an ethyl group, a propyl group, or an isopropyl group, preferably an ethyl group or an isopropyl group, and more preferably an ethyl group. Ａ and R Ｂ each independently represents an alkyl group having 1 to 4 carbon atoms. The alkyl group having 1 to 4 carbon atoms may be linear, branched, or cyclic, and specific examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a cyclopropyl group, an n-butyl group, an isobutyl group, an s-butyl group, a t-butyl group, and a cyclobutyl group. Of these, R Ａ and R Ｂ As the alkyl group, a methyl group or an ethyl group is preferred, and both of them are more preferably methyl groups or ethyl groups, and both of them are even more preferably methyl groups.

[0152] Examples of the acid amide derivative represented by formula (Z) include N,N-dimethylpropionamide, N,N-diethylpropionamide, N-ethyl-N-methylpropionamide, N,N-dimethylbutyric acid amide, N,N-diethylbutyric acid amide, N-ethyl-N-methylbutyric acid amide, N,N-dimethylisobutyric acid amide, N,N-diethylisobutyric acid amide, N-ethyl-N-methylisobutyric acid amide, etc. Among these, N,N-dimethylpropionamide and N,N-dimethylisobutyric acid amide are particularly preferred, and N,N-dimethylpropionamide is more preferred.

[0153] The acid amide derivative represented by formula (Z) may be synthesized by a substitution reaction between a corresponding carboxylic acid ester and an amine, or a commercially available product may be used.

[0154] Another example of a preferred amide solvent is a lactam compound represented by formula (Y).

[0155] In formula (Y), R １０１ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R １０２ represents an alkylene group having 1 to 6 carbon atoms. Specific examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, an n-propyl group, and an n-butyl group, and specific examples of the alkylene group having 1 to 6 carbon atoms include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group, but are not limited to these.

[0156] Specific examples of the lactam compound represented by formula (Y) include α-lactam compounds, β-lactam compounds, γ-lactam compounds, and δ-lactam compounds, and these can be used alone or in combination of two or more.

[0157] In a preferred embodiment of the present invention, the lactam compound represented by formula (Y) comprises 1-alkyl-2-pyrrolidone (N-alkyl-γ-butyrolactam), in a more preferred embodiment, it comprises N-methylpyrrolidone (NMP) or N-ethylpyrrolidone (NEP), and in an even more preferred embodiment, it comprises N-methylpyrrolidone (NMP).

[0158] The cleaning composition used in the present invention may contain water as a solvent, but usually only an organic solvent is used as the solvent from the viewpoint of avoiding corrosion of the substrate, etc. In this case, it is not excluded that the cleaning composition may contain water of hydration of salts or trace amounts of water contained in the organic solvent. The water content of the cleaning composition used in the present invention is usually 5 mass% or less.

[0159] The constituent elements and methodological elements of the above-described steps of the method for manufacturing a processed semiconductor substrate of the present invention may be modified in various ways without departing from the spirit and scope of the present invention. The method for manufacturing a processed semiconductor substrate of the present invention may include steps other than those described above.

[0160] The separation method of the present invention is a method for separating the semiconductor substrate and support substrate of a laminate of the present invention by irradiating light onto the release agent layer from the semiconductor substrate side or the support substrate side when the semiconductor substrate or support substrate of the laminate is optically transparent. In the laminate of the present invention, the semiconductor substrate and support substrate are temporarily bonded by the adhesive layer and the release agent layer in a suitably separable manner. Therefore, for example, when the support substrate is optically transparent, the semiconductor substrate and support substrate can be easily separated by irradiating light onto the release agent layer from the support substrate side of the laminate. Usually, the separation is performed after processing the semiconductor substrate of the laminate.

[0161] An example of a method for manufacturing a processed semiconductor substrate is described below with reference to the drawings. Figures 2A to 2E are diagrams illustrating one embodiment of manufacturing a thinned semiconductor substrate. First, a laminate is prepared ( Figure 2A ). The laminate shown in Figure 2A is the laminate shown in Figure 1 . Next, a polishing device (not shown) is used to polish the surface of the semiconductor substrate 1 opposite the surface on which the bumps 1a are present, thereby thinning the semiconductor substrate 1 ( Figure 2B ). The thinned semiconductor substrate 1 may also be subjected to the formation of through-hole electrodes, etc. Next, light L is irradiated onto the release agent layer 2 from the support substrate 4 side ( Figure 2C ). The release agent layer 2 absorbs the light and changes (e.g., separates or decomposes), facilitating separation of the thinned semiconductor substrate 1 and the support substrate 4. Next, the thinned semiconductor substrate 1 and the support substrate 4 are peeled off using a peeling device (not shown) ( Figure 2D ). At this time, the release agent layer 2 and the adhesive layer 3 are peeled off, thereby peeling off the thinned semiconductor substrate 1 and the support substrate 4. At this time, the release agent layer 2 remains on the semiconductor substrate 1 ( FIG. 2E ). Next, although not shown in the figure, the release agent layer 2 is dissolved and removed from the thinned semiconductor substrate 1 using a cleaning composition, thereby cleaning the thinned semiconductor substrate 1. In this manner, the thinned semiconductor substrate 1 is obtained.

[0162] 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.

[0163] [Devices] (1) Scanning electron microscope: Regulus 8420 manufactured by Hitachi High-Tech Corporation (2) Vacuum bonding device: XBS300 manufactured by SUSS Microtec K.K. (3) Laser peeling device: Laser debonder manufactured by Optopia Co., Ltd.

[0164] [1] Preparation of Release Agent Composition [Synthesis Example 1] 86.36 g of 1,4-dioxane and 86.36 g of toluene were added to 56.02 g of 1-phenylnaphthylamine, 50.00 g of 1-pyrenecarboxaldehyde (Maruzen Chemical Co., Ltd.), 6.67 g of 4-(trifluoromethyl)benzaldehyde, and 2.46 g of methanesulfonic acid, and the mixture was refluxed and stirred for 18 hours under a nitrogen atmosphere. After completion of the reaction, the mixture was diluted with 96 g of tetrahydrofuran, and the diluted solution was added dropwise to methanol to obtain a precipitate. The obtained precipitate was filtered, washed with methanol, and dried under reduced pressure at 60°C to obtain 72.12 g of a novolak resin (hereinafter abbreviated as PPNAPCA-F). The weight average molecular weight measured by GPC in terms of standard polystyrene was 1,100.

[0165] [Preparation Example 1] 3.6 g of the resin (PPNAPCA-F) obtained in Synthesis Example 1 was mixed with 0.72 g of TMOM-BP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) as a crosslinking agent, and the mixture was dissolved in 95.68 g of propylene glycol monomethyl ether acetate to prepare a solution. Finally, the obtained mixture was filtered through a 300 mesh nylon filter to obtain release agent composition-1.

[0166] Preparation Example 2 10 g of V886 (manufactured by Tokyo Chemical Industry Co., Ltd.) and 90 g of tetrahydrofuran (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed and stirred for 5 minutes using a mix rotor. Finally, the resulting mixture was filtered through a 300 mesh nylon filter to obtain release agent composition-2.

[0167] V886: structural formula below, 9,9'-[1,2-phenylenebis(methylene)]bis[N3,N3,N6,N6-tetrakis(4-methoxyphenyl)-9H-carbazole-3,6-diamine]

[0168] Preparation Example 3 10 g of carminic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) and 90 g of tetrahydrofuran (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed and stirred for 5 minutes using a mix rotor. Finally, the resulting mixture was filtered through a 300 mesh nylon filter to obtain release agent composition-3.

[0169] Carminic acid: structural formula below

[0170] Preparation Example 4 25 g of tannic acid (Kanto Chemical Co., Inc.) and 75 g of propylene glycol monomethyl ether acetate (Tokyo Chemical Industry Co., Ltd.) were mixed and stirred for 5 minutes using a mix rotor. Finally, the resulting mixture was filtered through a 300 mesh nylon filter to obtain release agent composition-4.

[0171] Tannic acid: structural formula below, molecular weight 1701.2

[0172] Preparation Example 5 30 g of tannic acid (Kanto Chemical Co., Inc.) and 70 g of propylene glycol monomethyl ether acetate (Tokyo Chemical Industry Co., Ltd.) were mixed and stirred for 5 minutes using a mix rotor. Finally, the resulting mixture was filtered through a 300-mesh nylon filter to obtain release agent composition-5.

[0173] [2] Preparation of adhesive composition [Preparation Example 6] 95 g of vinyl group-containing MQ resin (manufactured by Wacker Chemie), 93.4 g of p-menthane (manufactured by Nippon Terpene Chemical Co., Ltd.) as a solvent, and 0.41 g of 1,1-diphenyl-2-propyn-1-ol (manufactured by Tokyo Chemical Industry Co., Ltd.) were added to a 600 mL stirring vessel dedicated to a planetary centrifugal mixer, and the mixture was stirred for 5 minutes with a planetary centrifugal mixer to obtain a mixture (I). 19.0 g of SiH group-containing linear polydimethylsiloxane (manufactured by Wacker Chemie) having a viscosity of 100 mPa s, 29.5 g of vinyl group-containing linear polydimethylsiloxane (manufactured by Wacker Chemie) having a viscosity of 200 mPa s, and 1,000,000 mm ２ 65.76 g of polyorganosiloxane (manufactured by Wacker Chem, trade name AK1000000) and 0.41 g of 1-ethynyl-1-cyclohexanol (manufactured by Wacker Chem) were added and stirred for an additional 5 minutes with a planetary centrifugal mixer to obtain mixture (II). 0.20 g of platinum catalyst (manufactured by Wacker Chem) and 17.7 g of vinyl group-containing linear polydimethylsiloxane (manufactured by Wacker Chem) having a viscosity of 1000 mPa·s were stirred for 5 minutes with a planetary centrifugal mixer to obtain mixture (III). 14.9 g of mixture (III) was added to mixture (II) and stirred for an additional 5 minutes with a planetary centrifugal mixer. The resulting mixture was filtered through a 300 mesh nylon filter to obtain an adhesive composition.

[0174] [3] Investigation of Coverability and Cleanability of Electrode Substrates [Comparative Examples 1-1 to 1-4 and Examples 1-1 to 1-3] Each of the release agent compositions obtained in Preparation Examples 1 to 5 was applied to a silicon substrate with SnAg electrodes (bump height: 10 μm, bump diameter: 10 μm, pitch: 20 μm) and heated on a hot plate at 200°C for 1 minute to form a release agent layer. The substrate was then cut with a diamond pen, and a scanning electron microscope was used horizontally to confirm whether the electrodes were completely covered with the release agent layer. The film thickness of the release agent layer between the electrodes was also measured. If the electrodes were covered, it was marked with "○", and if they were not covered, it was marked with "×". Regarding the cleaning test, the substrate after measurement was immersed in N-methylpyrrolidone for 3 minutes, and the solvent was dried by spin drying. The substrate was then observed under a microscope. If no residue was observed, it was marked with "○", and if residue was observed, it was marked with "×". The results are shown in Table 1.

[0175] In Examples 1-1 to 1-3, the film thickness was lower than the electrode height, but the electrode could be covered. In addition, in Comparative Example 1-2, the coating film of Release Agent Composition-1 was cracked and uneven, so it was determined that coating at 3,500 nm was not possible.

[0176] [3] Preparation and Evaluation of Laminates for Evaluation [Example 2] The release agent composition-4 obtained in Preparation Example 4 was spin-coated onto a silicon substrate with 300 mm SnAg electrodes (bump height 10 μm, bump diameter 10 μm, pitch 20 μm) in the same manner as in Examples 1-3, and heated at 200°C for 1 minute to form a release agent coating layer on the sample substrate, which was a semiconductor substrate. The adhesive composition obtained in Preparation Example 5 was also spin-coated onto the release agent coating layer so that the film thickness in the final laminate was approximately 50 μm, and heated at 120°C for 90 seconds to form an adhesive coating layer on the release agent coating layer. Then, using a bonding device, the silicon substrate with electrodes and a glass wafer (EAGLE-XG, manufactured by Corning, thickness 700 μm) were bonded together so as to sandwich the release agent coating layer and the adhesive coating layer, and then the sample substrate was placed face down and post-heated on a hot plate at 200°C for 10 minutes to produce a laminate. The bonding was performed at a temperature of 23°C and a reduced pressure of 1,500 Pa. The resulting bonded substrate was irradiated with 308 nm excimer laser light at an energy of 300 mJ from a direction perpendicular to the glass wafer using a laser debonder. After the laser irradiation, it was confirmed whether peeling from the interface between the release agent layer and the adhesive layer was possible, and it was found that peeling was easy. Furthermore, the silicon substrate with the electrode after peeling was immersed in N-methylpyrrolidone for 3 minutes, and the solvent was dried by spin drying. When the substrate was observed under a microscope, no residue from the release agent layer was confirmed.

[0177] REFERENCE SIGNS LIST 1 semiconductor substrate 1a bump 2 release agent layer 3 adhesive layer 4 support substrate L light

Claims

1. A release agent composition for forming the release agent layer of a laminate having a light-transmitting support substrate, a semiconductor substrate having bumps on the support substrate side, a release agent layer interposed between the support substrate and the semiconductor substrate and in contact with the semiconductor substrate, and an adhesive layer interposed between the support substrate and the release agent layer and in contact with the release agent layer, the laminate being used to separate the semiconductor substrate from the support substrate after the release agent layer absorbs light irradiated from the support substrate side, the release agent composition containing a polyphenol compound selected from tannins and flavonoids.

2. The stripping composition of claim 1, wherein the polyphenol compound is tannic acid.

3. The stripping composition according to claim 1, wherein the content of the polyphenol compound in the stripping composition is 90 mass % or more based on the non-volatile content in the stripping composition.

4. A laminate comprising: a light-transmitting support substrate; a semiconductor substrate having bumps on the support substrate side; a release agent layer interposed between the support substrate and the semiconductor substrate and in contact with the semiconductor substrate; and an adhesive layer interposed between the support substrate and the release agent layer and in contact with the release agent layer, wherein the semiconductor substrate and the support substrate are separated after the release agent layer absorbs light irradiated from the support substrate side, and the release agent layer is formed from the release agent composition according to any one of claims 1 to 3.

5. The laminate according to claim 4, wherein the adhesive layer is a layer formed from an adhesive composition containing a compound having a siloxane structure.

6. The laminate of claim 5, wherein the adhesive composition contains a curable component (A).

7. The laminate according to claim 6, wherein the component (A) is a component that cures via a hydrosilylation reaction.

8. The laminate according to claim 6, wherein component (A) comprises: a polyorganosiloxane (a1) having a silicon-bonded alkenyl group having 2 to 40 carbon atoms; a polyorganosiloxane (a2) having a Si—H group; and a catalyst (A2).

9. The laminate according to claim 4, wherein the thickness of the release agent layer is 35% to 100% of the height of the bumps.

10. A method for manufacturing a processed semiconductor substrate, comprising: a first step in which the semiconductor substrate of the laminate described in claim 4 is processed; and a second step in which the semiconductor substrate processed in the first step is separated from the support substrate.

11. The method for producing a processed semiconductor substrate according to claim 10, wherein the second step includes irradiating the release agent layer with light.

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