Release agent composition for light irradiation stripping

Abstract

Provided is a release agent composition for forming a release agent layer in a laminate which can firmly bond a support substrate to a semiconductor substrate or an electronic device layer during processing of the semiconductor substrate or the electronic device layer, and which can prevent the support substrate from being adhered to the semiconductor substrate or the electronic device layer after processing of the substrate. The support substrate and the semiconductor substrate or the electronic device layer can be easily separated by light irradiation, the stripping agent layer is used for the laminated body and can be stripped by light irradiation, and the stripping agent composition contains a water solvent. A release agent composition for light irradiation release is used for forming a release agent layer of a laminate having a semiconductor substrate or an electronic device layer, a translucent support substrate, and a release agent layer provided between the semiconductor substrate or the electronic device layer and the support substrate, the electronic device layer includes a plurality of semiconductor chip substrates and a sealing resin disposed between the semiconductor chip substrates, and the laminate is used for peeling the semiconductor substrate or the electronic device layer from the support substrate after the release agent layer absorbs light irradiated from the support substrate side. The release agent composition contains a light-absorbing compound and a solvent, the light-absorbing compound contributes to easy separation of the semiconductor substrate or the electronic device layer from the support substrate by absorbing the light, and the solvent contains water.

Description

Technical Field

[0001] The present invention relates to a stripping agent composition for light irradiation stripping. Background Art

[0002] With regard to semiconductor wafers that were previously integrated in a two-dimensional plane direction, a semiconductor integration technology that further integrates (stacks) the plane in a three-dimensional direction is pursued for the purpose of further integration. This three-dimensional stacking is a technology that integrates into multiple layers while wiring through silicon vias (TSV). When integrating into multiple layers, the side opposite to the circuit surface formed (i.e., the back side) of each wafer to be integrated is thinned by grinding, and the thinned semiconductor wafers are stacked.

[0003] The semiconductor wafer before thinning (also referred to as wafer here) is bonded to a support body in order to be ground using a grinding device. The bonding at this time must be easy to peel off after grinding, so it is called temporary bonding. The temporary bonding must be easy to disassemble from the support body. When a large force is applied to the disassembly, the thinned semiconductor wafer is sometimes cut or deformed. In order to avoid such a situation, it is easy to disassemble. However, when the back of the semiconductor wafer is ground, it is not preferred that it is detached or offset due to the grinding stress. Therefore, the performance pursued by temporary bonding is: to withstand the stress during grinding and to be easy to disassemble after grinding.

[0004] For example, the following properties are sought: high stress (strong adhesive force) with respect to the planar direction during polishing, and low stress (weak adhesive force) with respect to the longitudinal direction during removal.

[0005] For such bonding and separation processes, methods using laser irradiation have been disclosed (see, for example, Patent Documents 1 and 2). However, with further progress in the semiconductor field in recent years, new technologies related to peeling by irradiation with light such as laser have been sought.

[0006] In addition, in the method of processing a substrate by temporarily bonding a support body, the substrate to be temporarily bonded includes, in addition to the semiconductor substrate for the purpose of thinning as described above, an electronic device layer including a plurality of semiconductor chip substrates and a sealing resin arranged between the semiconductor chip substrates.

[0007] Semiconductor packages (electronic components) including semiconductor elements (also called semiconductor chip substrates) have various forms depending on the corresponding sizes, such as WLP (Wafer Level Package) and PLP (Panel Level Package).

[0008] In order to achieve miniaturization of semiconductor packages, it is important to reduce the thickness of the substrate in the assembled components. However, if the thickness of the substrate is reduced, its strength is reduced, and the substrate is easily damaged when manufacturing the semiconductor package. In this regard, it is known that a substrate is temporarily bonded to a support body using an adhesive, and after processing the substrate, the substrate is separated from the support body (for example, see Patent Documents 3 and 4).

[0009] Prior art literature

[0010] Patent Literature

[0011] Patent Document 1: Japanese Patent Application Publication No. 2004-64040

[0012] Patent Document 2: Japanese Patent Application Publication No. 2012-106486

[0013] Patent Document 3: Japanese Patent Application Publication No. 2019-34541

[0014] Patent Document 4: Japanese Patent Application Publication No. 2020-107649 Summary of the invention

[0015] Problems to be solved by the invention

[0016] The above-mentioned patent documents 1 and 2 describe a laminated body, which has two layers, a bonding layer (adhesive layer) and a light conversion layer (also called a separation layer) containing a light absorber, stacked between the semiconductor substrate and the support in order to peel off the semiconductor substrate equivalent to the above-mentioned semiconductor chip from the support by laser irradiation.

[0017] In addition, the above-mentioned patent documents 3 and 4 describe a laminated body, which has two layers, an adhesive layer (adhesive layer) and a separation layer, stacked between the electronic device layer and the support body in order to peel off the above-mentioned electronic device layer having multiple semiconductor chip substrates arranged in a sealing resin layer from the support body by laser irradiation.

[0018] Furthermore, the separation layer described in the above-mentioned patent documents 1 to 4 is formed by a composition containing an organic solvent. From the perspective of the working environment and the safety of the composition in handling, waste liquid treatment, etc., it is ideal to reduce the amount of organic solvent used as much as possible. If the separation layer can be formed by a composition containing an aqueous solvent without containing an organic solvent, it is preferred from the perspective of safety and reduced environmental load.

[0019] In order to further advance the semiconductor field, there is a constant demand for the development of new types of stripper compositions to be used.

[0020] Therefore, the present invention is completed in view of the above situation, and its purpose is to provide a stripping agent composition, which is used to form the following stripping agent layer in the following stacked body, wherein the stacked body can firmly bond the supporting substrate to the semiconductor substrate or the electronic device layer when the semiconductor substrate or the electronic device layer is processed, and after the substrate is processed, the supporting substrate can be easily separated from the semiconductor substrate or the electronic device layer by light irradiation, the stripping agent layer is a stripping agent layer used for the stacked body that can be stripped by light irradiation, and the stripping agent composition contains an aqueous solvent.

[0021] Solutions for solving problems

[0022] The present inventors have conducted intensive studies to solve the above-mentioned technical problems, and as a result, have found that the above-mentioned technical problems can be solved, and have completed the present invention having the following gist.

[0023] That is, the present invention includes the following contents.

[0024] [1] A stripping agent composition for light irradiation stripping, which is used to form the following stripping agent layer of the following laminated body, the laminated body comprising: a semiconductor substrate or an electronic device layer, a light-transmitting supporting substrate, and a stripping agent layer provided between the semiconductor substrate or the electronic device layer and the supporting substrate, the electronic device layer comprising a plurality of semiconductor chip substrates and a sealing resin arranged between the semiconductor chip substrates, and the laminated body is used to: strip the semiconductor substrate or the electronic device layer from the supporting substrate after the stripping agent layer absorbs light irradiated from the supporting substrate side, the stripping agent composition containing: a light absorbing compound and a solvent, the light absorbing compound absorbing the light to facilitate the stripping of the semiconductor substrate or the electronic device layer from the supporting substrate, and the solvent containing water.

[0025] [2] The stripping agent composition according to [1], wherein the content of the water is 50% by mass or more relative to the solvent in the stripping agent composition.

[0026] [3] The stripping agent composition according to [2], wherein the content of the water is 98% by mass or more relative to the solvent in the stripping agent composition.

[0027] [4] The stripping agent composition according to [1], wherein, when the absorption spectrum of the light absorbing compound in the range of 250 nm to 800 nm is measured for the light absorbing compound, the absorption spectrum has a maximum value of the maximum absorbance between 250 nm and 350 nm in the range of 250 nm to 800 nm.

[0028] [5] The stripping agent composition according to [4], wherein the light absorbing compound is a polyphenol-based compound.

[0029] [6] The stripping agent composition according to [5], wherein the polyphenol compound is a compound selected from the group consisting of condensed tannins formed by polymerization of compounds having a flavanol skeleton, hydrolyzable tannins formed by ester bonding of aromatic compounds of gallic acid or ellagic acid with sugar, and flavonoids derived from compounds having a flavanone skeleton structure.

[0030] [7] The stripping agent composition according to [6], wherein the hydrolyzable tannin is tannic acid represented by the following formula (9).

[0031]

[0032] [8] The release agent composition according to any one of [1] to [7], further comprising a water-soluble dye.

[0033] Effects of the Invention

[0034] According to the present invention, a stripping agent composition can be provided, which is used to form the following stripping agent layer in the following stacked body, wherein the stacked body can firmly bond a supporting substrate to the semiconductor substrate or the electronic device layer when the semiconductor substrate or the electronic device layer is processed, and after the substrate is processed, the supporting substrate can be easily separated from the semiconductor substrate or the electronic device layer by light irradiation, the stripping agent layer is a stripping agent layer used for the stacked body that can be stripped by light irradiation, and the stripping agent composition contains an aqueous solvent. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] Figure 1 This is a schematic cross-sectional view of an example of the laminated body in the first embodiment.

[0036] Figure 2 This is a schematic cross-sectional view of another example of the laminated body in the first embodiment.

[0037] Figure 3 This is a schematic cross-sectional view of an example of a laminated body in the second embodiment.

[0038] Figure 4 It is a schematic cross-sectional view of another example of the laminated body in the second embodiment.

[0039] Figure 5 This is a schematic cross-sectional view for explaining a method for producing a laminated body showing an example of the second embodiment.

[0040] Figure 6 This is a schematic cross-sectional view for explaining a method for producing a laminated body showing an example of the second embodiment.

[0041] Figure 7 This is a schematic cross-sectional view for explaining a method for producing a laminated body showing an example of the second embodiment.

[0042] Figure 8 This is a schematic cross-sectional view for explaining a method for producing a laminated body showing an example of the second embodiment.

[0043] Fig. 9 This is a schematic cross-sectional view for explaining a method for processing a laminated body showing an example in the second embodiment.

[0044] Fig.10 This is a schematic cross-sectional view for explaining a method for processing a laminated body showing an example in the second embodiment.

[0045] Fig.11 This is a schematic cross-sectional view for explaining a method for separating a stacked body showing an example of the second embodiment.

[0046] Fig.12 This is a schematic cross-sectional view for explaining a method for separating a stacked body showing an example of the second embodiment.

[0047] Fig.13 This is a schematic cross-sectional view for explaining a method for cleaning a laminated body after separation, showing an example of the second embodiment. DETAILED DESCRIPTION

[0048] (Removal agent composition for light irradiation removal)

[0049] The release agent composition of the present invention is a composition that can be released by light irradiation.

[0050] The stripping agent composition of the present invention is a composition for easily stripping a semiconductor substrate or an electronic device layer from a supporting substrate.

[0051] The stripping agent composition of the present invention contains a light-absorbing compound and a solvent containing water. The light-absorbing compound helps facilitate the stripping of a semiconductor substrate or an electronic device layer and a supporting substrate by absorbing light.

[0052] The remover composition of the present invention may further contain a water-soluble dye in addition to the light-absorbing compound and the solvent containing water.

[0053] Furthermore, the remover composition of the present invention may contain other components in addition to the light absorbing compound, the water-containing solvent, and the water-soluble dye.

[0054] <Solvent>

[0055] The solvent contained in the release agent composition of the present invention contains water.

[0056] Conventionally, the release agent composition contains an organic solvent, but the present invention uses water as a solvent, thereby ensuring safety for the environment and human body, and further reducing the waste liquid treatment cost and environmental load.

[0057] In the present invention, the content of water is preferably 50% by mass or more, more preferably 98% by mass or more, and particularly preferably 100% by mass, based on the solvent in the release agent composition.

[0058] <Light-absorbing compounds>

[0059] For the light absorbing compound of the present invention, it is preferred that when the absorption spectrum of the light absorbing compound in the range of 250nm to 800nm ​​is measured, the absorption spectrum has a maximum value of the maximum absorbance between 250nm and 350nm in the range of 250nm to 800nm. For example, the absorption spectrum may have a maximum value between 260nm and 315nm. By having such light absorption characteristics, good peeling properties between the semiconductor substrate or the electronic device layer and the supporting substrate can be achieved.

[0060] The absorption spectrum can be measured using a spectrophotometer (for example, an ultraviolet-visible-near-infrared (UV-Vis-NIR) spectrophotometer).

[0061] As long as the measurement range includes 250 nm to 800 nm, a wider range may be used.

[0062] In the measurement of the absorption spectrum, it is preferable to form a film having a thickness that allows the presence of a local maximum value as a measurement sample. For example, the film thickness of the measurement sample is about 200 nm.

[0063] The light absorbing compound is preferably a polyphenol compound.

[0064] The polyphenol compound is preferably a compound selected from the group consisting of condensed tannins obtained by polymerizing compounds having a flavanol skeleton, hydrolyzable tannins obtained by esterifying aromatic compounds of gallic acid or ellagic acid with sugars, and flavonoids derived from compounds having a flavanone skeleton structure.

[0065] The polyphenol compound of the present invention refers to a plant component having a plurality of phenolic hydroxyl groups (hydroxyl groups bonded to an aromatic ring such as a benzene ring or a naphthalene ring) in the molecule.

[0066] The polyphenolic compounds of the present invention include tannins and flavonoids.

[0067] The tannin of the present invention refers to a water-soluble compound derived from plants that reacts with proteins, alkaloids, and metal ions to form a poorly soluble salt by strong bonding. The tannin is an aromatic compound that is commonly found in the plant kingdom and has many phenolic hydroxyl groups.

[0068] The tannin of the present invention includes condensed tannin and hydrolyzable tannin.

[0069] The condensed tannin of the present invention is a compound obtained by polymerizing a compound having a flavanol skeleton represented by the following formula (p).

[0070]

[0071] The hydrolyzable tannin of the present invention is a compound in which an aromatic compound of gallic acid or ellagic acid represented by the following formula (q) and a sugar such as glucose represented by the following formula (r) are ester-bonded.

[0072]

[0073]

[0074] As a preferred embodiment of the hydrolyzable tannin, tannic acid represented by the following formula (9) can be mentioned.

[0075]

[0076] The flavonoid of the present invention refers to a compound biosynthesized by various modifications of flavanone, which is a type of flavonoid, and for example, refers to a compound derived from a compound having a flavanone skeleton structure represented by the following formula (s).

[0077]

[0078] Preferred embodiments of flavonoids include flavonoids represented by the following formula (10) or (11).

[0079]

[0080] <Water-soluble pigment>

[0081] The release agent composition of the present invention may further contain a water-soluble coloring matter.

[0082] In the present invention, water is used as a solvent, so various water-soluble pigments can be mixed in the stripper composition. For example, a water-soluble pigment that shows absorption in a wavelength region different from the light absorption wavelength region shown by the above-mentioned light absorbing compound can be contained in the stripper composition. Thereby, the light absorption wavelength region of the stripper composition can be expanded, and the wavelength selectivity of the laser irradiation light can be expanded.

[0083] The water-soluble dye of the present invention is not particularly limited as long as it is a dye that is soluble in water, and can be appropriately used depending on the purpose. For example, water-soluble dyes represented by the following formulas (a) to (d) are preferably used.

[0084] As the water-soluble pigment represented by formula (a), for example, CHLORANTINE FAST RED 5B (manufactured by Tokyo Chemical Industry) can be used; as the water-soluble pigment represented by formula (b), for example, Chrome Pure Blue BX (manufactured by Tokyo Chemical Industry) can be used; as the water-soluble pigment represented by formula (d), for example, Acid Red 18 (manufactured by Tokyo Chemical Industry) can be used.

[0085]

[0086] <Other ingredients>

[0087] The release agent composition of the present invention may contain an organic solvent as a solvent in addition to water unless the effects of the present invention are impaired. However, in the present invention, it is preferred that the release agent composition contain no organic solvent as much as possible.

[0088] Specific examples of the organic solvent include aliphatic hydrocarbons, aromatic hydrocarbons, ketones, etc., but are not limited to these.

[0089] More specifically, examples of the organic solvent include, but are not limited to, hexane, heptane, octane, nonane, decane, undecane, dodecane, isododecane, menthane, limonene, toluene, xylene, mesitylene, cumene, MIBK (methyl isobutyl ketone), butyl acetate, diisobutyl ketone, 2-octanone, 2-nonanone, and 5-nonanone.

[0090] In addition, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutyrate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, and the like can also be mentioned.

[0091] <<Preparation of Release Agent Composition>>

[0092] The remover composition of the present invention can be prepared by mixing the above-mentioned light absorbing compound with the above-mentioned solvent containing water.

[0093] The mixing ratio of the light absorbing compound to the water-containing solvent is not particularly limited as long as the effect of the present invention is achieved, and can be appropriately selected according to the purpose. For example, the ratio of the light absorbing compound to the solvent by mass is preferably 0.1:9.9 to 5:5, and more preferably 0.5:9.5 to 3:7.

[0094] The remover composition of the present invention can be prepared by mixing the light absorbing compound, the solvent containing water, and the water-soluble dye.

[0095] The mixing ratio of the light absorbing compound, the water-containing solvent and the water-soluble pigment is not particularly limited as long as the effect of the present invention is achieved, and can be appropriately selected according to the purpose. For example, the ratio of light absorbing compound: solvent: water-soluble pigment is preferably 0.1-5: 0.1-5: 9.8-5 in terms of mass ratio, and more preferably 0.5-3: 0.5-3: 4-9.

[0096] (Laminated body)

[0097] The laminated body of the present invention comprises a semiconductor substrate or an electronic device layer, a supporting substrate, and a release agent layer for release by light irradiation.

[0098] The laminate of the present invention preferably further comprises an adhesive layer, that is, has a structure comprising a semiconductor substrate or an electronic device layer, a supporting substrate, a release agent layer for release by light irradiation, and an adhesive layer.

[0099] It should be noted that, when the release agent layer of the present invention is formed to have not only a release function of peeling off the semiconductor substrate or electronic device layer from the supporting substrate by light irradiation, but also a bonding function of bonding the semiconductor substrate or electronic device layer to the supporting substrate (that is, when the release agent layer is formed using a release agent composition containing components that perform two functions), the laminate may be formed not by a two-layer structure of a release agent layer and an adhesive layer, but by a single layer of a release agent layer having bonding properties.

[0100] The supporting substrate has light-transmitting properties.

[0101] The release agent layer for light irradiation release is provided between the semiconductor substrate or the electronic device layer and the support substrate.

[0102] The laminate is used to peel off the semiconductor substrate or the electronic device layer from the supporting substrate after the release agent layer absorbs light irradiated from the supporting substrate side.

[0103] The release agent layer for light irradiation removal is a layer formed of the above-mentioned release agent composition for light irradiation removal of the present invention.

[0104] The laminate of the present invention is used for temporary bonding for processing a semiconductor substrate or an electronic device layer, and can be suitably used for processing such as thinning a semiconductor substrate or an electronic device layer.

[0105] During the thinning process of the semiconductor substrate, the semiconductor substrate is supported by the supporting substrate via the adhesive layer. On the other hand, after the processing of the semiconductor substrate, the stripping agent layer is irradiated with light, and then the supporting substrate is separated from the semiconductor substrate. By the specific light absorbing compound contained in the stripping agent composition, in the stripping agent layer formed by the stripping agent composition, the specific light absorbing compound absorbs light (such as laser) to deteriorate the stripping agent layer (such as separation or decomposition). As a result, after the stripping agent layer is irradiated with light, the semiconductor substrate and the supporting substrate become easy to peel off.

[0106] Furthermore, while the electronic device layer is being processed such as being thinned, the electronic device layer is supported by the support substrate via the adhesive layer. On the other hand, after the electronic device layer is processed, the release agent layer is irradiated with light, and then the support substrate and the electronic device layer are separated.

[0107] The release agent layer of the present invention makes it easy to release the semiconductor substrate or the electronic device layer from the support substrate after irradiation with light. Furthermore, after the semiconductor substrate or the electronic device layer is released from the support substrate, the residue of the release agent layer and the adhesive layer remaining on the semiconductor substrate, the electronic device layer or the support substrate can be removed by, for example, a cleaning agent composition for cleaning semiconductor substrates.

[0108] The wavelength of the light used for stripping is preferably 250 to 600 nm, more preferably 250 to 370 nm. More suitable wavelengths are 308 nm, 343 nm, 355 nm, 365 nm, or 532 nm. The irradiation amount of light required for stripping is an irradiation amount that causes appropriate deterioration of the specific light absorbing compound, such as decomposition.

[0109] The light used for the stripping may be laser light or a non-laser light source such as an ultraviolet lamp.

[0110] The following describes each of the case where the laminated body includes a semiconductor substrate and the case where the laminated body includes an electronic device layer in detail.

[0111] In the following <First Embodiment>, a case where the laminated body has a semiconductor substrate will be described, and in the following <Second Embodiment>, a case where the laminated body has an electronic device layer will be described.

[0112] <First embodiment>

[0113] The laminated body having the semiconductor substrate is used for processing the semiconductor substrate. During the processing of the semiconductor substrate, the semiconductor substrate is bonded to the support substrate via the adhesive layer. After the processing of the semiconductor substrate, the release agent layer is irradiated with light, and then the semiconductor substrate is separated from the support substrate.

[0114] <<Semiconductor substrate>>

[0115] The main material constituting the entire semiconductor substrate is not particularly limited as long as it can be used for such an application, and examples thereof include silicon, silicon carbide, and compound semiconductors.

[0116] The shape of the semiconductor substrate is not particularly limited, and may be, for example, a disc-shaped semiconductor substrate. It should be noted that the disc-shaped semiconductor substrate does not need to have a completely circular surface shape, and for example, the periphery of the semiconductor substrate may have a straight portion called an orientation flat, or may have a cutout called a notch.

[0117] The thickness of the disk-shaped semiconductor substrate is not particularly limited and may be appropriately determined depending on the intended use of the semiconductor substrate, and is, for example, 500 to 1000 μm.

[0118] The diameter of the disk-shaped semiconductor substrate is not particularly limited and may be appropriately determined depending on the intended use of the semiconductor substrate, and is, for example, 100 to 1000 mm.

[0119] The semiconductor substrate may have a bump. A bump is a protruding terminal.

[0120] In the laminated body, when the semiconductor substrate has the bump, the semiconductor substrate has the bump on the supporting substrate side.

[0121] In a semiconductor substrate, bumps are usually formed on the surface where a circuit is formed. The circuit may be a single layer or a multilayer. There is no particular limitation on the shape of the circuit.

[0122] In the semiconductor substrate, the surface (back surface) opposite to the surface having the bumps is a surface to be processed.

[0123] The material, size, shape, structure, and density of the bumps included in the semiconductor substrate are not particularly limited.

[0124] Examples of the bump include a ball bump, a printed bump, a stud bump, and a plated bump.

[0125] Generally, the height, radius, and pitch of the bumps are appropriately determined based on the conditions that the bump height is about 1 to 200 μm, the bump radius is 1 to 200 μm, and the bump pitch is 1 to 500 μm.

[0126] Examples of materials for the bumps include low melting point solder, high melting point solder, tin, indium, gold, silver, copper, etc. The bumps may be made of a single component or multiple components. More specifically, SnAg bumps, SnBi bumps, Sn bumps, AuSn bumps, and other alloy platings based on Sn may be included.

[0127] Furthermore, the bump may have a stacked structure including a metal layer composed of at least any one of these components.

[0128] An example of a semiconductor substrate is a silicon wafer having a diameter of 300 mm and a thickness of about 770 μm.

[0129] <<Support substrate>>

[0130] The supporting substrate is not particularly limited as long as it is a member that is light-transmissive to the light irradiated to the adhesive layer and can support the semiconductor substrate when the semiconductor substrate is processed, and examples thereof include glass supporting substrates.

[0131] The shape of the support substrate is not particularly limited, and an example thereof may be a disk shape.

[0132] The thickness of the disk-shaped support substrate is not particularly limited and may be appropriately determined according to the size of the semiconductor substrate, etc., but is, for example, 500 to 1000 μm.

[0133] The diameter of the disk-shaped support substrate is not particularly limited and may be appropriately determined according to the size of the semiconductor substrate, etc., but is, for example, 100 to 1000 mm.

[0134] An example of the supporting substrate is a glass wafer having a diameter of 300 mm and a thickness of about 700 μm.

[0135] <<Release agent layer>>

[0136] The release agent layer is a layer formed of a release agent composition.

[0137] The release agent layer is provided between the semiconductor substrate and the support substrate.

[0138] The release agent layer may be in contact with the supporting substrate or may be in contact with the semiconductor substrate.

[0139] The release agent layer is formed using the above-mentioned release agent composition for light irradiation release of the present invention.

[0140] The stripping agent composition of the present invention can be suitably used to form a stripping agent layer of a laminate having a semiconductor substrate, a support substrate, and a stripping agent layer disposed between the semiconductor substrate and the support substrate. The laminate is used to strip the semiconductor substrate from the support substrate after the stripping agent layer absorbs light irradiated from the support substrate side.

[0141] One of the characteristics of the release agent layer obtained from the release agent composition of the present invention is that the semiconductor substrate and the supporting substrate can be easily peeled off after light irradiation.

[0142] When forming a release agent layer from the release agent composition, the specific light absorbing compound may crosslink itself or react with other components to form a crosslinked structure, or may not crosslink or react and maintain its structure, as long as the effect of the present invention is achieved.

[0143] In other words, in the release agent layer, the specific light absorbing compound may form a crosslinked structure by crosslinking itself or reacting with other components, or may exist while maintaining its structure.

[0144] The thickness of the release agent layer is not particularly limited and is generally 0.01 to 10 μm. From the viewpoint of maintaining film strength, it is preferably 0.05 μm or more, more preferably 0.1 μm or more, and further preferably 0.2 μm or more. From the viewpoint of avoiding unevenness caused by a thick film, it is preferably 8 μm or less, more preferably 5 μm or less, further preferably 2 μm or less, and further preferably 1 μm or less.

[0145] The method of forming the release agent layer from the release agent composition is described in detail in the explanation section of "Method for producing an example of a laminated body in the first embodiment" described below.

[0146] <<Adhesive layer>>

[0147] The adhesive layer is provided between the support substrate and the semiconductor substrate.

[0148] The adhesive layer is in contact with, for example, a semiconductor substrate. The adhesive layer may be in contact with, for example, a supporting substrate.

[0149] The adhesive layer is not particularly limited, but is preferably a layer formed of an adhesive composition.

[0150] <<Adhesive composition>>

[0151] Examples of the adhesive composition include, but are not limited to, silicone-based adhesives, acrylic resin-based adhesives, epoxy resin-based adhesives, polyamide-based adhesives, polystyrene-based adhesives, polyimide adhesives, and phenolic resin-based adhesives.

[0152] Among them, polysiloxane-based adhesives are preferred as adhesive compositions because they exhibit appropriate adhesion during processing of semiconductor substrates and the like, can be appropriately peeled off after processing, have excellent heat resistance, and can be appropriately removed by a cleaning composition.

[0153] In a preferred embodiment, the adhesive composition contains polyorganosiloxane.

[0154] Furthermore, in another preferred embodiment, the adhesive composition contains a component that cures by a hydrosilylation reaction.

[0155] For example, the adhesive composition used in the present invention contains a cured component (A) that becomes an adhesive component. The adhesive composition used in the present invention may also contain a cured component (A) that becomes an adhesive component and a component (B) that does not cause a curing reaction. Here, as a component (B) that does not cause a curing reaction, for example, polyorganosiloxane can be cited. It should be noted that in the present invention, "does not cause a curing reaction" does not mean that no curing reaction is caused, but refers to the curing reaction that occurs when the curing component (A) does not cause curing.

[0156] In a preferred embodiment, the component (A) may be a component that is cured by a hydrosilylation reaction, or may be a polyorganosiloxane component (A') that is cured by a hydrosilylation reaction.

[0157] In another preferred embodiment, component (A) contains, as an example of component (A'), 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 platinum group metal catalyst (A2). The alkenyl group having 2 to 40 carbon atoms may be optionally substituted. Examples of substituents include halogen atoms, nitro groups, cyano groups, amino groups, hydroxyl groups, carboxyl groups, aryl groups, heteroaryl groups, and the like.

[0158] In another preferred embodiment, the polyorganosiloxane component (A') that is cured by a hydrosilylation reaction comprises a polysiloxane (A1) and a platinum group metal catalyst (A2), wherein the polysiloxane (A1) comprises a siloxane unit (Q unit) selected from the group consisting of SiO2, R 1 R 2 R 3 SiO 1 / 2 The siloxane unit (M unit), R 4 R 5 SiO 2 / 2 The siloxane units (D units) and R 6 SiO 3 / 2The polysiloxane (A1) comprises a polyorganosiloxane (a1') and a polyorganosiloxane (a2'), wherein the polyorganosiloxane (a1') comprises a siloxane unit (Q' unit) represented by SiO2, a R 1 'R 2 'R 3 'SiO 1 / 2 The siloxane units (M' units), R 4 'R 5 'SiO 2 / 2 The siloxane units (D' units) and R 6 'SiO 3 / 2 The polyorganosiloxane (a2') comprises one or more units selected from the group consisting of siloxane units (T' units) represented by SiO2, and at least one unit selected from the group consisting of M' units, D' units and T' units, wherein the polyorganosiloxane (a2') comprises a siloxane unit (Q" unit) represented by SiO2, R 1 ”R 2 ”R 3 "SiO 1 / 2 The siloxane units (M" units), R 4 ”R 5 "SiO 2 / 2 The siloxane units (D" units) and R 6 "SiO 3 / 2 The siloxane units (T" units) shown in the figure contain one or more units selected from the group consisting of M" units, D" units and T" units.

[0159] It should be noted that (a1′) is an example of (a1), and (a2′) is an example of (a2).

[0160] R 1 ~R 6 is a group or atom bonded to a silicon atom, each independently representing 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.

[0161] R 1 '~R 6 ' is a group bonded to a silicon atom, each independently represents an optionally substituted alkyl group or an optionally substituted alkenyl group, R 1 '~R 6 At least one of ' is an optionally substituted alkenyl group. 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.

[0162] R 1 ”~R 6 " is a group or atom bonded to a silicon atom, each independently representing an optionally substituted alkyl group, or a hydrogen atom, R 1 ”~R 6 " is 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, a heteroaryl group, and the like.

[0163] The alkyl group may be any of linear, branched, or cyclic, preferably linear or branched. 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 further preferably 10 or less.

[0164] Specific examples of the optionally substituted linear or branched alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 1-methyl n-butyl, 2-methyl n-butyl, 3-methyl n-butyl, 1,1-dimethyl n-propyl, 1,2-dimethyl n-propyl, 2,2-dimethyl n-propyl, 1-ethyl n-propyl, n-hexyl, 1-methyl n-pentyl, 2-methyl n-pentyl, 3-methyl n-pentyl, 4-methyl n-pentyl, 1,1 The present invention is not limited to 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, 1-ethyl-2-methyl-n-propyl, etc., and the number of carbon atoms thereof is usually 1 to 14, preferably 1 to 10, and more preferably 1 to 6. Among them, methyl is particularly preferred.

[0165] Specific examples of the optionally substituted cyclic alkyl group include cyclopropyl, cyclobutyl, 1-methyl-cyclopropyl, 2-methyl-cyclopropyl, cyclopentyl, 1-methyl-cyclobutyl, 2-methyl-cyclobutyl, 3-methyl-cyclobutyl, 1,2-dimethyl-cyclopropyl, 2,3-dimethyl-cyclopropyl, 1-ethyl-cyclopropyl, 2-ethyl-cyclopropyl, cyclohexyl, 1-methyl-cyclopentyl, 2-methyl-cyclopentyl, 3-methyl-cyclopentyl, 1-ethyl-cyclobutyl, 2-ethyl-cyclobutyl, 3-ethyl-cyclobutyl, 1,2-dimethyl-cyclobutyl, 1,3-dimethyl-cyclobutyl, 2,2-dimethyl-cyclobutyl, 2,3-dimethyl-cyclobutyl, 2,4-dimethyl The cycloalkyl groups include, but are not limited to, cyclobutyl, 3,3-dimethyl-cyclobutyl, 1-n-propyl-cyclopropyl, 2-n-propyl-cyclopropyl, 1-isopropyl-cyclopropyl, 2-isopropyl-cyclopropyl, 1,2,2-trimethyl-cyclopropyl, 1,2,3-trimethyl-cyclopropyl, 2,2,3-trimethyl-cyclopropyl, 1-ethyl-2-methyl-cyclopropyl, 2-ethyl-1-methyl-cyclopropyl, 2-ethyl-2-methyl-cyclopropyl and 2-ethyl-3-methyl-cyclopropyl; and bicycloalkyl groups such as dicyclobutyl, dicyclopentyl, dicyclohexyl, dicycloheptyl, dicyclooctyl, dicyclononyl and dicyclodecyl. The number of carbon atoms thereof is usually 3 to 14, preferably 4 to 10, and more preferably 5 to 6.

[0166] The alkenyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is usually 2 to 40, preferably 30 or less, more preferably 20 or less, and further preferably 10 or less.

[0167] Specific examples of the optionally substituted linear or branched alkenyl group include, but are not limited to, vinyl, allyl, butenyl, pentenyl, etc., and the number of carbon atoms thereof is usually 2 to 14, preferably 2 to 10, and more preferably 1 to 6. Among them, vinyl and 2-propenyl are particularly preferred.

[0168] Specific examples of the optionally substituted cyclic alkenyl group include, but are not limited to, cyclopentenyl and cyclohexenyl. The number of carbon atoms in the cyclic alkenyl group is usually 4 to 14, preferably 5 to 10, and more preferably 5 to 6.

[0169] As described above, the polysiloxane (A1) includes the polyorganosiloxane (a1') and the polyorganosiloxane (a2'), and the alkenyl groups contained in the polyorganosiloxane (a1') and the hydrogen atoms (Si-H groups) contained in the polyorganosiloxane (a2') form a crosslinked structure by a hydrosilylation reaction using a platinum group metal catalyst (A2) and cure. As a result, a cured film is formed.

[0170] The polyorganosiloxane (a1') comprises one or more units selected from the group consisting of Q' units, M' units, D' units and T' units, and comprises at least one selected from the group consisting of M' units, D' units and T' units. As the polyorganosiloxane (a1'), two or more polyorganosiloxanes satisfying such conditions may be used in combination.

[0171] 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' unit and M' unit), (D' unit and M' unit), (T' unit and M' unit), (Q' unit, T' unit and M' unit).

[0172] In addition, when the polyorganosiloxane (a1') includes two or more polyorganosiloxanes, the combination of (Q' unit and M' unit) and (D' unit and M' unit), the combination of (T' unit and M' unit) and (D' unit and M' unit), and the combination of (Q' unit, T' unit and M' unit) and (T' unit and M' unit) are preferred, but not limited to these.

[0173] The polyorganosiloxane (a2') contains one or more units selected from the group consisting of Q" units, M" units, D" units and T" units, and contains at least one selected from the group consisting of M" units, D" units and T" units. As the polyorganosiloxane (a2'), two or more polyorganosiloxanes satisfying such conditions may be used in combination.

[0174] 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), (Q" units, "T" units and "M" units).

[0175] The polyorganosiloxane (a1′) is composed of siloxane units formed by bonding silicon atoms to alkyl and / or alkenyl groups. 1 '~R 6 The ratio of alkenyl groups in all substituents represented by ' is preferably 0.1 to 50.0 mol%, more preferably 0.5 to 30.0 mol%, and the remaining R 1 '~R 6 ' can be set to an alkyl group.

[0176] The polyorganosiloxane (a2') is composed of siloxane units formed by bonding silicon atoms with alkyl groups and / or hydrogen atoms. 1 ”~R 6The ratio of all substituents and hydrogen atoms in the substituent atoms represented by " is preferably 0.1 to 50.0 mol%, more preferably 10.0 to 40.0 mol%, and the remaining R 1 ”~R 6 " can be set to an alkyl group.

[0177] When component (A) contains (a1) and (a2), in a preferred embodiment of the present invention, the molar ratio of alkenyl groups contained in polyorganosiloxane (a1) to hydrogen atoms constituting Si—H bonds contained in polyorganosiloxane (a2) is in the range of 1.0:0.5 to 1.0:0.66.

[0178] 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 preferably 5,000 to 50,000 from the viewpoint of achieving the effects of the present invention with good reproducibility.

[0179] It should be noted that in the present invention, the weight average molecular weight, number average molecular weight and dispersity of polyorganosiloxane (excluding the above-mentioned organosiloxane polymer) can be measured, for example, using a GPC apparatus (EcoSEC, HLC-8320GPC manufactured by TOSOH Co., Ltd.) and a GPC column (TSKgel SuperMultiporeHZ-N, TSKgelSuperMultiporeHZ-H manufactured by TOSOH Co., Ltd.), with the column temperature set to 40°C, tetrahydrofuran used as an eluent (elution solvent), the flow rate (flow velocity) set to 0.35 mL / min, and polystyrene (Shodex manufactured by Showa Denko K.K.) used as a standard sample.

[0180] The viscosity of polyorganosiloxane (a1) and polyorganosiloxane (a2) is not particularly limited, and each is usually 10 to 1,000,000 (mPa·s), and preferably 50 to 10,000 (mPa·s) from the viewpoint of achieving the effects of the present invention with good reproducibility. It should be noted that the viscosity of polyorganosiloxane (a1) and polyorganosiloxane (a2) is a value measured at 25° C. using an E-type rotational viscometer.

[0181] The polyorganosiloxane (a1) and the polyorganosiloxane (a2) react with each other to form a film by a hydrosilylation reaction. Therefore, the curing mechanism is different from the mechanism via a silanol group, and therefore, any siloxane does not need to contain a silanol group or a functional group such as an alkoxy group that forms a silanol group by hydrolysis.

[0182] In a preferred embodiment of the present invention, the adhesive composition contains the polyorganosiloxane component (A') and a platinum group metal catalyst (A2).

[0183] Such a platinum-based metal catalyst is a catalyst for promoting the hydrosilylation reaction between the alkenyl group of the polyorganosiloxane (a1) and the Si—H group of the polyorganosiloxane (a2).

[0184] Specific examples of the platinum-based metal catalyst include platinum-based catalysts such as platinum black, platinum tetrachloride, chloroplatinic acid, a reaction product of chloroplatinic acid and a monohydric alcohol, a complex of chloroplatinic acid and olefins, and bisacetoacetate platinum, but are not limited thereto.

[0185] Examples of the complex of platinum and olefins include a complex of divinyltetramethyldisiloxane and platinum, but the complex is not limited thereto.

[0186] The amount of the platinum group metal catalyst (A2) is not particularly limited, but is usually within a range of 1.0 to 50.0 ppm based on the total amount of the polyorganosiloxane (a1) and the polyorganosiloxane (a2).

[0187] The polyorganosiloxane component (A') may contain a polymerization inhibitor (A3) for the purpose of suppressing the progress of the hydrosilylation reaction.

[0188] The polymerization inhibitor is not particularly limited as long as it can inhibit the progress of the hydrosilylation reaction, and specific examples thereof include alkynyl alcohols such as 1-ethynyl-1-cyclohexanol and 1,1-diphenyl-2-propyn-1-ol.

[0189] The amount of the polymerization inhibitor is not particularly limited, but is usually 1000.0 ppm or more based on the total amount of polyorganosiloxane (a1) and polyorganosiloxane (a2) from the viewpoint of obtaining the effect thereof and 10000.0 ppm or less from the viewpoint of preventing excessive inhibition of the hydrosilylation reaction.

[0190] An example of the adhesive composition used in the present invention may also contain a cured component (A) and a component (B) that does not cause a curing reaction and serves as a release agent component. By including such a component (B) in the adhesive composition, the obtained adhesive layer can be appropriately released with good reproducibility.

[0191] As such a component (B), a non-curable polyorganosiloxane is typically mentioned, and specific examples thereof include epoxy-containing polyorganosiloxane, methyl-containing polyorganosiloxane, phenyl-containing polyorganosiloxane, etc., but the present invention is not limited thereto.

[0192] In addition, as component (B), polydimethylsiloxane can be listed. The polydimethylsiloxane is optionally modified. As the optionally modified polydimethylsiloxane, for example, epoxy-containing polydimethylsiloxane, unmodified polydimethylsiloxane, phenyl-containing polydimethylsiloxane, etc. can be listed, but it is not limited thereto.

[0193] Preferred examples of the polyorganosiloxane as the component (B) include epoxy-containing polyorganosiloxane, methyl-containing polyorganosiloxane, phenyl-containing polyorganosiloxane, and the like, but are not limited thereto.

[0194] The weight average molecular weight of the polyorganosiloxane as component (B) is not particularly limited, but is usually 100,000 to 2,000,000. From the viewpoint of achieving the effect of the present invention with good reproducibility, it is preferably 200,000 to 1,200,000, and more preferably 300,000 to 900,000. In addition, the dispersity thereof is not particularly limited, but is usually 1.0 to 10.0. From the viewpoint of achieving appropriate peeling with good reproducibility, it is preferably 1.5 to 5.0, and more preferably 2.0 to 3.0. It should be noted that the weight average molecular weight and dispersity can be measured by the above-mentioned method related to polyorganosiloxane.

[0195] The viscosity of the polyorganosiloxane as component (B) is not particularly limited, but is usually 1,000 to 2,000,000 mm 2 / s. It should be noted that the viscosity of the polyorganosiloxane as the component (B) is represented by the kinematic viscosity, which is centistokes (cSt) = mm 2 / s. It can also be calculated by dividing the viscosity (mPa·s) by the density (g / cm 3 That is, the value can be obtained from the viscosity and density measured at 25°C using an E-type rotational viscometer, or from the kinematic viscosity (mm 2 / s) = viscosity (mPa·s) / density (g / cm 3 ) is calculated using this formula.

[0196] Examples of the epoxy-containing polyorganosiloxane include: 11 R 12 SiO 2 / 2 The siloxane units (D 10 Units) of polyorganosiloxane.

[0197] R 11 is a group bonded to a silicon atom, represents an alkyl group, and R 12 It is a group bonded to a silicon atom and represents an epoxy group or an organic group containing an epoxy group. Specific examples of the alkyl group include those described above.

[0198] The epoxy group in the organic group containing an epoxy group may be an independent epoxy group that is not condensed with other rings, or may be an epoxy group that forms a condensed ring with other rings, such as 1,2-epoxycyclohexyl group.

[0199] Specific examples of the organic group containing an epoxy group include a 3-glycidoxypropyl group and a 2-(3,4-epoxycyclohexyl)ethyl group, but are not limited thereto.

[0200] In the present invention, a preferred example of the epoxy-containing polyorganosiloxane is an epoxy-containing polydimethylsiloxane, but the present invention is not limited thereto.

[0201] The epoxy-containing polyorganosiloxane comprises the above-mentioned siloxane units (D 10 Unit), but except for D 10 In addition to the T unit, Q unit, M unit and / or T unit may be included.

[0202] In a preferred embodiment of the present invention, specific examples of epoxy-containing polyorganosiloxanes include: 10 Polyorganosiloxane composed of units; containing D 10 Units and Q units of polyorganosiloxane; containing D 10 Units and M units of polyorganosiloxane; containing D 10 Units and T units of polyorganosiloxane; containing D 10 Unit, Q unit and M unit of polyorganosiloxane; containing D 10 Unit, M unit and T unit of polyorganosiloxane; containing D 10 Unit, Q unit, M unit and T unit of polyorganosiloxane, etc.

[0203] The epoxy-containing polyorganosiloxane is preferably an epoxy-containing polydimethylsiloxane having an epoxy value of 0.1 to 5. The weight average molecular weight is not particularly limited but is usually 1,500 to 500,000, and is preferably 100,000 or less from the viewpoint of suppressing precipitation in the composition.

[0204] Specific examples of the epoxy-containing polyorganosiloxane include polyorganosiloxanes represented by formulae (E1) to (E3), but are not limited thereto.

[0205]

[0206] (m1 and n1 represent the number of each repeating unit and are positive integers.)

[0207]

[0208] (m2 and n2 represent the number of repeating units and are positive integers, and R is an alkylene group having 1 to 10 carbon atoms.)

[0209]

[0210] (m3, n3 and o3 represent the number of each repeating unit and are positive integers, and R is an alkylene group having 1 to 10 carbon atoms.)

[0211] Examples of the methyl group-containing polyorganosiloxane include: 210 R 220 SiO 2 / 2 The siloxane units (D 200 Units), preferably comprising R 21 R 21 SiO 2 / 2 The siloxane units (D 20 Units) of polyorganosiloxane.

[0212] R 210 and R 220 is a group bonded to a silicon atom, each independently represents an alkyl group, at least one of which is a methyl group, and specific examples of the alkyl group include those described above.

[0213] R 21 is a group bonded to a silicon atom, and represents an alkyl group. Specific examples of the alkyl group include the above examples. 21 , preferably methyl.

[0214] In the present invention, polydimethylsiloxane is mentioned as a preferred example of the methyl group-containing polyorganosiloxane, but the present invention is not limited to this.

[0215] The methyl-containing polyorganosiloxane comprises the above-mentioned siloxane units (D 200 Unit or D 20 Unit), but except for D 200 Unit and D 20 In addition to the T unit, Q unit, M unit and / or T unit may be included.

[0216] In one embodiment of the present invention, specific examples of methyl-containing polyorganosiloxanes include: 200 Polyorganosiloxane composed of units; containing D 200 Units and Q units of polyorganosiloxane; containing D 200 Units and M units of polyorganosiloxane; containing D 200 Units and T units of polyorganosiloxane; containing D 200 Unit, Q unit and M unit of polyorganosiloxane; containing D 200Unit, M unit and T unit of polyorganosiloxane; containing D 200 A polyorganosiloxane containing A unit, Q unit, M unit and T unit.

[0217] In a preferred embodiment of the present invention, specific examples of methyl-containing polyorganosiloxanes include: 20 Polyorganosiloxane composed of units; containing D 20 Units and Q units of polyorganosiloxane; containing D 20 Units and M units of polyorganosiloxane; containing D 20 Units and T units of polyorganosiloxane; containing D 20 Unit, Q unit and M unit of polyorganosiloxane; containing D 20 Unit, M unit and T unit of polyorganosiloxane; containing D 20 A polyorganosiloxane containing A unit, Q unit, M unit and T unit.

[0218] Specific examples of the methyl group-containing polyorganosiloxane include polyorganosiloxane represented by formula (M1), but are not limited thereto.

[0219]

[0220] (n4 represents the number of repeating units, which is a positive integer.)

[0221] Examples of the phenyl group-containing polyorganosiloxane include: 31 R 32 SiO 2 / 2 The siloxane units (D 30 Units) of polyorganosiloxane.

[0222] R 31 is a group bonded to a silicon atom, representing a phenyl group or an alkyl group, R 32 It is a group bonded to a silicon atom and represents a phenyl group. Specific examples of the alkyl group include those described above, and a methyl group is preferred.

[0223] The phenyl-containing polyorganosiloxane comprises the above-mentioned siloxane units (D 30 Unit), but except for D 30 In addition to the T unit, Q unit, M unit and / or T unit may be included.

[0224] In a preferred embodiment of the present invention, specific examples of phenyl-containing polyorganosiloxanes include: 30 Polyorganosiloxane composed of units; containing D 30 Units and Q units of polyorganosiloxane; containing D 30 Units and M units of polyorganosiloxane; containing D30 Units and T units of polyorganosiloxane; containing D 30 Unit, Q unit and M unit of polyorganosiloxane; containing D 30 Unit, M unit and T unit of polyorganosiloxane; containing D 30 A polyorganosiloxane containing A unit, Q unit, M unit and T unit.

[0225] Specific examples of the phenyl group-containing polyorganosiloxane include polyorganosiloxanes represented by the formula (P1) or (P2), but are not limited thereto.

[0226]

[0227] (m5 and n5 represent the number of each repeating unit and are positive integers.)

[0228]

[0229] (m6 and n6 represent the number of each repeating unit and are positive integers.)

[0230] The polyorganosiloxane as the release agent component (B) may be a commercially available product or a synthesized polyorganosiloxane.

[0231] Examples of commercially available polyorganosiloxanes include Wacker Chemie products such as the Wackersilicon Fluid AK series (AK 50, AK 350, AK 1000, AK 10000, AK 1000000), GENIOPLAST GUM, Shin-Etsu Chemical Co., Ltd. dimethyl silicone oils (KF-96L, KF-96A, KF-96, KF-96H, KF-69, KF-965, KF-968), and cyclic dimethyl silicone oil (KF-995); Gelest Co., Ltd. epoxy-containing polyorganosiloxanes (trade names: CMS-227, ECMS-327); Shin-Etsu Chemical Co., Ltd. epoxy-containing polyorganosiloxanes (KF-101, KF-1001, KF-1005, X-22-343); and Dow Chemical Co., Ltd. epoxy-containing polyorganosiloxanes (KF-102, KF-103, KF-104, KF-1056, X-22-347). Epoxy-containing polyorganosiloxane manufactured by Corning (BY16-839); phenyl-containing polyorganosiloxane manufactured by Gelest (PMM-1043, PMM-1025, PDM-0421, PDM-0821), phenyl-containing polyorganosiloxane manufactured by Shin-Etsu Chemical Co., Ltd. (KF50-3000CS), phenyl-containing polyorganosiloxane manufactured by Momentive (TSF431, TSF433), etc., but not limited to these.

[0232] In one embodiment, the adhesive composition used in the present invention contains both a curable component (A) and a component (B) that does not cause a curing reaction. In another embodiment, the adhesive composition contains a polyorganosiloxane as the component (B).

[0233] An example of the adhesive composition used in the present invention may contain component (A) and component (B) in an arbitrary ratio. If the balance between adhesion and releasability is taken into consideration, the ratio of component (A) to component (B) is preferably 99.995:0.005 to 30:70, and more preferably 99.9:0.1 to 75:25 in terms of mass ratio [(A):(B)].

[0234] That is, when the polyorganosiloxane component (A') that cures by hydrosilylation reaction is included, the ratio of component (A') to component (B) is preferably 99.995:0.005 to 30:70, and more preferably 99.9:0.1 to 75:25 in terms of mass ratio [(A'):(B)].

[0235] The viscosity of the adhesive composition used in the present invention is not particularly limited, but is usually 500 to 20,000 mPa·s at 25° C., and preferably 1,000 to 10,000 mPa·s.

[0236] One example of the adhesive composition used in the present invention can be produced by mixing the component (A), the component (B) when used, and a solvent.

[0237] The mixing order is not particularly limited. As an example of a method for easily and reproducibly manufacturing an adhesive composition, for example, there can be cited: a method of dissolving component (A) and component (B) in a solvent; a method of dissolving a part of component (A) and component (B) in a solvent, dissolving the rest in a solvent, and mixing the resulting solutions, but the present invention is not limited thereto. It should be noted that when preparing the adhesive composition, it can also be heated appropriately within a range in which the components are not decomposed or deteriorated.

[0238] In the present invention, for the purpose of removing foreign matter, the solvent, solution, etc. used may be filtered using a filter or the like during the preparation of the adhesive composition or after all the components are mixed.

[0239] The thickness of the adhesive layer possessed by the laminate of the present invention is not particularly limited and is generally 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 further preferably 30 μm or more. From the viewpoint of avoiding unevenness caused by a thick film, it is preferably 200 μm or less, more preferably 150 μm or less, further preferably 120 μm or less, and further preferably 70 μm or less.

[0240] The method of forming an adhesive layer from the adhesive composition is described in detail in the explanation section of "Method for producing an example of a laminated body in the first embodiment" described below.

[0241] An example of the structure of the laminated body according to the first embodiment will be described below using the drawings.

[0242] Figure 1 A schematic cross-sectional view showing an example of the laminated body according to the first embodiment.

[0243] Figure 1 The laminated body includes a semiconductor substrate 1, an adhesive layer 2, a release agent layer 3, and a support substrate 4 in this order.

[0244] The adhesive layer 2 and the release agent layer 3 are provided between the semiconductor substrate 1 and the support substrate 4. The adhesive layer 2 is in contact with the semiconductor substrate 1. The release agent layer 3 is in contact with the adhesive layer 2 and the support substrate 4.

[0245] In addition, another example of the structure of the laminated body of the first embodiment is shown in Figure 2 .

[0246] When the release agent layer of the present invention is a release agent layer having adhesive properties having both release and adhesive functions, the laminate may be formed of a single layer of a release agent layer having adhesive properties instead of a two-layer structure of the release agent layer and the adhesive layer.

[0247] Figure 2 A schematic cross-sectional view showing another example of the laminated body.

[0248] Figure 2 The laminated body comprises a semiconductor substrate 1, a release agent layer 5 having adhesive properties, and a support substrate 4 in this order.

[0249] The release agent layer 5 is provided between the semiconductor substrate 1 and the support substrate 4. The release agent layer 5 can be produced by mixing the constituent components of the release agent composition forming the release agent and the constituent components of the adhesive composition forming the adhesive layer.

[0250] <<Method for producing an example of a laminate in the first embodiment>>

[0251] In the laminated body of the first embodiment, Figure 1 The laminate shown is an example, and a method for producing the following laminate will be described.

[0252] The laminate of the present invention can be manufactured, for example, by the following method, which comprises: a first step of applying an adhesive composition to the surface of a semiconductor substrate and, if necessary, heating it to form an adhesive coating layer; a second step of applying a release agent composition to the surface of a supporting substrate and, if necessary, heating it to form a release agent coating layer; and a third step of subjecting the adhesive coating layer of the semiconductor substrate and the release agent coating layer of the supporting substrate to at least one of a heating treatment and a decompression treatment while applying a load in the thickness direction of the semiconductor substrate and the supporting substrate to make them closely attached, and then subjecting them to a post-heating treatment, thereby manufacturing a laminate.

[0253] It should be noted that in Figure 1 In the laminate, a semiconductor substrate 1, an adhesive layer 2, a release agent layer 3, and a supporting substrate 4 are sequentially stacked, so the above-mentioned manufacturing method is listed as an example, but for example, in the case of manufacturing a laminate in which a semiconductor substrate 1, a release agent layer 3, an adhesive layer 2, and a supporting substrate 4 are sequentially stacked, it can be manufactured by the following method, the method comprising: a first step, applying a release agent composition to the surface of the semiconductor substrate, and heating it if necessary to form a release agent coating layer; a second step, applying an adhesive composition to the surface of the supporting substrate, and heating it if necessary to form an adhesive coating layer; and a third step, applying a load in the thickness direction of the semiconductor substrate and the supporting substrate to the release agent coating layer of the semiconductor substrate and the adhesive coating layer of the supporting substrate while performing at least one of a heating treatment and a decompression treatment, and then performing a post-heating treatment to form a laminate.

[0254] In addition, as long as the effect of the present invention is not impaired, the coating and heating of each composition may be performed sequentially on either substrate.

[0255] The coating method is not particularly limited, but is usually a spin coating method. It is also possible to form a coating film separately by a spin coating method or the like, and to attach the coating film in a sheet form as the adhesive coating layer.

[0256] The heating temperature of the applied adhesive composition varies depending on the type and amount of the adhesive components contained in the adhesive composition; whether a solvent is contained; the boiling point of the solvent used; the desired thickness of the adhesive layer, etc., and therefore cannot be generally specified, but is usually 80 to 150°C, and the heating time is usually 30 seconds to 5 minutes.

[0257] When the adhesive composition contains a solvent, the adhesive composition after application is usually heated.

[0258] The heating temperature of the stripper composition after coating varies according to the type and amount of the stripper component contained in the stripper composition; the thickness of the desired stripper layer, etc., and therefore cannot be generally specified. From the perspective of achieving an appropriate stripper layer with good reproducibility, it is 80°C or more and 300°C or less, and the heating time is appropriately determined in the range of 10 seconds to 10 minutes according to the heating temperature. The heating temperature is preferably 100°C or more and 280°C or less, more preferably 150°C or more and 250°C or less. The heating time is preferably 30 seconds or more and 8 minutes or less, more preferably 1 minute or more and 5 minutes or less.

[0259] Heating can be performed using a hot plate, an oven, or the like.

[0260] The thickness of the adhesive coating layer obtained by applying the adhesive composition and heating it if necessary is generally about 5 to 500 μm, and is appropriately determined so as to finally be within the above-mentioned thickness range of the adhesive layer.

[0261] The film thickness of the release agent coating layer obtained by applying the release agent composition and heating it if necessary is generally about 5 nm to 100 μm, and is appropriately determined so that the thickness of the release agent layer finally falls within the above-mentioned range.

[0262] In the present invention, such coating layers can be put together in a mutually contacting manner, and a load in the thickness direction of the semiconductor substrate and the supporting substrate is applied to make the two layers close to each other while performing a heating treatment or a decompression treatment or both, and then a post-heating treatment is performed, thereby obtaining the laminate of the present invention. It should be noted that the treatment conditions of any of the heating treatment, the decompression treatment, and the combination of the two are appropriately determined based on various situations such as the type of the adhesive composition, the specific composition of the stripper composition, the phase of the film obtained from the two compositions, the film thickness, and the bonding strength obtained.

[0263] The heating treatment temperature is usually appropriately determined within the range of 20 to 150° C. from the viewpoint of removing the solvent from the composition, softening the adhesive coating layer and achieving appropriate bonding with the release agent coating layer, etc. In particular, from the viewpoint of suppressing or avoiding excessive curing and unnecessary deterioration of the adhesive component (A), it is preferably 130° C. or less, more preferably 90° C. or less. The heating time is appropriately determined depending on the heating temperature and the type of adhesive, and is usually 30 seconds or more, preferably 1 minute or more, from the viewpoint of reliably achieving appropriate bonding. From the viewpoint of suppressing deterioration of the adhesive layer and other members, it is usually 10 minutes or less, preferably 5 minutes or less.

[0264] The reduced pressure treatment may be carried out by exposing the adhesive coating layer and the release agent coating layer in contact with each other to a gas pressure of 10 to 10000 Pa. The time for the reduced pressure treatment is usually 1 to 30 minutes.

[0265] From the viewpoint of obtaining a laminate in which the substrates can be well separated with good reproducibility, the two layers in contact with each other are preferably bonded together by a reduced pressure treatment, more preferably a combined heating treatment and a reduced pressure treatment.

[0266] 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 and the support substrate and the two layers therebetween and allows them to be firmly adhered to each other, but is usually in the range of 10 to 1000N.

[0267] From the viewpoint of achieving a sufficient curing speed, the post-heating temperature is preferably 120° C. or higher, and from the viewpoint of preventing deterioration of the substrate and each layer, the post-heating temperature is preferably 260° C. or lower.

[0268] From the perspective of achieving proper bonding between the substrate and the layers constituting the laminate, the post-heating time is usually more than 1 minute, preferably more than 5 minutes. From the perspective of suppressing or avoiding the adverse effects of excessive heating on the layers, the post-heating time is usually less than 180 minutes, preferably less than 120 minutes.

[0269] Heating can be performed using a hot plate, an oven, etc. When post-heating is performed using a hot plate, the semiconductor substrate and the support substrate of the stack can be heated with either side facing downward. From the perspective of achieving appropriate peeling with good reproducibility, post-heating is preferably performed with the semiconductor substrate facing downward.

[0270] It should be noted that one of the purposes of the post-heat treatment is to achieve a more appropriate adhesive layer and release agent layer as a self-supporting film, and in particular, to appropriately achieve curing by a hydrosilylation reaction.

[0271] <Second Implementation Method>

[0272] The laminate having the electronic device layer is used for processing the electronic device layer. During the processing of the electronic device layer, the electronic device layer is bonded to the support substrate via the adhesive layer. After the processing of the electronic device layer, the release agent layer is irradiated with light, and then the electronic device layer is separated from the support substrate.

[0273] <<Electronic device layer>>

[0274] The electronic device layer refers to a layer having electronic devices, and in the present invention, refers to a layer in which a plurality of semiconductor chip substrates are buried in a sealing resin, that is, refers to a layer including a plurality of semiconductor chip substrates and a sealing resin arranged between the semiconductor chip substrates.

[0275] Here, "electronic device" refers to a component that constitutes at least a part of an electronic component. There is no particular limitation on the electronic device, and it can be an electronic device in which various mechanical structures and circuits are formed on the surface of a semiconductor substrate. The electronic device is preferably a composite of a component composed of a metal or semiconductor and a resin that seals or insulates the component. The electronic device can be an electronic device in which the redistribution layer and / or semiconductor element or other element described later is sealed or insulated with a sealing material or an insulating material, and has a single-layer or multi-layer structure.

[0276] <<Support substrate>>

[0277] As the supporting substrate, there can be exemplified the same supporting substrate as that described in the column of <<Supporting substrate>> in the <First embodiment> described above.

[0278] <<Release agent layer>>

[0279] The release agent layer is formed using the above-mentioned adhesive composition for release by light irradiation of the present invention.

[0280] The details of the release agent layer are as described in the column of the above-mentioned <<Release agent layer>> in the above-mentioned <First embodiment>.

[0281] <<Adhesive layer>>

[0282] The adhesive layer is formed using the above-mentioned adhesive composition.

[0283] The details of the adhesive layer are as described in the column of the above-mentioned <<Adhesive layer>> in the above-mentioned <First embodiment>.

[0284] An example of the structure of the laminated body according to the second embodiment will be described below with reference to the drawings.

[0285] Figure 3 A schematic cross-sectional view showing an example of a laminate according to the second embodiment.

[0286] Figure 3 The laminated body includes a supporting substrate 24, a release agent layer 23, an adhesive layer 22, and an electronic device layer 26 in this order.

[0287] The electronic device layer 26 includes a plurality of semiconductor chip substrates 21 and a sealing resin 25 as a sealing material disposed between the semiconductor chip substrates 21 .

[0288] The adhesive layer 22 and the release agent layer 23 are provided between the electronic device layer 26 and the support substrate 24. The adhesive layer 22 is in contact with the electronic device layer 26. The release agent layer 23 is in contact with the adhesive layer 22 and the support substrate 24.

[0289] In addition, another example of the structure of the laminated body of the second embodiment is shown in Figure 4 .

[0290] When the release agent layer of the present invention is a release agent layer having adhesive properties having both release and adhesive functions, the laminate may be formed of a single layer of a release agent layer having adhesive properties instead of a two-layer structure of the release agent layer and the adhesive layer.

[0291] Figure 4 A schematic cross-sectional view showing another example of the laminated body.

[0292] Figure 4 The laminated body includes a supporting substrate 24, a release agent layer 27 having adhesive properties, and an electronic device layer 26 in this order.

[0293] The release agent layer 27 having adhesive properties is provided between the support substrate 24 and the electronic device layer 26. The release agent layer 27 having adhesive properties can be produced by mixing components of a release agent composition forming a release agent with components of an adhesive composition forming an adhesive layer.

[0294] <<Method for producing an example of a laminated body in the second embodiment>>

[0295] In the laminated body of the second embodiment, Figure 3 The laminate shown is an example, and a method for producing the following laminate will be described.

[0296] The laminate of the present invention can be manufactured, for example, by the following method, which includes: a first step, applying a release agent composition on the surface of the above-mentioned supporting substrate to form a release agent coating layer (further heating to form a release agent layer as needed); a second step, applying an adhesive composition on the surface of the above-mentioned release agent coating layer or release agent layer to form an adhesive coating layer (further heating to form an adhesive layer as needed); a third step, placing a semiconductor chip substrate on the adhesive coating layer or the adhesive layer, and bonding the semiconductor chip substrate to the adhesive coating layer or the adhesive layer while performing at least any one of a heating treatment and a decompression treatment; a fourth step, curing the adhesive coating layer by post-heating the adhesive coating layer to form an adhesive layer; and a fifth step, sealing the semiconductor chip substrate fixed on the adhesive layer with a sealing resin.

[0297] When the third step is described in more detail, for example, the step of the following embodiment (i) can be cited.

[0298] (i) placing a semiconductor chip substrate on an adhesive coating layer or an adhesive layer, applying a load in the thickness direction of the semiconductor chip substrate and the supporting substrate to make them closely fit together while performing at least one of a heating treatment and a decompression treatment, thereby bonding the semiconductor chip substrate to the adhesive coating layer or the adhesive layer.

[0299] It should be noted that the post-heating treatment of the adhesive coating layer specified in the fourth step to cure it and the step of forming the adhesive layer can be performed after the semiconductor chip substrate is bonded to the adhesive coating layer in the third step, or can be performed together with the third step. For example, the semiconductor chip substrate can be placed on the adhesive coating layer, and the adhesive coating layer can be heated to cure while applying a load in the thickness direction of the semiconductor chip substrate and the supporting substrate, thereby performing the close bonding of the semiconductor chip substrate and the adhesive coating layer and curing from the adhesive coating layer to the adhesive layer at the same time, and bonding the adhesive layer to the semiconductor chip substrate.

[0300] In addition, the step of post-heating the adhesive coating layer to solidify it as specified in the fourth step to form the adhesive layer can be performed before the third step, or the semiconductor chip substrate can be placed on the adhesive layer and the adhesive layer and the semiconductor chip substrate can be bonded together while applying a load in the thickness direction of the semiconductor chip substrate and the supporting substrate.

[0301] The coating method, the release agent composition after coating, the heating temperature of the adhesive composition, the heating method, etc. are as described in the above <<Method for producing an example of a laminate in the first embodiment>> of the above <First embodiment>.

[0302] The method for producing the laminated body according to the second embodiment will be described below in more detail with reference to the drawings.

[0303] like Figure 5 As shown, a release agent coating layer 23' formed of a release agent composition is formed on a support substrate 24. At this time, the release agent coating layer 23' may be heated to form the release agent layer 23.

[0304] Then, if Figure 6 As shown, an adhesive coating layer 22' made of an adhesive composition is formed on the release coating layer 23' or the release layer 23. At this time, the adhesive coating layer 22' may be heated to form the adhesive layer 22.

[0305] Then, if Figure 7 As shown, a semiconductor chip substrate 21 is placed on an adhesive layer 22 or an adhesive coating layer 22', and a load in the thickness direction of the semiconductor chip substrate 21 and the support substrate 24 is applied to make them close while performing at least one of a heating treatment and a decompression treatment, so that the semiconductor chip substrate 21 is attached to the adhesive layer 22 or the adhesive coating layer 22'. When the semiconductor chip substrate 21 is attached to the adhesive coating layer 22', the adhesive coating layer 22' is cured by post-heating to form an adhesive layer 22, and the semiconductor chip substrate 21 is fixed to the adhesive layer 22.

[0306] It should be noted that the release agent layer 23 may be formed by simultaneously performing a post-heat treatment on the release agent coating layer 23 ′ when the adhesive coating layer 22 ′ is post-heated.

[0307] Then, if Figure 8 As shown in FIG. 1 , the semiconductor chip substrate 21 fixed on the adhesive layer 22 is sealed using a sealing resin 25. Figure 8 In the embodiment, a plurality of semiconductor chip substrates 21 temporarily bonded to a support substrate 24 via an adhesive layer 22 are sealed with a sealing resin 25. An electronic device layer 26 having semiconductor chip substrates 21 and sealing resin 25 disposed between the semiconductor chip substrates 21 is formed on the adhesive layer 22, so that the electronic device layer 26 becomes a base material layer in which a plurality of semiconductor chip substrates are embedded in the sealing resin.

[0308] <<<Sealing process>>>

[0309] The semiconductor chip substrate 21 is sealed using a sealing material.

[0310] As a sealing material for sealing the semiconductor chip substrate 21, a member capable of insulating or sealing a member made of metal or semiconductor is used.

[0311] In the present invention, a resin composition is used as the sealing material, for example. The type of the sealing resin is not particularly limited as long as it can seal and / or insulate a metal or a semiconductor, and for example, epoxy resins or silicone resins are preferably used.

[0312] The sealing material may contain other components such as fillers in addition to the resin component. Examples of the filler include spherical silica particles.

[0313] In the sealing process, the sealing resin heated to, for example, 130 to 170° C. is supplied to the adhesive layer 22 in a manner that maintains a high viscosity and covers the semiconductor chip substrate 21, and compression molding is performed, thereby forming a layer formed of the sealing resin 25 on the adhesive layer 22. At this time, the temperature condition is, for example, 130 to 170° C. In addition, the pressure applied to the semiconductor chip substrate 21 is, for example, 50 to 500 N / cm 2 .

[0314] (Method for manufacturing processed semiconductor substrate or electronic device layer)

[0315] By using the laminated body of the present invention, a method for producing a processed semiconductor substrate or a method for producing a processed electronic device layer can be provided.

[0316] The "processed semiconductor substrate manufacturing method" uses the laminate described in the column of the above <First Embodiment> of the above (laminated body). In addition, the "processed electronic device layer manufacturing method" uses the laminate described in the column of the above <Second Embodiment> of the above (laminated body).

[0317] The “method for producing a processed semiconductor substrate” will be described in the following <Third Embodiment>, and the “method for producing a processed electronic device layer” will be described in the following <Fourth Embodiment>.

[0318] <Third Implementation Plan>

[0319] The method for manufacturing a processed semiconductor substrate of the present invention includes the following step 5A and the following step 6A.

[0320] Here, step 5A is a step of processing the semiconductor substrate in the stacked body described in the above-mentioned column of <First Embodiment>.

[0321] In addition, step 6A is a step of separating the semiconductor substrate processed in step 5A from the support substrate.

[0322] In the 5A step, the processing performed on the semiconductor substrate refers to, for example, processing on the opposite side of the circuit surface of the wafer, and the wafer thinning by grinding the back side of the wafer can be cited. Then, for example, through silicon vias (TSV) are formed, and then the thinned wafer is peeled off from the supporting substrate to form a stack of wafers for three-dimensional mounting. In addition, for example, the formation of the back electrode of the wafer is also performed before and after the three-dimensional mounting. In the thinning and TSV processes of the wafer, heat of about 250 to 350°C is applied in a state bonded to the supporting substrate. The stack of the present invention usually includes an adhesive layer and has heat resistance to the load.

[0323] It should be noted that the processing is not limited to the above processing, and includes, for example, a semiconductor component mounting process when temporary bonding with a support substrate is performed in order to support a base material for mounting a semiconductor component.

[0324] In step 6A, the method of separating (peeling off) the semiconductor substrate from the supporting substrate includes, but is not limited to, mechanical peeling using a tool having a sharp portion after irradiating the peeling agent layer with light, peeling by tearing between the supporting body and the semiconductor wafer, etc.

[0325] By irradiating the release agent layer with light from the support substrate side, the release agent layer is degraded (eg, separated or decomposed) as described above, and then, for example, one of the substrates is pulled up to easily separate the semiconductor substrate from the support substrate.

[0326] It is not necessary to irradiate the release agent layer with light on the entire area of ​​the release agent layer. Even if the areas irradiated with light and the areas not irradiated with light are mixed, as long as the peeling ability of the release agent layer as a whole is sufficiently improved, the semiconductor substrate can be separated from the supporting substrate by a slight external force such as pulling up the supporting substrate. The ratio and positional relationship of the areas irradiated with light and the areas not irradiated with light vary depending on the type of adhesive used, its specific composition; the thickness of the adhesive layer; the thickness of the release agent layer; the intensity of the irradiated light, etc., but if a person skilled in the art is skilled in the art, appropriate conditions can be set without excessive experiments. Due to such a situation, according to the method for manufacturing a processed semiconductor substrate of the present invention, for example, when the supporting substrate of the stacked body used is light-transmissive, the light irradiation time can be shortened when peeling is performed by irradiating light from the supporting substrate side. As a result, not only can an improvement in throughput be expected, but also physical stress used for peeling can be avoided, and the semiconductor substrate can be easily and efficiently separated from the supporting substrate only by irradiation with light.

[0327] Generally, the irradiation dose of light used for peeling is 50 to 3000 mJ / cm 2 The irradiation time is appropriately determined according to the wavelength and the irradiation amount.

[0328] The wavelength of the light used for stripping is preferably 250 to 600 nm, and more preferably 250 to 370 nm, as described above. More suitable wavelengths are 308 nm, 343 nm, 355 nm, 365 nm, or 532 nm. The irradiation amount of light required for stripping is an irradiation amount that causes appropriate deterioration of the specific light absorbing compound, such as decomposition.

[0329] The light used for the stripping may be laser light or a non-laser light source such as an ultraviolet lamp.

[0330] The cleaning composition may be sprayed on the surface of at least any one of the separated semiconductor substrate and the supporting substrate, or the separated semiconductor substrate or the supporting substrate may be immersed in the cleaning composition to clean the substrate.

[0331] Alternatively, the surface of a processed semiconductor substrate or the like may be cleaned using a removal tape or the like.

[0332] The constituent elements and method elements related to the above-mentioned steps of the method for manufacturing a processed semiconductor substrate of the present invention may be variously modified without departing from the gist of the present invention.

[0333] The method for producing a processed semiconductor substrate of the present invention may include steps other than the above-mentioned steps.

[0334] In the peeling method of the present invention, when the semiconductor substrate or the supporting substrate of the laminated body of the present invention is light-transmissive, the semiconductor substrate and the supporting substrate of the laminated body are separated by irradiating the peeling agent layer with light from the semiconductor substrate side or the supporting substrate side.

[0335] In the laminate of the present invention, the semiconductor substrate and the support substrate are temporarily bonded appropriately and releasably by the adhesive layer and the release agent layer, so that, for example, when the support substrate is light-transmissive, the semiconductor substrate and the support substrate can be easily separated by irradiating the release agent layer with light from the support substrate side of the laminate. Usually, the peeling is performed after the semiconductor substrate of the laminate is processed.

[0336] <Fourth Implementation Plan>

[0337] The method for producing a processed electronic device layer of the present invention includes the following step 5B and the following step 6B.

[0338] Here, step 5B is a step of processing the electronic device layer in the laminate described in the section of the above-mentioned <Second Embodiment>.

[0339] In addition, step 6B is a step of separating the electronic device layer processed in step 5B from the supporting substrate.

[0340] Examples of the processing performed on the electronic device layer in step 5B include a grinding step and a wiring layer forming step.

[0341] <<Grinding process>>

[0342] The grinding step is a step of grinding the resin portion of the sealing resin 25 layer in the electronic device layer 26 so that a portion of the semiconductor chip substrate 21 is exposed after the above-mentioned sealing step.

[0343] Grinding of sealing resin parts, for example Fig. 9 As shown, this is performed by grinding the sealing resin 25 layer to a thickness substantially the same as that of the semiconductor chip substrate 21 .

[0344] <<Wiring layer formation process>>

[0345] The wiring layer forming step is a step of forming a wiring layer on the exposed semiconductor chip substrate 21 after the above-mentioned grinding step.

[0346] exist Fig.10 In the embodiment, a wiring layer 28 is formed on an electronic device layer 26 including a semiconductor chip substrate 21 and a sealing resin 25 .

[0347] The wiring layer 28 is also called RDL (Redistribution Layer), which is a thin-film wiring body that constitutes wiring connected to the substrate, and can have a single-layer or multi-layer structure. The wiring layer can be made of a conductor (such as aluminum, copper, titanium, nickel, gold, silver and other metals and silver-tin alloys) on a dielectric (silicon oxide (SiO X ), photosensitive resins such as photosensitive epoxy resins, etc.) form a layer of wiring between them, but is not limited to this.

[0348] As a method of forming the wiring layer 28 , for example, the following method can be cited.

[0349] First, silicon oxide (SiO X ), photosensitive resin and other dielectric layers. The dielectric layer composed of silicon oxide can be formed, for example, by sputtering, vacuum evaporation, etc. The dielectric layer formed of the photosensitive resin can be formed, for example, by applying the photosensitive resin on the layer of the sealing resin 25 by spin coating, dipping, roller blade, spray coating, slit coating, etc.

[0350] Next, wiring is formed on the dielectric layer using a conductor such as a metal. As a method for forming wiring, for example, a known semiconductor process method such as photolithography (resist photolithography) or etching can be used. Examples of such photolithography include photolithography using a positive resist material and photolithography using a negative resist material.

[0351] In the method for manufacturing the laminated body of the fourth embodiment, bumps may be further formed or components may be mounted on the wiring layer 28. The components may be mounted on the wiring layer 28 using, for example, a chip mounter or the like.

[0352] The laminated body of the fourth embodiment may be a laminated body produced by a process based on a fan-out technology in which terminals provided on a semiconductor chip substrate are mounted on a wiring layer extending outside a chip region.

[0353] In step 6B, the method of separating (peeling off) the electronic device layer from the supporting substrate includes, but is not limited to, mechanical peeling using a tool having a sharp portion after irradiating the peeling agent layer with light, peeling by tearing between the supporting body and the electronic device layer, etc.

[0354] By irradiating the release agent layer with light from the support substrate side, the release agent layer is degraded (eg, separated or decomposed) as described above, and then, for example, one of the substrates is pulled up to easily separate the electronic device layer from the support substrate.

[0355] Figure 11-12is a schematic cross-sectional view for explaining a method for separating a laminated body. Fig.13 This is a schematic cross-sectional view for explaining a method for cleaning a laminated body after separation. Figure 11 to Figure 13 , which can illustrate an embodiment of a method for manufacturing a semiconductor package (electronic component).

[0356] like Fig.11 As shown, the step of separating the laminated body is a step of irradiating the release agent layer 23 with light (arrow) via the support substrate 24 to change the release agent layer 23 , thereby separating the electronic device layer 26 from the support substrate 24 .

[0357] After the release agent layer 23 is irradiated with light (arrow) to deteriorate the release agent layer 23, Fig.12 As shown, the support substrate 24 is separated from the electronic device layer 26 .

[0358] The conditions and method of irradiating the adhesive layer with light are as described in the above-mentioned section of <Third Embodiment>.

[0359] The substrate may be cleaned by spraying the cleaning composition on the surface of at least any one of the separated electronic device layer and the supporting substrate, or by immersing the separated electronic device layer or the supporting substrate in the cleaning composition.

[0360] Alternatively, the surface of the processed electronic device layer or the like may be cleaned using a removal tape or the like.

[0361] For example, in Fig.12 In the present invention, after the separation process, the adhesive layer 22 and the release agent layer 23 are attached to the electronic device layer 26. By using a cleaning agent composition such as an acid or an alkali, the adhesive layer 22 and the release agent layer 23 are decomposed and removed. By removing the release agent layer and the adhesive layer, the following can be appropriately obtained: Fig.13 The processed electronic device layer (electronic component) is shown.

[0362] The constituent elements and method elements related to the above-mentioned steps of the method for producing a processed electronic device layer of the present invention may be variously modified without departing from the gist of the present invention.

[0363] The method for producing a processed electronic device layer of the present invention may include steps other than the above-mentioned steps.

[0364] In the laminate of the present invention, the electronic device layer and the supporting substrate are temporarily bonded appropriately and releasably by the adhesive layer, so that, for example, when the supporting substrate is light-transmissive, the electronic device layer and the supporting substrate can be easily separated by irradiating light to the release agent layer from the supporting substrate side of the laminate. Usually, the peeling is performed after the electronic device layer of the laminate is processed.

[0365] Example

[0366] Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples. The apparatus used is as follows.

[0367] [Device]

[0368] (1) Mixer: ARE-500, a rotary and revolving mixer manufactured by THINKY Co., Ltd.

[0369] (2) Viscometer: TVE-22H rotary viscometer manufactured by Toki Sangyo Co., Ltd.

[0370] (3) Transmittance measuring device: UV3600Plus manufactured by Shimadzu Corporation.

[0371] (4) Vacuum bonding device: manual bonding machine manufactured by SUSS MicroTec Co., Ltd.

[0372] (5) Laser irradiation device: NC-LD300-EXC manufactured by OPTEK Corporation.

[0373] [Preparation Example 1]

[0374] In a 100 mL glass bottle, 2.5 g of tannic acid (produced by Kanto Chemical) and 47.5 g of pure water were added and stirred to prepare a composition (1).

[0375] [Preparation Example 2]

[0376] In a 100 mL glass bottle, 2.5 g of tannic acid (manufactured by Kanto Chemical Industry), 0.25 g of Acid Red 18 (manufactured by Tokyo Chemical Industry) and 47.25 g of pure water were added and stirred to prepare a composition (2).

[0377] [Preparation Example 3]

[0378] In a 100 mL glass bottle, 2.5 g of tannic acid (produced by Kanto Chemical Industry), 0.25 g of CHLORANTINE FAST RED 5B (produced by Tokyo Chemical Industry) and 47.25 g of pure water were added and stirred to prepare a composition (3).

[0379] [Preparation Example 4]

[0380] In a 100 mL glass bottle, 2.5 g of tannic acid (produced by Kanto Chemical Industry), 0.25 g of Chrome Pure Blue BX (produced by Tokyo Chemical Industry), and 47.25 g of pure water were added and stirred to prepare a composition (4).

[0381] [Preparation Example 5]

[0382] An adhesive composition (A) for use in the bonding test of Example 2 below was prepared as follows.

[0383] In a 600 mL stirring container for a stirrer, 80 g of an MQ resin containing polysiloxane and a vinyl group (manufactured by Wacker Chemie) as the polyorganosiloxane (a1), 2.52 g of a SiH group-containing linear polydimethylsiloxane (manufactured by Wacker Chemie) having a viscosity of 100 mPa·s as the polyorganosiloxane (a2), 5.89 g of a SiH group-containing linear polydimethylsiloxane (manufactured by Wacker Chemie) having a viscosity of 70 mPa·s as the polyorganosiloxane (a2), and 0.22 g of 1-ethynylcyclohexanol (manufactured by Wacker Chemie) as a polymerization inhibitor (A3) were added, and the mixture was stirred for 5 minutes using a stirrer.

[0384] To the obtained mixture, 3.96 g of a mixture obtained by stirring for 5 minutes with a stirrer was added 0.147 g of a platinum catalyst (manufactured by Wacker Chemie) as a platinum group metal catalyst (A2) and 5.81 g of a vinyl-containing linear polydimethylsiloxane (manufactured by Wacker Chemie) having a viscosity of 1000 mPa·s as a polyorganosiloxane (a1), and the mixture was stirred for 5 minutes with a stirrer.

[0385] Finally, the obtained mixture was filtered through a 300-mesh nylon filter to obtain an adhesive composition (A). The viscosity of the adhesive measured with a viscometer was 10,000 mPa·s.

[0386] In order to confirm the wavelength region in which the release agent layer formed using the release agent composition for photo-irradiation release of the present invention can absorb light when irradiated with laser, the transmittance at an arbitrary wavelength was measured as described in Example 1 below.

[0387] [Example 1] Measurement of transmittance

[0388] The compositions (1) to (4) obtained in Preparation Examples 1 to 4 were applied onto a quartz substrate using a spin coater and heated on a hot plate at 250° C. for 5 minutes to form a thin film having a thickness of 200 nm.

[0389] The obtained quartz substrate coated with the stripping agent composition and a quartz substrate not coated with anything as a reference were fixed to a workbench in the apparatus, and the transmittance of the layer coated on the quartz substrate was measured at every 0.5 nm in the wavelength range of 190 to 800 nm. The transmittance results at 308, 355, and 532 nm are shown in the following Table 1.

[0390] In order to confirm whether the release agent layer formed using the release agent composition for photo-irradiation release of the present invention can be easily removed by laser irradiation, a laminate described in Example 2 below was prepared and a laser irradiation test described in Example 3 below was performed.

[0391] [Example 2] Preparation of laminate

[0392] The adhesive composition (A) was applied to a 100 mm silicon wafer (thickness: 500 μm) as a wafer on the device side by a spin coater to form an adhesive composition layer (A) of 30 μm. A 100 mm glass wafer (EAGLE-XG, manufactured by Corning, thickness 500 μm) was prepared as a wafer (support) on the carrier side, and the above-mentioned compositions (1) to (4) were applied by a spin coater, and heated on a 250°C hot plate for 5 minutes to form composition layers (1) to (4) of 200 nm. The adhesive composition layer (A) and the composition layers (1) to (4) were laminated in a vacuum laminating device in such a manner as to sandwich them, thereby producing a laminate. Then, the device side wafer was heated on a hot plate at 200°C for 10 minutes to cure each composition layer, thereby obtaining a laminate (1) to (4).

[0393] The laminates using the composition layers (1) to (4) correspond to the laminates (1) to (4), respectively.

[0394] [Example 3] Laser irradiation test

[0395] A laser irradiation device was used to irradiate the glass wafer at an output of 250 mJ / cm 2 The obtained laminates (1) to (4) were irradiated with laser light to check whether the glass wafer could be peeled off. After laser irradiation, the glass wafer was lifted up with tweezers, and the case where it could be easily peeled off was marked as "○", and the case where it could not be peeled off was marked as "×".

[0396] The test results of Example 3 are shown in Table 1 below.

[0397] [Table 1]

[0398]

[0399] According to the above-described examples, it was confirmed that the composition layers (1) to (4) formed using the release agent composition for light irradiation release specified in the present invention exhibited good laser release properties.

[0400] In the composition layers (2) to (4), a tendency was observed that the transmittance on the high wavelength side decreased as a whole, and it was confirmed that the light absorption wavelength region of the release agent composition could be expanded by mixing a water-soluble dye.

[0401] The stripping agent composition for light irradiation stripping specified in the present invention is completed without using an organic solvent. On this basis, it can be effectively formed in the following stacked body, and the stripping agent layer used for the stacked body can firmly bond the supporting substrate to the semiconductor substrate or the electronic device layer when the semiconductor substrate or the electronic device layer is processed, and after the substrate is processed, the supporting substrate can be easily separated from the semiconductor substrate or the electronic device layer by light irradiation.

[0402] Description of Reference Numerals

[0403] 1: semiconductor substrate; 2: adhesive layer; 3: release agent layer; 4: supporting substrate; 5: release agent layer with adhesive properties; 21: semiconductor chip substrate; 22: adhesive layer; 23: release agent layer; 24: supporting substrate; 25: sealing resin; 26: electronic device layer; 27: release agent layer with adhesive properties; 28: wiring layer.

Claims

1. A release agent composition for photo-irradiation release, which is used to form the following release agent layer of the following laminated body, The laminate comprises: a semiconductor substrate or an electronic device layer, a light-transmitting support substrate, and a release agent layer provided between the semiconductor substrate or the electronic device layer and the support substrate. The electronic device layer includes a plurality of semiconductor chip substrates and a sealing resin disposed between the semiconductor chip substrates. The laminate is used to peel the semiconductor substrate or the electronic device layer from the support substrate after the release agent layer absorbs light irradiated from the support substrate side. The stripping agent composition contains: a light absorbing compound and a solvent, wherein the light absorbing compound helps to facilitate the stripping of the semiconductor substrate or the electronic device layer from the supporting substrate by absorbing the light, The solvent contains water.

2. The stripping agent composition according to claim 1, wherein The content of the water is 50% by mass or more based on the solvent in the release agent composition.

3. The stripping agent composition according to claim 2, wherein The content of the water is 98% by mass or more based on the solvent in the release agent composition.

4. The stripping agent composition according to claim 1, wherein When the absorption spectrum of the light absorbing compound in the range of 250 nm to 800 nm is measured, the absorption spectrum has a maximum value with the highest absorbance between 250 nm and 350 nm in the range of 250 nm to 800 nm.

5. The stripping agent composition according to claim 4, wherein The light absorbing compound is a polyphenol compound.

6. The stripping agent composition according to claim 5, wherein The polyphenolic compound is a compound selected from the group consisting of condensed tannins obtained by polymerizing compounds having a flavanol skeleton, hydrolyzable tannins obtained by esterifying aromatic compounds of gallic acid or ellagic acid with sugar, and flavonoids derived from compounds having a flavanone skeleton structure.

7. The stripping agent composition according to claim 6, wherein The hydrolyzable tannin is tannic acid represented by the following formula (9):

8. The release agent composition according to any one of claims 1 to 7, wherein The stripping agent composition further contains a water-soluble pigment.

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