Laminate and production method for processed compound-semiconductor substrate

Abstract

A laminate comprising a compound-semiconductor substrate, a support substrate, and an adhesive layer provided between the compound-semiconductor substrate and the support substrate.

Description

Stacked body and method for manufacturing processed compound semiconductor substrate

[0001] The present invention relates to a method for manufacturing a laminate and a processed compound semiconductor substrate.

[0002] BACKGROUND ART Compound semiconductor chips using compound semiconductors such as silicon carbide (SiC) and gallium nitride (GaN) are used in SiC power semiconductor elements, GaN HEMTs (High Electron Mobility Transistors), and the like.

[0003] As a method for manufacturing a power semiconductor device using a Si substrate, for example, a method for manufacturing a power semiconductor device has been proposed, which includes the steps of: forming a gate electrode on one surface of a semiconductor substrate; polishing the semiconductor substrate from the other surface opposite to the one surface on which the gate electrode is formed, to form the semiconductor substrate to a predetermined thickness; forming an alloy on the other surface of the semiconductor substrate, which serves as a drain electrode, containing impurities of the same conductivity type as the semiconductor substrate; and diffusing the impurities contained in the alloy into the semiconductor substrate to form an impurity layer of the same conductivity type as the semiconductor substrate, which has a higher concentration than the semiconductor substrate (see Patent Document 1).

[0004] Japanese Patent Application Laid-Open No. 2000-252466

[0005] Since a compound semiconductor substrate is harder than a Si substrate, heat generation and warping are likely to occur when the compound semiconductor substrate is subjected to mechanical processing such as polishing, cutting, and drilling.

[0006] An object of the present invention is to provide a laminate that can be used to fabricate a processed compound semiconductor substrate with reduced warpage, and a method for manufacturing a processed compound semiconductor substrate using the laminate.

[0007] The present inventors have conducted extensive research to solve the above problems, and as a result have found that the above problems can be solved, and have completed the present invention having the following gist.

[0008] That is, the present invention includes the following. [1] A laminate having a compound semiconductor substrate temporarily bonded when processing the compound semiconductor substrate, the laminate having the compound semiconductor substrate, a support substrate, and an adhesive layer provided between the compound semiconductor substrate and the support substrate. [2] The laminate according to [1], further having a release agent layer provided between the compound semiconductor substrate and the support substrate. [3] The compound semiconductor in the compound semiconductor substrate is SiC, GaN, GaAs, Ga ２ O ３

[0023] The laminate according to [1] or [2], which contains at least one of AlGaAs and AlGaAs. [4] The laminate according to any of [1] to [3], wherein the adhesive layer is an adhesive layer formed from an adhesive composition. [5] The laminate according to any of [1] to [4], wherein the adhesive layer is a heat-resistant adhesive layer. [6] A method for producing a processed compound semiconductor substrate, comprising: a processing step in which the compound semiconductor substrate of the laminate according to any of [1] to [5] is processed; and a separation step in which the processed compound semiconductor substrate is separated from the support substrate. [7] A method for producing a processed compound semiconductor substrate according to [6], which further comprises a cleaning step in which the processed compound semiconductor substrate is cleaned after the separation step.

[0009] According to the present invention, it is possible to provide a laminate that can be used to fabricate a processed compound semiconductor substrate with reduced warpage, and a method for manufacturing a processed compound semiconductor substrate using the laminate.

[0010] FIG. 1 is a schematic cross-sectional view of an example of a laminate. FIG. 2 is a schematic cross-sectional view of another example of a laminate. FIG. 3A is a schematic cross-sectional view (part 1) for explaining an example of a method for manufacturing a laminate. FIG. 3B is a schematic cross-sectional view (part 2) for explaining an example of a method for manufacturing a laminate. FIG. 3C is a schematic cross-sectional view (part 3) for explaining an example of a method for manufacturing a laminate. FIG. 4A is a schematic cross-sectional view (part 1) for explaining an example of a method for manufacturing a processed compound semiconductor substrate. FIG. 4B is a schematic cross-sectional view (part 2) for explaining an example of a method for manufacturing a processed compound semiconductor substrate. FIG. 4C is a schematic cross-sectional view (part 3) for explaining an example of a method for manufacturing a processed compound semiconductor substrate. FIG. 4D is a schematic cross-sectional view (part 4) for explaining an example of a method for manufacturing a processed compound semiconductor substrate. FIG. 4E is a schematic cross-sectional view (part 5) for explaining an example of a method for manufacturing a processed compound semiconductor substrate.

[0011] (Laminate) The laminate of the present invention has a compound semiconductor substrate, a support substrate, and an adhesive layer. In the laminate, the adhesive layer is provided between the compound semiconductor substrate and the support substrate. The laminate may further have a release agent layer. The laminate is a laminate to which a compound semiconductor substrate is temporarily bonded when the compound semiconductor substrate is processed.

[0012] The laminate of the present invention is used for temporarily bonding a compound semiconductor substrate when the compound semiconductor substrate is processed. While the compound semiconductor substrate is being processed, such as being thinned, the compound semiconductor substrate is supported by a support substrate. On the other hand, after the compound semiconductor substrate is processed, the support substrate and the compound semiconductor substrate are separated. When the compound semiconductor substrate is processed, such as being thinned, the compound semiconductor substrate may warp. By supporting the compound semiconductor substrate by the support substrate via the adhesive layer when the compound semiconductor substrate is processed, warping of the compound semiconductor substrate caused by processing can be suppressed.

[0013] Residues of the release agent layer or adhesive layer remaining on the compound semiconductor substrate or the support substrate after the compound semiconductor substrate and the support substrate are separated can be removed, for example, with a cleaning composition for cleaning compound semiconductor substrates and the like.

[0014] <Compound Semiconductor Substrate> Examples of the compound semiconductor substrate include a substrate in which a large number of compound semiconductor chip precursors are arranged, which are processed and divided into individual compound semiconductor chips. Examples of the compound semiconductor chip include power semiconductors and GaN HEMTs. Compound semiconductors in the compound semiconductor substrate include, for example, SiC, GaN, GaAs, Ga ２ O ３ and AlGaAs. When the compound semiconductor substrate is made of two or more types of compound semiconductors, the two or more types of compound semiconductors are, for example, stacked in layers. For example, a transistor is formed on the surface of the compound semiconductor substrate. Examples of the transistor include a bipolar transistor and a field effect transistor.

[0015] The shape of the compound semiconductor substrate is not particularly limited, but may be, for example, a disk shape. The disk-shaped compound semiconductor substrate does not need to have a perfectly circular surface; for example, the outer periphery of the compound semiconductor substrate may have a straight line portion called an orientation flat, or a notch. The thickness of the disk-shaped compound semiconductor substrate may be determined appropriately depending on the intended use of the compound semiconductor substrate, and is not particularly limited, but is, for example, 500 to 1,000 μm. The diameter of the disk-shaped compound semiconductor substrate may be determined appropriately depending on the intended use of the compound semiconductor substrate, and is not particularly limited, but is, for example, 100 to 1,000 mm.

[0016] <Support Substrate> The support substrate is not particularly limited as long as it is a member that can support the compound semiconductor substrate when the compound semiconductor substrate is processed, and examples thereof include a glass support substrate and a sapphire support substrate.

[0017] The shape of the support substrate is not particularly limited, but may be, for example, a disk shape. The surface of the disk-shaped support substrate does not need to be perfectly circular; for example, the outer periphery of the support substrate may have a straight line portion called an orientation flat, or a notch. The thickness of the disk-shaped support substrate may be determined appropriately depending on the size of the compound semiconductor substrate, etc., and is not particularly limited, but is, for example, 500 to 1,000 μm. The diameter of the disk-shaped support substrate may be determined appropriately depending on the size of the compound semiconductor substrate, etc., and is not particularly limited, but is, for example, 100 to 1,000 mm.

[0018] An example of the support substrate is a glass wafer or a sapphire wafer having a diameter of about 300 mm and a thickness of about 700 μm.

[0019] When the laminate is peeled off by light irradiation, the support substrate used is, for example, a substrate that is optically transparent to the light used. Examples of such a substrate include a glass support substrate and a sapphire support substrate.

[0020] <Adhesive Layer> The adhesive layer is provided between the support substrate and the compound semiconductor substrate. The adhesive layer is in contact with, for example, the compound semiconductor substrate. The adhesive layer may be in contact with, for example, the support substrate. The adhesive layer is, for example, an adhesive layer formed from an adhesive composition.

[0021] Because compound semiconductor substrates are harder than Si substrates, heat is likely to be generated when the compound semiconductor substrate is subjected to mechanical processing such as polishing, cutting, and drilling. This is also one aspect of the challenges when processing compound semiconductor substrates. Increasing the processing speed of the compound semiconductor substrate further increases the heat generation. Therefore, it is preferable that the adhesive layer has heat resistance. That is, the adhesive layer is preferably a heat-resistant adhesive layer. Decomposition of the adhesive layer can result in problems such as a decrease in the adhesive strength of the adhesive layer, making the compound semiconductor substrate more likely to separate from the support substrate during processing, or an increase in the adhesive strength of the adhesive layer, making it difficult to separate the compound semiconductor substrate from the support substrate after processing. By having a heat-resistant adhesive layer, the adhesive layer is less likely to decompose even when heat is generated during processing of the compound semiconductor substrate, thereby avoiding such problems. Furthermore, the heat-resistant adhesive layer can also increase the processing speed. The heat resistance of the adhesive layer is not particularly limited, but the 1% weight loss temperature in thermogravimetric analysis (TGA) is preferably 200° C. or higher, more preferably 250° C. or higher, and particularly preferably 300° C. or higher. The upper limit of the 1% weight loss temperature is not particularly limited, but the 1% weight loss temperature may be 500° C. or lower, 400° C. or lower, or 300° C. or lower.

[0022] The thickness of the adhesive layer is not particularly limited, but is usually 5 to 500 μm. From the viewpoint of maintaining film strength, it is preferably 10 μm or more, more preferably 20 μm or more, and even more preferably 30 μm or more. From the viewpoint of avoiding non-uniformity due to a thick film, it is preferably 200 μm or less, more preferably 150 μm or less, even more preferably 120 μm or less, and even more preferably 100 μm or less.

[0023] <<Adhesive Composition>> Examples of adhesive compositions include, but are not limited to, polysiloxane-based adhesives, acrylic resin-based adhesives, epoxy resin-based adhesives, polyamide-based adhesives, polystyrene-based adhesives, polyimide adhesives, phenolic resin-based adhesives, etc. Among these, polysiloxane-based adhesives are preferred as the adhesive composition because they exhibit suitable adhesive performance during processing of compound semiconductor substrates, etc., are suitable for releasability after processing, have excellent heat resistance, and can be suitably removed with a cleaning composition.

[0024] The adhesive composition may be, for example, a water-dispersed adhesive, a solvent-based adhesive, a reactive adhesive, or a hot-melt adhesive. Water-dispersed adhesives include, for example, polyvinyl acetate, ethylene-vinyl acetate copolymer, acrylic resin, urea resin, melamine resin, aqueous polymer, and isocyanate curing component as adhesive components. Solvent-based adhesives include, for example, chloroprene rubber, nitrile rubber, and polyvinyl acetate as adhesive components. Reactive adhesives include, for example, thermosetting adhesives, anaerobic curing adhesives, moisture-curing adhesives, ultraviolet-curing adhesives, and two-component adhesives. Hot-melt adhesives include, for example, non-reactive adhesives and reactive adhesives. Examples of thermosetting reactive adhesives include epoxy resin-based adhesives, silicone resin-based adhesives, and acrylic resin-based adhesives. Examples of anaerobic curing reactive adhesives include acrylic resin-based adhesives. Examples of moisture-curing reactive adhesives include silicone resin-based adhesives, cyanoacrylate resin-based adhesives, and urethane resin-based adhesives. Examples of ultraviolet-curing adhesives in the reactive adhesives include acrylic resin adhesives and epoxy resin adhesives. Examples of two-component adhesives in the reactive adhesives include epoxy resin adhesives, acrylic resin adhesives, urethane resin adhesives, and silicone resin adhesives. Examples of non-reactive adhesives in the hot melt adhesives include EVA resin adhesives, synthetic rubber adhesives, polyamide resin adhesives, and polyester resin adhesives. Examples of reactive adhesives in the hot melt adhesives include PUR (urethane resin reactive) adhesives and POR (olefin resin reactive) adhesives.

[0025] Examples of adhesive compositions are shown below.

[0026] <<<First Embodiment of Adhesive Composition>>> First embodiment of the adhesive composition contains, for example, an adhesive component. First embodiment of the adhesive composition may further contain a release agent component, a solvent, etc.

[0027] -Adhesive Component- The adhesive component is not particularly limited, but is preferably a component that cures, and more preferably a component that cures by a hydrosilylation reaction. The component that cures by a hydrosilylation reaction is not particularly limited, but preferably contains a component having an alkenyl group having 2 to 40 carbon atoms bonded to a silicon atom (hereinafter sometimes referred to as "component (A-1)"), a component having a Si-H group (hereinafter sometimes referred to as "component (A-2)"), and a catalyst (A-3).

[0028] --Component (A-1) and Component (A-2)-- The adhesive component preferably contains component (A-1). The adhesive component preferably contains component (A-2). Hereinafter, the combination of component (A-1), component (A-2), and catalyst (A-3) may be referred to as "curable component (A)" or "component (A)."

[0029] From the viewpoint of optimally achieving the effects of the present invention, component (A-1) preferably contains a polyorganosiloxane (a1) having an alkenyl group having 2 to 40 carbon atoms bonded to a silicon atom. From the viewpoint of optimally achieving the effects of the present invention, component (A-2) preferably contains a polyorganosiloxane (a2) having a Si—H group. Here, the alkenyl group having 2 to 40 carbon atoms may be substituted. Examples of the substituent include a halogen atom, a nitro group, a cyano group, an amino group, a hydroxy group, a carboxyl group, an aryl group, and a heteroaryl group.

[0030] In another preferred embodiment, the adhesive composition that cures by a hydrosilylation reaction is ２ Siloxane units (Q units) represented by R １ R ２ R ３ SiO １／２ Siloxane units (M units) represented by R ４ R ５ SiO ２／２ Siloxane units (D units) represented by the formula: and R ６ SiO ３／２and a catalyst (A-3), wherein the polysiloxane (A1) contains one or more units selected from the group consisting of siloxane units (T units) represented by the following formula: ２ Siloxane units (Q′ units) represented by R １ 'R ２ 'R ３ 'SiO １／２ Siloxane units (M′ units) represented by R ４ 'R ５ 'SiO ２／２ Siloxane units (D′ units) represented by the formula: ６ 'SiO ３／２ and a polyorganosiloxane (a1') containing at least one unit selected from the group consisting of M' units, D' units, and T' units, and SiO ２ Siloxane units (Q″ units) represented by R １ "R ２ "R ３ "SiO １／２ Siloxane units (M″ units) represented by R ４ "R ５ "SiO ２／２ Siloxane units (D″ units) represented by the formula: ６ "SiO ３／２ and a polyorganosiloxane (a2') containing one or more units selected from the group consisting of siloxane units (T" units) represented by the following formula: and containing at least one unit selected from the group consisting of M" units, D" units, and T" units. Note that (a1') is an example of (a1), and (a2') is an example of (a2).

[0031] R １ ~R ６ are groups or atoms bonded to the silicon atom, and each independently represents an optionally substituted alkyl group, an optionally substituted alkenyl group, or a hydrogen atom. Examples of the substituent include a halogen atom, a nitro group, a cyano group, an amino group, a hydroxyl group, a carboxyl group, an aryl group, and a heteroaryl group.

[0032] R １ '~R６ R ′ is a group bonded to a silicon atom, and each independently represents an optionally substituted alkyl group or an optionally substituted alkenyl group. １ '~R ６ At least one of the groups ' is an alkenyl group which may be substituted. Examples of the substituent include a halogen atom, a nitro group, a cyano group, an amino group, a hydroxy group, a carboxyl group, an aryl group, and a heteroaryl group.

[0033] R １ "~R ６ " are groups or atoms bonded to the silicon atom, and each independently represents an optionally substituted alkyl group or a hydrogen atom, but R １ "~R ６ At least one of " is a hydrogen atom. Examples of the substituent include a halogen atom, a nitro group, a cyano group, an amino group, a hydroxy group, a carboxyl group, an aryl group, and a heteroaryl group.

[0034] As described above, polysiloxane (A1) contains polyorganosiloxane (a1') and polyorganosiloxane (a2'), and the alkenyl group contained in polyorganosiloxane (a1') and the hydrogen atom (Si-H group) contained in polyorganosiloxane (a2') form a crosslinked structure through a hydrosilylation reaction with catalyst (A-3), and then the crosslinked structure is cured. As a result, a cured film is formed.

[0035] When one embodiment (part 1) of the adhesive composition contains (a1) and (a2), in a preferred aspect of the present invention, the molar ratio of the alkenyl groups contained in the polyorganosiloxane (a1) to the hydrogen atoms constituting the Si—H bonds contained in the polyorganosiloxane (a2) is in the range of 1.0:0.5 to 1.0:0.66.

[0036] The weight average molecular weight of polysiloxanes such as polyorganosiloxane (a1) and polyorganosiloxane (a2) is not particularly limited, but is usually 500 to 1,000,000, and from the viewpoint of realizing the effects of the present invention with good reproducibility, it is preferably 5,000 to 50,000. In the present invention, the weight average molecular weight, number average molecular weight, and dispersity of the polyorganosiloxane can be measured using, for example, a GPC apparatus (EcoSEC, HLC-8320GPC manufactured by Tosoh Corporation) and a GPC column (TSKgel SuperMultiporeHZ-N, TSKgel SuperMultiporeHZ-H manufactured by Tosoh Corporation), a column temperature of 40 ° C., tetrahydrofuran as an eluent (elution solvent), a flow rate (flow rate) of 0.35 mL / min, and polystyrene (Shodex manufactured by Showa Denko K.K.) as a standard sample.

[0037] --Catalyst (A-3)-- The catalyst (A-3) is not particularly limited as long as it is a catalyst that promotes the hydrosilylation reaction between an alkenyl group and a Si—H group. Examples of the catalyst (A-3) include platinum group metal catalysts. Platinum group metal catalysts are platinum-based metal catalysts.

[0038] Specific examples of platinum-based metal catalysts that can be used include known platinum-based compounds (platinum or compounds containing platinum). Specific examples include platinum fine powder, platinum black, chloroplatinic acid, alcohol-modified chloroplatinic acid, complexes of chloroplatinic acid and diolefins, platinum-olefin complexes, platinum-carbonyl complexes (platinum bis(acetoacetate), platinum bis(acetylacetonate), etc.), chloroplatinic acid-alkenylsiloxane complexes (chloroplatinic acid-divinyltetramethyldisiloxane complex, chloroplatinic acid-tetravinyltetramethylcyclotetrasiloxane complex, etc.), platinum-alkenylsiloxane complexes (platinum-divinyltetramethyldisiloxane complex, platinum-tetravinyltetramethylcyclotetrasiloxane complex, etc.), and complexes of chloroplatinic acid and acetylene alcohols. Among these, platinum-alkenylsiloxane complexes are particularly preferred due to their high hydrosilylation reaction-accelerating effect. These hydrosilylation reaction catalysts may be used either individually or in combination of two or more.

[0039] The content of catalyst (A-3) in one embodiment (part 1) of the adhesive composition is not particularly limited, but is, for example, in the range of 0.1 to 50.0 ppm relative to the total mass of component (A-1) and component (A-2).

[0040] --Polymerization Inhibitor-- The adhesive component may contain a polymerization inhibitor for the purpose of inhibiting the progress of the hydrosilylation reaction.

[0041] -Release Agent Component- The release agent component is not particularly limited, but from the viewpoint of more suitably obtaining the effects of the present invention, polyorganosiloxane is preferred. The polyorganosiloxane used as the release agent component usually does not react with the adhesive component. For example, the polyorganosiloxane used as the release agent component is a component that does not undergo a hydrosilylation reaction.

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

[0043] The content of the release agent component in one embodiment (part 1) of the adhesive composition is not particularly limited, but from the viewpoint of suitably obtaining the effects of the present invention, it is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and particularly preferably 0.10% by mass or more, relative to the non-volatile content of the adhesive composition. The upper limit is not particularly limited, but is, for example, preferably 30% by mass or less, more preferably 25% by mass or less, and particularly preferably 20% by mass or less. The non-volatile content of the adhesive composition refers to components other than the solvent in the adhesive composition.

[0044] -Solvent- One embodiment (part 1) of the adhesive composition may contain a solvent for purposes such as adjusting viscosity. Specific examples include, but are not limited to, aliphatic hydrocarbons, aromatic hydrocarbons, and ketones. More specific examples include, but are not limited to, hexane, heptane, octane, nonane, isononane, decane, undecane, dodecane, isododecane, menthane, limonene, toluene, xylene, mesitylene, cumene, MIBK (methyl isobutyl ketone), butyl acetate, diisobutyl ketone, 2-octanone, 2-nonanone, 5-nonanone, cyclohexanone, propylene glycol monomethyl ether acetate, and propylene glycol monomethyl ether. Such solvents may be used alone or in combination of two or more.

[0045] When one embodiment (No. 1) of the adhesive composition contains a solvent, the content of the solvent is appropriately set taking into consideration the desired viscosity of the composition, the coating method to be used, the thickness of the thin film to be produced, and the like, but is, for example, in the range of about 10 to 90 mass % with respect to the entire composition.

[0046] The viscosity of one embodiment (part 1) of the adhesive composition is not particularly limited, but is usually 500 to 20,000 mPa·s, and preferably 1,000 to 1,0000 mPa·s at 25°C.

[0047] One embodiment (part 1) of the adhesive composition includes, for example, the temporary adhesives described in International Publication Nos. 2017 / 221772 and 2018 / 216732, the contents of which are incorporated herein by reference in their entirety to the same extent as if set forth in their entirety.

[0048] <<<<One Embodiment (Part 2) of Adhesive Composition>>> One embodiment (Part 2) of the adhesive composition contains a linear polyorganosiloxane (a1) having a silicon-bonded alkenyl group having 2 to 40 carbon atoms, and a linear polyorganosiloxane (a2) having a Si—H group. One embodiment (Part 2) of the adhesive composition does not contain a polyorganosiloxane having Q units.

[0049] While investigating the temporary bonding of a compound semiconductor substrate and a support substrate, the present inventors found that when an adhesive composition contained a polyorganosiloxane having Q units (e.g., an MQ resin), gas was generated during high-temperature treatment. The generation of gas can lead to undesired peeling due to a decrease in temporary adhesive strength, or to poor peeling during the peeling process. Therefore, the present inventors discovered that gas generation during high-temperature treatment can be suppressed by not including a polyorganosiloxane having Q units in the adhesive composition.

[0050] Q units are SiO ２ The polyorganosiloxane having Q units may have M units, D units, or T units. The M units are represented by R １ｘ R ２ｘ R ３ｘ SiO １／２ The D unit is a siloxane unit represented by R ４ｘ R ５ｘ SiO ２／２ The T unit is a siloxane unit represented by R ６ｘ SiO ３／２ R is a siloxane unit represented by the formula: １ｘ ~R ６ｘare, for example, each independently a monovalent chemical group that is an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or a hydrogen atom, and are bonded to a silicon atom by a Si-C bond or a Si-H bond. An example of an alkyl group having 1 to 10 carbon atoms is a methyl group. An example of an alkenyl group having 2 to 10 carbon atoms is a vinyl group.

[0051] - Linear Polyorganosiloxane (a1) In one embodiment (part 2) of the adhesive composition, the linear polyorganosiloxane (a1) has an alkenyl group having 2 to 40 carbon atoms bonded to a silicon atom. The linear polyorganosiloxane (a1) in one embodiment (part 2) of the adhesive composition is represented, for example, by the following formula (a1). (In formula (a1), R １ａ each independently represents an alkenyl group having 2 to 40 carbon atoms or an alkyl group which may be substituted. １ａ At least one of the groups is an alkenyl group having 2 to 40 carbon atoms. s represents an integer of 1 or more.

[0052] In one example, R １ａ At least two of the groups are alkenyl groups. In one example, the average degree of polymerization, represented by s+2, is 50 to 2000.

[0053] The alkenyl group may be linear, branched, or cyclic, and the number of carbon atoms therein is not particularly limited, but is usually 2 to 40, preferably 30 or less, more preferably 20 or less, and even more preferably 10 or less. Specific examples of the alkenyl group include a vinyl group, an allyl group, a butenyl group, and a pentenyl group.

[0054] R １ａThe optionally substituted alkyl group in may be linear, branched, or cyclic, but is preferably a linear or branched alkyl group, and the number of carbon atoms therein is not particularly limited, but is usually 1 to 40, preferably 30 or less, more preferably 20 or less, and even more preferably 10 or less. Examples of the substituent include a halogen atom, a nitro group, a cyano group, an amino group, a hydroxy group, a carboxyl group, an aryl group, and a heteroaryl group. Specific examples of the optionally substituted straight-chain or branched-chain alkyl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, an s-butyl group, a tertiary butyl group, an n-pentyl group, a 1-methyl-n-butyl group, a 2-methyl-n-butyl group, a 3-methyl-n-butyl group, a 1,1-dimethyl-n-propyl group, a 1,2-dimethyl-n-propyl group, a 2,2-dimethyl-n-propyl group, a 1-ethyl-n-propyl group, an n-hexyl group, a 1-methyl-n-pentyl group, a 2-methyl-n-pentyl group, a 3-methyl-n-pentyl group, and a 4-methyl-n-pentyl group. Examples of such alkyl groups include, but are not limited to, a 1,1-dimethyl-n-butyl group, a 1,2-dimethyl-n-butyl group, a 1,3-dimethyl-n-butyl group, a 2,2-dimethyl-n-butyl group, a 2,3-dimethyl-n-butyl group, a 3,3-dimethyl-n-butyl group, a 1-ethyl-n-butyl group, a 2-ethyl-n-butyl group, a 1,1,2-trimethyl-n-propyl group, a 1,2,2-trimethyl-n-propyl group, a 1-ethyl-1-methyl-n-propyl group, and a 1-ethyl-2-methyl-n-propyl group, and the number of carbon atoms is usually 1 to 14, preferably 1 to 10, and more preferably 1 to 6. Of these, a methyl group is particularly preferred.

[0055] The viscosity of the linear polyorganosiloxane (a1) in one embodiment (part 2) of the adhesive composition is not particularly limited, but is typically 10 to 100,000 mPa s, and preferably 100 to 10,000 mPa s, at 25° C. In the present invention, the viscosity is measured at 25° C. using an E-type rotational viscometer.

[0056] - Linear Polyorganosiloxane (a2) - The linear polyorganosiloxane (a2) in one embodiment (part 2) of the adhesive composition has a Si-H group. The linear polyorganosiloxane (a2) in one embodiment (part 2) of the adhesive composition is represented by, for example, the following formula (a2). (In formula (a2), R １ｂ each independently represents an alkyl group which may be substituted; a and d are 0 or 1, and a+d=2; b and c are each independently an integer of 0 or more; at least one of c and d is not 0; a+b+c+d represents an integer of 5 to 80.

[0057] The linear polyorganosiloxane (a2) represented by formula (a2) satisfies, for example, the following formula (a21): 0.05≦(c+d) / (a+b+c+d)≦0.70 (a2-1)

[0058] R １ｂ Specific examples and preferred examples of the optionally substituted alkyl group in R １ａ Specific examples and preferred examples of the optionally substituted alkyl group in the above formula (1) are mentioned.

[0059] The viscosity of the linear polyorganosiloxane (a2) in one embodiment (part 2) of the adhesive composition is not particularly limited, but is typically 10 to 100,000 mPa·s, preferably 100 to 10,000 mPa·s at 25°C.

[0060] The weight average molecular weight of the polysiloxanes such as polyorganosiloxane (a1) and polyorganosiloxane (a2) in one embodiment (part 2) of the adhesive composition is not particularly limited, but is typically 500 to 1,000,000, and from the viewpoint of realizing the effects of the present invention with good reproducibility, it is preferably 5,000 to 50,000.

[0061] In one embodiment (part 2) of the adhesive composition, the mass ratio (a1:a2) of the linear polyorganosiloxane (a1) to the linear polyorganosiloxane (a2) is not particularly limited, but is preferably 15:1 to 1:1, and more preferably 10:1 to 5:1.

[0062] In one embodiment (part 2) of the adhesive composition, the total content of the linear polyorganosiloxane (a1) and the linear polyorganosiloxane (a2) is not particularly limited, but is preferably 80% by mass to 99.9% by mass, more preferably 95% by mass to 99% by mass, based on the film-constituting components. In the present invention, the film-constituting components refer to components other than the solvent contained in the composition.

[0063] - Catalyst (a3) ​​- One embodiment (part 2) of the adhesive composition may contain a catalyst (a3) ​​to promote the hydrosilylation reaction between the linear polyorganosiloxane (a1) and the linear polyorganosiloxane (a2). The catalyst (a3) ​​is not particularly limited as long as it is a catalyst that promotes the hydrosilylation reaction between an alkenyl group and a Si—H group. Examples of the catalyst (a3) ​​include platinum group metal catalysts. The platinum group metal catalyst is a platinum-based metal catalyst.

[0064] Specific examples of platinum-based metal catalysts that can be used include known platinum-based compounds (platinum or compounds containing platinum), such as those listed in the description of catalyst (A-3) in one embodiment (part 1) of the adhesive composition.

[0065] The content of the catalyst (a3) ​​in one embodiment (part 2) of the adhesive composition is not particularly limited, but is, for example, in the range of 0.1 to 50.0 ppm relative to the total mass of the linear polyorganosiloxane (a1) and the linear polyorganosiloxane (a2).

[0066] Polymerization Inhibitor (a4)—The adhesive composition may contain a polymerization inhibitor (a4) for the purpose of inhibiting the progress of the hydrosilylation reaction. The polymerization inhibitor (a4) is not particularly limited as long as it is capable of inhibiting the progress of the hydrosilylation reaction. Specific examples include, but are not limited to, alkynyl alkyl alcohols optionally substituted with an aryl group, such as 1-ethynyl-1-cyclohexanol and 1,1-diphenyl-2-propyn-1-ol.

[0067] In one embodiment (part 2) of the adhesive composition, the linear polyorganosiloxane (a1), the linear polyorganosiloxane (a2), the catalyst (a3), and the polymerization inhibitor (a4) are sometimes referred to as adhesive components.

[0068] -Release Agent Component- From the viewpoint of optimally achieving the effects of the present invention, one embodiment (part 2) of the adhesive composition preferably does not contain a release agent component. The release agent component is not particularly limited, but from the viewpoint of more optimally achieving the effects of the present invention, polyorganosiloxane is preferred. The polyorganosiloxane used as the release agent component does not usually react with the adhesive component. For example, the polyorganosiloxane used as the release agent component is a component that does not undergo a hydrosilylation reaction.

[0069] The polyorganosiloxane is not particularly limited, and examples thereof include polydimethylsiloxane, epoxy group-containing polyorganosiloxane, phenyl group-containing polyorganosiloxane, and carbinol-modified polyorganosiloxane.

[0070] -Solvent- One embodiment (part 2) of the adhesive composition may contain a solvent for purposes such as adjusting viscosity. Specific examples include, but are not limited to, aliphatic hydrocarbons, aromatic hydrocarbons, and ketones. More specific examples include, but are not limited to, hexane, heptane, octane, nonane, isononane, decane, undecane, dodecane, isododecane, menthane, limonene, toluene, xylene, mesitylene, cumene, MIBK (methyl isobutyl ketone), butyl acetate, diisobutyl ketone, 2-octanone, 2-nonanone, 5-nonanone, cyclohexanone, propylene glycol monomethyl ether acetate, and propylene glycol monomethyl ether. Such solvents may be used alone or in combination of two or more.

[0071] When one embodiment (part 2) of the adhesive composition contains a solvent, the content of the solvent is appropriately set taking into consideration the desired viscosity of the composition, the coating method to be used, the thickness of the thin film to be produced, and the like, but is, for example, in the range of about 10 to 90 mass % with respect to the entire composition.

[0072] The viscosity of the adhesive composition according to one embodiment (part 2) is not particularly limited, but is usually 500 to 20,000 mPa·s, and preferably 1,000 to 1,0000 mPa·s at 25°C.

[0073] <<<<One Embodiment (Part 3) of Adhesive Composition>>> One embodiment (Part 3) of the adhesive composition is an adhesive composition including: Resin A, which includes a repeating unit represented by formula (1) below and has a weight average molecular weight of 500 to 500,000; and Resin B, which includes a siloxane skeleton: (In formula (1), R １ ~R ３ are each independently a hydrogen atom, a hydroxyl group, or a monovalent organic group having 1 to 20 carbon atoms, and R １ ~R ３ At least one of R is a hydroxy group. ４ is a hydrogen atom or a monovalent organic group having 1 to 30 carbon atoms which may have a substituent.

[0074] An example of an embodiment (part 3) of the adhesive composition is the adhesive composition described in JP 2018-64092 A. The contents of this publication are incorporated herein by reference to the same extent as if set forth in their entirety.

[0075] <<<<One Embodiment (Part 4) of Adhesive Composition>>> One embodiment (Part 4) of the adhesive composition is a temporary adhesive containing a compound containing a lipophilic group and a fluorine atom, and a compound containing a silicon atom. The compound containing a lipophilic group and a fluorine atom is preferably liquid at 25°C. The compound containing a lipophilic group and a fluorine atom preferably has a 10% thermal mass loss temperature of 250°C or higher when heated from 25°C at a rate of 20°C / min. The compound containing a silicon atom preferably has a crosslinkable group. The temporary adhesive preferably further contains a crosslinking agent that crosslinks the crosslinkable group. The compound containing a silicon atom preferably has a Si—H structure. The compound containing a vinyl group preferably has a siloxane bond.

[0076] An example of an embodiment (part 4) of the adhesive composition is the temporary adhesive described in International Publication No. 2016 / 181879, the contents of which are incorporated herein by reference in their entirety to the same extent as if set forth in full.

[0077] <<<<One Embodiment (Part 5) of Adhesive Composition>>> One embodiment (Part 5) of the adhesive composition is an adhesive composition containing, as resin component (P), a hydrocarbon resin (P1) and a resin (P2) (excluding the hydrocarbon resin (P1)) having a glass transition temperature of 180°C or higher. The resin (P2) preferably has a structural unit (u21) derived from a monomer containing a maleimide skeleton. The structural unit (u21) is preferably a structural unit represented by the following general formula (p2-1): [In the formula, R ｕ１０ represents an organic group having 1 to 30 carbon atoms.

[0078] The resin (P2) preferably further includes a structural unit (u22) derived from a cycloolefin. The structural unit (u22) is preferably a structural unit represented by the following general formula (p2-2): [In the formula, R ｕ１１ ~R ｕ１４ each independently represents an organic group having 1 to 30 carbon atoms or a hydrogen atom, and n is an integer of 0 to 2.

[0079] An example of an embodiment (part 5) of the adhesive composition is the adhesive composition described in JP 2018-188613 A. The contents of this publication are incorporated herein by reference to the same extent as if set forth in their entirety.

[0080] <<<Sixth Embodiment of Adhesive Composition>>> One sixth embodiment of the adhesive composition is a bonding composition including a tackifier and a compound selected from the group consisting of rubber, styrene-isoprene-styrene, styrene-butadiene-styrene, halogenated butyl rubber, and mixtures thereof.

[0081] An example of an embodiment (No. 6) of the adhesive composition is the bonding composition described in JP-A-2010-506406, the contents of which are incorporated herein by reference in their entirety to the same extent as if set forth in full.

[0082] <<<<One Embodiment (Part 7) of the Adhesive Composition>>> One embodiment (Part 7) of the adhesive composition is a bonding composition dispersed or dissolved in a solvent system and comprising a compound selected from the group consisting of imide, amide-imide, and amide-imide-siloxane polymers and oligomers. The compound is preferably selected from the group consisting of polymers and oligomers having repeating units of Formula (I) and Formula (II) below, and further has end-capping groups derived from a compound selected from the group consisting of an aromatic monoamine, an aliphatic monoamine, an alicyclic monoamine, and phthalic anhydride. wherein R is and, (In the formula, R １ is alkyl-substituted phenyl, and and X is selected from the group consisting of phenyl sulfone, aromatic compounds which may have an ether bridge, aliphatic compounds, and alicyclic compounds. (Wherein Z is and and a moiety having an ether bridge selected from the group consisting of:

[0083] An example of an embodiment (part 7) of the adhesive composition is the bonding composition described in JP-A-2010-531385, the contents of which are incorporated herein by reference in their entirety to the same extent as if set forth in full.

[0084] The adhesive layer may also be the separation layer described in JP 2019-5999 A. The adhesive layer may also be the adhesive layer described in JP 2017-108116 A. The adhesive layer may also be the temporary adhesive material for wafer processing described in JP 2018-046095 A. In addition, in these publications, when the adhesive layer is composed of multiple layers, the multiple layers may be considered as adhesive layers in the laminate of the present invention, or the multiple layers may be considered as a laminate structure of adhesive layers and release agent layers in the laminate of the present invention. The contents of these publications are incorporated herein to the same extent as if they were expressly set forth in their entirety.

[0085] <Release Agent Layer> The laminate may have a release agent layer. In a laminate having a release agent layer, the compound semiconductor substrate and the support substrate are separated, for example, by irradiating the release agent layer with light. The release agent layer is provided between the compound semiconductor substrate and the support substrate. The release agent layer is in contact with, for example, an adhesive layer. The release agent layer is provided between, for example, an adhesive layer and the support substrate. The release agent layer is formed, for example, from a release agent composition.

[0086] The thickness of the release agent layer is not particularly limited, but is usually 5 nm to 100 μm, in one embodiment 10 nm to 10 μm, in another embodiment 50 nm to 1 μm, and in still another embodiment 100 nm to 700 nm.

[0087] <<Release Agent Composition>> The release agent composition contains, for example, at least an organic resin or a polynuclear phenol derivative, and further contains other components as necessary. The organic resin is preferably one that can exhibit suitable release ability, and when the compound semiconductor substrate and the support substrate are separated by irradiating the release agent layer with light, the organic resin is one that absorbs light and suitably undergoes a change in quality, such as decomposition, required to improve the release ability.

[0088] A laminate having a release agent layer formed from the release agent composition can be peeled off without applying an excessive load for peeling, for example, by irradiating the release agent layer with a laser. The release agent layer provided in the laminate has an adhesive strength that is reduced by, for example, laser irradiation compared to before irradiation. That is, in the laminate, for example, while a compound semiconductor substrate is being processed, such as thinned, the compound semiconductor substrate is suitably supported on a laser-transparent support substrate via an adhesive layer and a release agent layer. After processing is completed, by irradiating a laser from the support substrate side, the laser that has transmitted through the support substrate is absorbed by the release agent layer, causing alteration (e.g., separation) of the release agent layer at the interface between the release agent layer and the adhesive layer, at the interface between the release agent layer and the support substrate, or inside the release agent layer. As a result, suitable peeling (separation) can be achieved without applying an excessive load for peeling.

[0089] Examples of organic resins include novolac resins, etc. Details of these will be described later.

[0090] In a preferred embodiment, the release agent composition contains at least a novolac resin, and further contains other components such as a crosslinker, an acid generator, an acid, a surfactant, a solvent, etc., as needed. In another preferred embodiment, the release agent composition contains at least a polynuclear phenol derivative and a crosslinker, and further contains other components such as an acid generator, an acid, a surfactant, a solvent, etc. In another preferred embodiment, the release agent composition contains at least an organic resin and a branched-chain polysilane, and further contains other components such as a crosslinker, an acid generator, an acid, a surfactant, a solvent, etc., as needed.

[0091] <<<Novolac Resin>>> A novolac resin is a resin obtained by, for example, subjecting at least one of a phenolic compound, a carbazole compound, and an aromatic amine compound to a condensation reaction with at least one of an aldehyde compound, a ketone compound, and a divinyl compound in the presence of an acid catalyst.

[0092] Examples of phenolic compounds include phenols, naphthols, anthrols, and hydroxypyrenes. Examples of phenols include phenol, cresol, xylenol, resorcinol, bisphenol A, p-tert-butylphenol, p-octylphenol, 9,9-bis(4-hydroxyphenyl)fluorene, and 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane. Examples of naphthols include 1-naphthol, 2-naphthol, 1,5-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, and 9,9-bis(6-hydroxynaphthyl)fluorene. Examples of anthrols include 9-anthrole. Examples of hydroxypyrenes include 1-hydroxypyrene and 2-hydroxypyrene. Examples of the carbazole compound include carbazole, 1,3,6,8-tetranitrocarbazole, 3,6-diaminocarbazole, 3,6-dibromo-9-ethylcarbazole, 3,6-dibromo-9-phenylcarbazole, 3,6-dibromocarbazole, 3,6-dichlorocarbazole, 3-amino-9-ethylcarbazole, 3-bromo-9-ethylcarbazole, 4,4'-bis(9H-carbazol-9-yl)biphenyl, 4-glycidylcarbazole, 4-hydroxycarbazole, 9-(1H-benzotriazol-1-yl)methylcarbazole, 4 ... Examples of aromatic amine compounds include diphenylamine and N-phenyl-1-naphthylamine. These compounds may be used alone or in combination of two or more. These compounds may have a substituent.For example, they may have a substituent on the aromatic ring.

[0093] Examples of aldehyde compounds include formaldehyde, paraformaldehyde, acetaldehyde, propylaldehyde, butyraldehyde, isobutyraldehyde, valeraldehyde, capronaldehyde, 2-methylbutyraldehyde, hexylaldehyde, undecanoic aldehyde, 7-methoxy-3,7-dimethyloctyl aldehyde, cyclohexane aldehyde, 3-methyl-2-butyraldehyde, glyoxal, malonaldehyde, succinaldehyde, glutaraldehyde, and adipic acid. Examples of the ketone compound include saturated aliphatic aldehydes such as benzoic acid aldehyde, unsaturated aliphatic aldehydes such as acrolein and methacrolein, heterocyclic aldehydes such as furfural and pyridine aldehyde, and aromatic aldehydes such as benzaldehyde, naphthyl aldehyde, anthryl aldehyde, phenanthryl aldehyde, salicyl aldehyde, phenylacetaldehyde, 3-phenylpropionaldehyde, tolyl aldehyde, (N,N-dimethylamino)benzaldehyde, and acetoxybenzaldehyde. Among these, aromatic aldehydes are preferred. Examples of the ketone compound include diaryl ketone compounds such as diphenyl ketone, phenyl naphthyl ketone, dinaphthyl ketone, phenyl tolyl ketone, and ditolyl ketone. Examples of divinyl compounds include divinylbenzene, dicyclopentadiene, tetrahydroindene, 4-vinylcyclohexene, 5-vinylnoborna-2-ene, divinylpyrene, limonene, 5-vinylnorbornadiene, etc. These can be used alone or in combination of two or more.

[0094] The novolac resin is, for example, a novolac resin that absorbs light irradiated from the support substrate side and changes in quality, for example, by photolysis.

[0095] The novolac resin contains, for example, at least one of a structural unit represented by the following formula (C1-1), a structural unit represented by the following formula (C1-2), and a structural unit represented by the following formula (C1-3).

[0096]

[0097] In the formula, C １ represents a group derived from an aromatic compound containing a nitrogen atom, C ２ represents a group containing a tertiary carbon atom having at least one member selected from the group consisting of a secondary carbon atom, a quaternary carbon atom, and an aromatic ring in a side chain, and C ３ represents a group derived from an aliphatic polycyclic compound, C ４ represents a group derived from phenol, a group derived from bisphenol, a group derived from naphthol, a group derived from biphenyl, or a group derived from biphenol.

[0098] That is, the novolac resin contains, for example, one or more of the following structural units: A structural unit having a bond between a group derived from an aromatic compound containing a nitrogen atom and a group containing a tertiary carbon atom having at least one carbon atom selected from the group consisting of a secondary carbon atom, a quaternary carbon atom, and an aromatic ring in its side chain (formula (C1-1)); A structural unit having a bond between a group derived from an aromatic compound containing a nitrogen atom and a group derived from an aliphatic polycyclic compound (formula (C1-2)); A structural unit having a bond between a group derived from a phenol, a group derived from a bisphenol, a group derived from a naphthol, a group derived from a biphenyl, or a group derived from a biphenol and a group containing a tertiary carbon atom having at least one carbon atom selected from the group consisting of a quaternary carbon atom and an aromatic ring in its side chain (formula (C1-3)).

[0099] In a preferred embodiment, the novolak resin contains either or both of a structural unit (formula (C1-1)) having a bond between a group derived from an aromatic compound containing a nitrogen atom and a group containing a tertiary carbon atom having at least one kind selected from the group consisting of a secondary carbon atom, a quaternary carbon atom, and an aromatic ring in its side chain, and a structural unit (formula (C1-2)) having a bond between a group derived from an aromatic compound containing a nitrogen atom and a group derived from an aliphatic polycyclic compound.

[0100] C １ Examples of the group derived from an aromatic compound containing a nitrogen atom include, but are not limited to, a group derived from carbazole, a group derived from N-phenyl-1-naphthylamine, and a group derived from N-phenyl-2-naphthylamine.２ Examples of the group containing a tertiary carbon atom having at least one selected from the group consisting of a secondary carbon atom, a quaternary carbon atom, and an aromatic ring in a side chain include, but are not limited to, a group derived from 1-naphthaldehyde, a group derived from 1-pyrenecarboxaldehyde, a group derived from 4-(trifluoromethyl)benzaldehyde, and a group derived from acetaldehyde. ３ The group derived from an aliphatic polycyclic compound of can be, but is not limited to, a group derived from dicyclopentadiene. ４ is a group derived from phenol, a group derived from bisphenol, a group derived from naphthol, a group derived from biphenyl, or a group derived from biphenol.

[0101] In a preferred embodiment, the novolak resin contains, as the structural unit represented by formula (C1-1), for example, a structural unit represented by formula (C1-1-1) below.

[0102]

[0103] In formula (C1-1-1), R ９０１ and R ９０２ represents a substituent substituted on the ring, and each independently represents a halogen atom, a nitro group, a cyano group, an amino group, a hydroxy group, a carboxy group, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group. ９０３ represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group. ９０４ represents a hydrogen atom, an optionally substituted aryl group, or an optionally substituted heteroaryl group. ９０５ represents an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted heteroaryl group. ９０４ and R ９０５The groups may be bonded to each other to form a divalent group. Examples of substituents on the alkyl and alkenyl groups include halogen atoms, nitro groups, cyano groups, amino groups, hydroxy groups, carboxy groups, aryl groups, and heteroaryl groups. Examples of substituents on the aryl and heteroaryl groups include halogen atoms, nitro groups, cyano groups, amino groups, hydroxy groups, carboxy groups, alkyl groups, and alkenyl groups. １ and h ２ each independently represents an integer of 0 to 3.

[0104] The number of carbon atoms in the optionally substituted alkyl group and the optionally substituted alkenyl group is usually 40 or less, and from the viewpoint of solubility, it is preferably 30 or less, more preferably 20 or less. The number of carbon atoms in the optionally substituted aryl group and heteroaryl group is usually 40 or less, and from the viewpoint of solubility, it is preferably 30 or less, more preferably 20 or less.

[0105] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0106] Specific examples of the structural unit represented by formula (C1-1-1) are listed below, but the present invention is not limited to these.

[0107]

[0108] In a preferred embodiment, the novolak resin contains, as the structural unit represented by formula (C1-1), for example, a structural unit represented by the following formula (C1-1-2).

[0109]

[0110] In formula (C1-1-2), Ar ９０１ and Ar ９０２ each independently represents an aromatic ring such as a benzene ring or a naphthalene ring, and R ９０１ ~R ９０５ and h １ and h ２ has the same meaning as above.

[0111] Specific examples of the structural unit represented by formula (C1-1-2) are listed below, but the present invention is not limited to these.

[0112]

[0113] In a preferred embodiment, the novolak resin contains, as the structural unit represented by formula (C1-2), for example, a structural unit represented by the following formula (C1-2-1) or (C1-2-2).

[0114]

[0115] In the above formula, R ９０６ ~R ９０９ are substituents bonded to the ring, each independently representing a halogen atom, a nitro group, a cyano group, an amino group, a hydroxy group, a carboxy group, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group, and specific examples and suitable numbers of carbon atoms of the halogen atom, the optionally substituted alkyl group, the optionally substituted alkenyl group, and the optionally substituted aryl group are the same as those described above, and h ３ ~h ６ each independently represents an integer of 0 to 3; R ９０１ ~R ９０３ and h １ and h ２ has the same meaning as above.

[0116] Specific examples of the structural units represented by formulae (C1-2-1) and (C1-2-2) are listed below, but are not limited to these.

[0117]

[0118] Specific examples of the structural unit represented by formula (C1-3) are listed below, but the present invention is not limited to these.

[0119]

[0120] As described above, novolac resins are resins obtained by, for example, condensation reaction of at least one of a phenolic compound, a carbazole compound, and an aromatic amine compound with at least one of an aldehyde compound, a ketone compound, and a divinyl compound in the presence of an acid catalyst. In this condensation reaction, for example, 0.1 to 10 equivalents of the aldehyde compound or ketone compound are typically used per equivalent of the benzene ring constituting the ring of the carbazole compound.

[0121] In the condensation reaction, an acid catalyst is usually used. Examples of the acid catalyst include, but are not limited to, mineral acids such as sulfuric acid, phosphoric acid, and perchloric acid; organic sulfonic acids such as p-toluenesulfonic acid and p-toluenesulfonic acid monohydrate; and carboxylic acids such as formic acid and oxalic acid. The amount of the acid catalyst cannot be generally specified because it is determined appropriately depending on the type of acid used, etc., but is usually determined appropriately in the range of 0.001 to 10,000 parts by mass per 100 parts by mass of the carbazole compound.

[0122] The condensation reaction can be carried out without a solvent if either the starting compounds or the acid catalyst used are liquid, but is usually carried out using a solvent. Such a solvent is not particularly limited as long as it does not inhibit the reaction, and typical examples include ether compounds such as cyclic ether compounds such as tetrahydrofuran and dioxane.

[0123] The reaction temperature is usually appropriately set within the range of 40° C. to 200° C. The reaction time cannot be generally defined since it varies depending on the reaction temperature, but is usually appropriately set within the range of 30 minutes to 50 hours.

[0124] After the reaction is completed, if necessary, purification and isolation are carried out according to a standard method, and the obtained novolak resin is used for preparing a release agent composition. A person skilled in the art can determine the production conditions of the novolak resin without undue burden based on the above explanation and technical common sense, and therefore can produce the novolak resin.

[0125] The weight-average molecular weight of the organic resin such as a novolac resin is usually 500 to 200,000. From the viewpoint of ensuring solubility in a solvent, mixing well with the branched-chain polysilane when formed into a film, and obtaining a uniform film, the weight-average molecular weight is preferably 100,000 or less, more preferably 50,000 or less, even more preferably 10,000 or less, still more preferably 5,000 or less, and still more preferably 3,000 or less. From the viewpoint of improving the strength of the film, the weight-average molecular weight is preferably 600 or more, more preferably 700 or more, even more preferably 800 or more, still more preferably 900 or more, and still more preferably 1,000 or more. In the present invention, the weight average molecular weight, number average molecular weight, and dispersity of an organic resin such as a polymer novolac resin can be measured, for example, using a GPC apparatus (EcoSEC, HLC-8320GPC, manufactured by Tosoh Corporation) and a GPC column (TSKgel SuperMultiporeHZ-N, TSKgel SuperMultiporeHZ-H, manufactured by Tosoh Corporation), at a column temperature of 40°C, using tetrahydrofuran as an eluent (elution solvent), at a flow rate (flow rate) of 0.35 mL / min, and using polystyrene (manufactured by Sigma-Aldrich) as a standard sample.

[0126] The organic resin contained in the release agent composition is preferably a novolac resin, and therefore, the release agent composition preferably contains only a novolac resin as the organic resin, but may contain other polymers together with the novolac resin for the purpose of adjusting the film properties, etc. Examples of such other polymers include polyacrylic acid ester compounds, polymethacrylic acid ester compounds, polyacrylamide compounds, polymethacrylamide compounds, polyvinyl compounds, polystyrene compounds, polymaleimide compounds, polymaleic anhydrides, polyacrylonitrile compounds, etc.

[0127] The content of the novolac resin in the release agent composition is not particularly limited, but is preferably 70% by mass or more based on the total amount of polymers contained in the release agent composition. The content of the novolac resin in the release agent composition is not particularly limited, but is preferably 50 to 100% by mass based on the film-constituting components. In the present invention, the film-constituting components refer to components other than the solvent contained in the composition.

[0128] <<<Polynuclear Phenol Derivative>>> The polynuclear phenol derivative is represented, for example, by formula (P) below.

[0129] In formula (P), Ar represents an arylene group, and the number of carbon atoms therein is not particularly limited, but is usually 6 to 60. From the viewpoint of preparing a release agent composition having excellent uniformity and reproducibly obtaining a release agent layer having higher flatness, the number of carbon atoms therein is preferably 30 or less, more preferably 20 or less, even more preferably 18 or less, and still more preferably 12 or less.

[0130] Specific examples of such an arylene group include 1,2-phenylene, 1,3-phenylene, 1,4-phenylene; 1,5-naphthalenediyl, 1,8-naphthalenediyl, 2,6-naphthalenediyl, 2,7-naphthalenediyl, 1,2-anthracenediyl, 1,3-anthracenediyl, 1,4-anthracenediyl, 1,5-anthracenediyl, 1,6-anthracenediyl, 1,7-anthracenediyl, 1,8-anthracenediyl, and 2,3-anthracenediyl. Examples of the anthracene-4,4′-diyl group include, but are not limited to, groups derived by removing two hydrogen atoms on the aromatic ring of a fused-ring aromatic hydrocarbon compound, such as anthracene-4,6-diyl, 2,7-anthracene-4,9-diyl, 2,10-anthracene-4,10-diyl, and 9,10-anthracene-4,4′-diyl group, and groups derived by removing two hydrogen atoms on the aromatic ring of a biphenyl-4,4′-diyl group and para-terphenyl-4,4″-diyl group.

[0131] From the viewpoint of providing a release agent layer exhibiting good releasability and reproducibly obtaining a laminate from which the support substrate can be easily separated, the polynuclear phenol derivative represented by formula (P) is preferably a polynuclear phenol derivative represented by formula (P-1), more preferably a polynuclear phenol derivative represented by formula (P-1-1), and even more preferably a polynuclear phenol derivative represented by formula (P1).

[0132]

[0133] The content of the polynuclear phenol derivative in the stripping composition is not particularly limited, but is preferably 50 to 100% by mass based on the film-constituting components.

[0134] <<<Branched Polysilane>>> The release agent composition may contain a branched polysilane. The branched polysilane has a Si—Si bond and a branched structure. By including a branched polysilane in the release agent composition, the release agent layer formed from the obtained film cannot be suitably removed by any of organic solvents, acids, and chemical solutions used in the production of semiconductor devices (such as alkaline developers and hydrogen peroxide solutions), but can be suitably removed by the cleaning composition. As a result, by separating the compound semiconductor substrate and the support substrate of the laminate and then cleaning each substrate with the cleaning composition, the residue of the release agent layer on the substrate can be suitably removed. Although the reason for this is not clear, depending on the type of polysilane terminal group (terminal substituent (atom)), the polysilane can react with an organic resin to form crosslinks. Furthermore, since branched-chain polysilanes have more terminal groups (terminal substituent (atom)) than linear polysilanes, branched-chain polysilanes are thought to have more crosslinking points than linear polysilanes. It is speculated that moderate and suitable curing via such more crosslinking points in the branched-chain polysilanes can achieve both the property of being resistant to removal by organic solvents, acids, and chemical solutions used in the production of semiconductor devices (such as alkaline developers and hydrogen peroxide solutions), and the property of being easily removed by cleaning compositions.

[0135] The branched polysilane preferably contains a structural unit represented by formula (B).

[0136]

[0137] In formula (B), R Ｂ represents a hydrogen atom, a hydroxy group, a silyl group, or an organic group, and specific examples of such organic groups include hydrocarbon groups (optionally substituted alkyl groups, optionally substituted alkenyl groups, optionally substituted aryl groups, and optionally substituted aralkyl groups), and ether groups corresponding to these hydrocarbon groups (optionally substituted alkoxy groups, optionally substituted aryloxy groups, and optionally substituted aralkyloxy groups), and the organic group is usually often a hydrocarbon group such as an alkyl group, alkenyl group, aryl group, or aralkyl group. Furthermore, a hydrogen atom, a hydroxy group, an alkoxy group, a silyl group, or the like is often substituted at the terminal.

[0138] R Ｂ When is the organic group or silyl group, at least one of the hydrogen atoms may be substituted with a substituent, specific examples of which include a hydroxy group, an alkyl group, an aryl group, and an alkoxy group.

[0139] From the viewpoint of preventing unintended peeling when the laminate is brought into contact with an organic solvent, an acid, or a chemical solution used in the manufacture of semiconductor elements (such as an alkaline developer or hydrogen peroxide solution), and from the viewpoint of suitably removing residues of the release agent layer on the substrate when the compound semiconductor substrate and the support substrate of the laminate are separated and then washed with the cleaning agent composition, R Ｂ is preferably an alkyl group or an aryl group, more preferably an aryl group, even more preferably a phenyl group, a 1-naphthyl group or a 2-naphthyl group, and even more preferably a phenyl group.

[0140] The branched-chain polysilane may contain, in addition to the structural unit represented by formula (B), a structural unit represented by formula (S) below or a structural unit represented by formula (N) below. However, from the viewpoint of suppressing unintended peeling when the laminate is brought into contact with any of an organic solvent, an acid, or a chemical solution used in the production of semiconductor devices (such as an alkaline developer or hydrogen peroxide solution), and from the viewpoint of suitably removing residue of the release agent layer on the substrate when the compound semiconductor substrate and the supporting substrate of the laminate are separated and then each substrate is washed with a cleaning composition, the content of the structural unit represented by formula (B) in the branched-chain polysilane is usually 50 mol % or more, preferably 60 mol % or more, more preferably 70 mol % or more, still more preferably 80 mol % or more, even more preferably 90 mol % or more, and still more preferably 95 mol % or more, of all structural units.

[0141] (R Ｓ１ and Ｓ２ is R Ｂ It has the same meaning as

[0142] The terminal group (terminal substituent (atom)) of the branched chain polysilane may usually be a hydrogen atom, a hydroxy group, a halogen atom (such as a chlorine atom), an alkyl group, an aryl group, an alkoxy group, a silyl group, etc. Among these, a hydroxy group, a methyl group, or a phenyl group is often used, and a methyl group is particularly preferred, and the terminal group may also be a trimethylsilyl group.

[0143] In one embodiment, the average degree of polymerization of the branched-chain polysilane, in terms of silicon atoms (i.e., the average number of silicon atoms per molecule), is usually 2 to 100, preferably 3 to 80, more preferably 5 to 50, and even more preferably 10 to 30. In one embodiment, the upper limit of the weight-average molecular weight of the branched-chain polysilane is usually 30,000, preferably 20,000, more preferably 10,000, even more preferably 5,000, even more preferably 2,000, and even more preferably 1,500, and the lower limit is usually 50, preferably 100, more preferably 150, even more preferably 200, even more preferably 300, and even more preferably 500. The average degree of polymerization and weight-average molecular weight of the branched polysilane can be measured, for example, using a GPC apparatus (EcoSEC, HLC-8220GPC manufactured by Tosoh Corporation) and GPC columns (Shodex KF-803L, KF-802, and KF-801 manufactured by Showa Denko K.K., used in this order), at a column temperature of 40°C, using tetrahydrofuran as an eluent (elution solvent), at a flow rate (flow rate) of 1.00 mL / min, and using polystyrene (manufactured by Sigma-Aldrich) as a standard sample. If the degree of polymerization and weight-average molecular weight of the branched-chain polysilane used are too small, the branched-chain polysilane may be vaporized by heating when forming a film that serves as a release agent layer or when processing the resulting laminate comprising the release agent layer, or problems may occur due to poor film strength. On the other hand, if the degree of polymerization and molecular weight of the branched-chain polysilane used are too large, sufficient solubility may not be ensured depending on the type of solvent used in preparing the release agent composition, causing precipitation in the composition, or mixing with the resin may be insufficient, making it difficult to reproducibly obtain a highly uniform film. Therefore, from the viewpoint of more reproducibly obtaining a laminate comprising a release agent layer that contributes to the favorable production of semiconductor elements, it is desirable that the degree of polymerization and weight-average molecular weight of the branched-chain polysilane satisfy the above-mentioned ranges.

[0144] From the viewpoint of reproducibly obtaining a release agent layer having excellent heat resistance, the 5% weight loss temperature of the branched chain polysilane is usually 300° C. or higher, preferably 350° C. or higher, more preferably 365° C. or higher, even more preferably 380° C. or higher, even more preferably 395° C. or higher, and even more preferably 400° C. or higher. The 5% weight loss temperature of the branched chain polysilane can be measured, for example, by using a NETZSCH 2010SR thermometer in air, by increasing the temperature from room temperature (25° C.) to 400° C. at a rate of 10° C. / min.

[0145] When the compound semiconductor substrate and the support substrate of the laminate are separated and then each substrate is washed with a cleaning composition, from the viewpoints of suitably removing the residue of the release agent layer on the substrate and reproducibly preparing a release agent composition with excellent uniformity, the branched-chain polysilane is preferably soluble in any one of ether compounds such as tetrahydrofuran, aromatic compounds such as toluene, glycol ether ester compounds such as propylene glycol monomethyl ether acetate, ketone compounds such as cyclohexanone and methyl ethyl ketone, and glycol ether compounds such as propylene glycol monomethyl ether. In this case, "dissolution" means that when dissolution is attempted using a shaker at room temperature (25°C) to give a 10% by mass solution, dissolution can be visually confirmed within 1 hour.

[0146] The branched chain polysilane may be in either a solid or liquid state at room temperature.

[0147] Branched chain polysilanes can be produced by reference to known methods described in, for example, JP 2011-208054 A, JP 2007-106894 A, JP 2007-145879 A, ​​WO 2005 / 113648 A, etc., or can be obtained as commercially available products. Specific examples of commercially available products include, but are not limited to, silicon materials polysilanes OGSOL SI-20-10 and SI-20-14 manufactured by Osaka Gas Chemicals Co., Ltd.

[0148] Suitable examples of branched polysilanes include, but are not limited to, the following: (Ph represents a phenyl group, R Ｅeach independently represents a terminal substituent, represents an atom or a group, n ｂ indicates the number of repeating units.)

[0149] The content of the branched-chain polysilane in the stripper composition is usually 10 to 90% by mass relative to the film-constituting components. From the viewpoint of reproducibly realizing a film that cannot be suitably removed by organic solvents, acids, or chemical solutions used in the production of semiconductor elements (such as alkaline developers and hydrogen peroxide solutions) but can be suitably removed by the cleaning composition, the content is preferably 15 to 80% by mass, more preferably 20 to 70% by mass, even more preferably 25 to 60% by mass, and still more preferably 30 to 50% by mass.

[0150] <<<Crosslinking Agent>>> The release agent composition may contain a crosslinking agent. The crosslinking agent may undergo a crosslinking reaction by self-condensation, but when crosslinkable substituents are present in the novolak resin, the crosslinking agent can undergo a crosslinking reaction with the crosslinkable substituents.

[0151] Specific examples of crosslinking agents are not particularly limited, but typically include phenol-based crosslinking agents, melamine-based crosslinking agents, urea-based crosslinking agents, and thiourea-based crosslinking agents, each of which has a crosslinking group, such as an alkoxymethyl group (e.g., hydroxymethyl group, methoxymethyl group, or butoxymethyl group), in the molecule; these may be low-molecular-weight compounds or high-molecular-weight compounds. The crosslinking agent contained in the release agent composition usually has two or more crosslinking groups, but from the viewpoint of achieving more suitable curing with good reproducibility, the number of crosslinking groups contained in the crosslinking agent compound is preferably 2 to 10, and more preferably 2 to 6. From the viewpoint of achieving higher heat resistance, the crosslinking agent contained in the release agent composition preferably has an aromatic ring (e.g., a benzene ring or a naphthalene ring) in the molecule; a typical example of such a crosslinking agent includes, but is not limited to, a phenol-based crosslinking agent.

[0152] A phenolic crosslinking agent having a crosslinking group is a compound having a crosslinking group bonded to an aromatic ring and at least one of a phenolic hydroxy group and an alkoxy group derived from the phenolic hydroxy group. Examples of the alkoxy group derived from the phenolic hydroxy group include, but are not limited to, a methoxy group and a butoxy group. The aromatic ring to which the crosslinking group is bonded and the aromatic ring to which the phenolic hydroxy group and / or the alkoxy group derived from the phenolic hydroxy group are bonded are not limited to non-fused aromatic rings such as a benzene ring, but may also be a fused aromatic ring such as a naphthalene ring or anthracene. When multiple aromatic rings are present in the molecule of the phenolic crosslinking agent, the crosslinking group, the phenolic hydroxy group, and the alkoxy group derived from the phenolic hydroxy group may be bonded to the same aromatic ring or to different aromatic rings in the molecule. The aromatic ring to which the crosslinking group, the phenolic hydroxy group, and the alkoxy group derived from the phenolic hydroxy group are bonded may be further substituted with a hydrocarbon group such as an alkyl group (e.g., methyl, ethyl, or butyl), an aryl group (e.g., phenyl), or a halogen atom (e.g., fluorine).

[0153] For example, specific examples of phenol-based crosslinking agents having a crosslinking group include compounds represented by any of formulas (L1) to (L4).

[0154]

[0155] In each formula, each R' independently represents a fluorine atom, an aryl group, or an alkyl group, each R'' independently represents a hydrogen atom or an alkyl group, and L １ and L ２ each independently represents a single bond, a methylene group, or a propane-2,2-diyl group; L ３is determined depending on q1 and represents a single bond, a methylene group, a propane-2,2-diyl group, a methanetriyl group, or an ethane-1,1,1-triyl group; t11, t12, and t13 are integers that satisfy 2≦t11≦5, 1≦t12≦4, 0≦t13≦3, and t11+t12+t13≦6; t21, t22, and t23 are integers that satisfy 2≦t21≦4, 1≦t22≦3, 0≦t23≦2, and t21+t22+t23≦5; t24, t25, and t26 are integers that satisfy 2≦t24≦4, 1≦t25≦3, 0≦t26≦2, and t24+t25+t26≦5; and t27, t28, and t29 are integers that satisfy 0≦t27≦4, 0≦t28≦ t31, t32, and t33 are integers that satisfy 2≦t31≦4, 1≦t32≦3, 0≦t33≦2, and t31+t32+t33≦5; t41, t42, and t43 are integers that satisfy 2≦t41≦3, 1≦t42≦2, 0≦t43≦1, and t41+t42+t43≦4; q1 is 2 or 3, and q2 represents the number of repetitions and is an integer of 0 or more. Specific examples of the aryl group and alkyl group include the same as those described below, although a phenyl group is preferred as the aryl group, and a methyl group or a t-butyl group is preferred as the alkyl group.

[0156] Specific examples of compounds represented by formulas (L1) to (L4) are listed below, but are not limited to these. These compounds may be synthesized by known methods or are available as products from, for example, Asahi Organic Chemicals Co., Ltd. or Honshu Chemical Industry Co., Ltd.

[0157]

[0158]

[0159]

[0160]

[0161] The melamine-based crosslinking agent having a crosslink-forming group is a melamine derivative, a 2,4-diamino-1,3,5-triazine derivative, or a 2-amino-1,3,5-triazine derivative in which at least one hydrogen atom of an amino group bonded to the triazine ring is substituted with a crosslink-forming group, and the triazine ring may further have a substituent such as an aryl group such as a phenyl group. Specific examples of melamine-based crosslinking agents having a crosslinking group include mono-, bis-, tris-, tetrakis-, pentakis- or hexakisalkoxymethylmelamines such as N,N,N',N',N",N"-hexakis(methoxymethyl)melamine and N,N,N',N',N",N"-hexakis(butoxymethyl)melamine; and mono-, bis-, tris- or tetrakisalkoxymethylbenzoguanamines such as N,N,N',N'-tetrakis(methoxymethyl)benzoguanamine and N,N,N',N'-tetrakis(butoxymethyl)benzoguanamine, but are not limited to these.

[0162] A urea-based crosslinking agent having a crosslink-forming group is a derivative of a urea bond-containing compound and has a structure in which at least one hydrogen atom of an NH group constituting a urea bond is substituted with a crosslink-forming group. Specific examples of the urea-based crosslinking agent having a crosslink-forming group include mono-, bis-, tris-, or tetrakisalkoxymethylglycolurils such as 1,3,4,6-tetrakis(methoxymethyl)glycoluril and 1,3,4,6-tetrakis(butoxymethyl)glycoluril, and mono-, bis-, tris-, or tetrakisalkoxymethylureas such as 1,3-bis(methoxymethyl)urea and 1,1,3,3-tetrakismethoxymethylurea, but are not limited to these.

[0163] A thiourea-based crosslinking agent having a crosslink-forming group is a derivative of a thiourea bond-containing compound, and has a structure in which at least one hydrogen atom of an NH group constituting a thiourea bond is substituted with a crosslink-forming group. Specific examples of thiourea-based crosslinking agents having a crosslink-forming group include, but are not limited to, mono-, bis-, tris-, or tetrakis-alkoxymethylthioureas such as 1,3-bis(methoxymethyl)thiourea and 1,1,3,3-tetrakismethoxymethylthiourea.

[0164] The amount of crosslinking agent contained in the release agent composition cannot be generally defined because it differs depending on the coating method used, the desired film thickness, etc., but is usually 0.01 to 50% by mass relative to the organic resin or polynuclear phenol derivative. From the viewpoint of achieving suitable curing and reproducibly obtaining a laminate in which the compound semiconductor substrate and the support substrate can be easily separated, the amount is preferably 0.1% by mass or more, more preferably 1% by mass or more, even more preferably 3% by mass or more, still more preferably 5% by mass or more, and is preferably 45% by mass or less, more preferably 40% by mass or less, even more preferably 35% by mass or less, and still more preferably 30% by mass or less.

[0165] <<<Acid Generator and Acid>>> The stripping composition may contain an acid generator or an acid for the purpose of promoting the crosslinking reaction or the like.

[0166] Examples of the acid generator include thermal acid generators and photoacid generators. The thermal acid generator is not particularly limited as long as it generates an acid by heat, and specific examples include, but are not limited to, 2,4,4,6-tetrabromocyclohexadienone, benzoin tosylate, 2-nitrobenzyl tosylate, K-PURE (registered trademark) CXC-1612, CXC-1614, TAG-2172, TAG-2179, TAG-2678, TAG2689, and TAG2700 (manufactured by King Industries), and SI-45, SI-60, SI-80, SI-100, SI-110, and SI-150 (manufactured by Sanshin Chemical Industry Co., Ltd.), and other organic sulfonic acid alkyl esters.

[0167] Examples of the photoacid generator include an onium salt compound, a sulfonimide compound, and a disulfonyldiazomethane compound.

[0168] Specific examples of the onium salt compound include iodonium salt compounds such as diphenyliodonium hexafluorophosphate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-normal butanesulfonate, diphenyliodonium perfluoro-normal octanesulfonate, diphenyliodonium camphorsulfonate, bis(4-tert-butylphenyl)iodonium camphorsulfonate, and bis(4-tert-butylphenyl)iodonium trifluoromethanesulfonate; and sulfonium salt compounds such as triphenylsulfonium nitrate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium nonafluoro-normal butanesulfonate, triphenylsulfonium camphorsulfonate, and triphenylsulfonium trifluoromethanesulfonate, but are not limited to these.

[0169] Specific examples of the sulfonimide compound include N-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluoronormalbutanesulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, and N-(trifluoromethanesulfonyloxy)naphthalimide, but are not limited to these.

[0170] Specific examples of the disulfonyldiazomethane compound include, but are not limited to, bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(2,4-dimethylbenzenesulfonyl)diazomethane, methylsulfonyl-p-toluenesulfonyldiazomethane, and the like.

[0171] Specific examples of acids include arylsulfonic acids and pyridinium salts such as p-toluenesulfonic acid, pyridinium p-toluenesulfonate (pyridinium paratoluenesulfonate), pyridinium trifluoromethanesulfonate, pyridinium phenolsulfonic acid, 5-sulfosalicylic acid, 4-phenolsulfonic acid, 4-chlorobenzenesulfonic acid, benzenedisulfonic acid, and 1-naphthalenesulfonic acid, and salts thereof; arylcarboxylic acids and salts thereof such as salicylic acid, benzoic acid, hydroxybenzoic acid, and naphthalenecarboxylic acid; linear or cyclic alkylsulfonic acids and salts thereof such as trifluoromethanesulfonic acid and camphorsulfonic acid; and linear or cyclic alkylcarboxylic acids and salts thereof such as citric acid, but are not limited to these.

[0172] The amounts of the acid generator and acid contained in the stripping composition cannot be generally defined because they vary depending on the type of crosslinking agent used, the heating temperature during film formation, and the like, but are usually 0.01 to 5 mass % based on the film-constituting components.

[0173] <<<Surfactant>>> The stripper composition may contain a surfactant for the purposes of adjusting the liquid properties of the composition itself and the film properties of the resulting film, and for the purpose of preparing a highly uniform stripper composition with good reproducibility. The surfactant may be used alone or in combination of two or more. The amount of the surfactant is usually 2 mass% or less based on the film-constituting components of the stripper composition.

[0174] <<<Solvent>>> The release agent composition preferably contains a solvent. As such a solvent, for example, a high-polarity solvent that can well dissolve the film-constituting components such as the above-mentioned organic resin, polynuclear phenol derivative, branched-chain polysilane, and crosslinking agent can be used. If necessary, a low-polarity solvent may be used for the purpose of adjusting viscosity, surface tension, etc. In the present invention, a low-polarity solvent is defined as one having a relative dielectric constant of less than 7 at a frequency of 100 kHz, and a high-polarity solvent is defined as one having a relative dielectric constant of 7 or more at a frequency of 100 kHz. The solvents can be used alone or in combination of two or more.

[0175] Examples of highly polar solvents include amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylisobutyramide, N-methylpyrrolidone, and 1,3-dimethyl-2-imidazolidinone; ketone solvents such as ethyl methyl ketone, isophorone, and cyclohexanone; cyano solvents such as acetonitrile and 3-methoxypropionitrile; polyhydric alcohol solvents such as ethylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, 1,3-butanediol, and 2,3-butanediol; monohydric alcohol solvents other than aliphatic alcohols such as propylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monophenyl ether, triethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, benzyl alcohol, 2-phenoxyethanol, 2-benzyloxyethanol, 3-phenoxybenzyl alcohol, and tetrahydrofurfuryl alcohol; and sulfoxide solvents such as dimethyl sulfoxide.

[0176] Examples of low-polarity solvents include chlorine-based solvents such as chloroform and chlorobenzene; aromatic hydrocarbon-based solvents such as alkylbenzenes such as toluene, xylene, tetralin, cyclohexylbenzene and decylbenzene; aliphatic alcohol-based solvents such as 1-octanol, 1-nonanol and 1-decanol; ether-based solvents such as tetrahydrofuran, dioxane, anisole, 4-methoxytoluene, 3-phenoxytoluene, dibenzyl ether, diethylene glycol dimethyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether and triethylene glycol butyl methyl ether; and ester-based solvents such as methyl benzoate, ethyl benzoate, butyl benzoate, isoamyl benzoate, bis(2-ethylhexyl) phthalate, dibutyl maleate, dibutyl oxalate, hexyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate and diethylene glycol monobutyl ether acetate.

[0177] The content of the solvent is determined appropriately taking into consideration the viscosity of the desired composition, the coating method to be used, the thickness of the film to be produced, and the like, but is 99% by mass or less of the entire composition, and preferably 70 to 99% by mass of the entire composition, i.e., the amount of the film-constituting components in this case is 1 to 30% by mass of the entire composition.

[0178] The viscosity and surface tension of the stripping composition are appropriately adjusted by changing the types of solvents used, their ratios, the concentrations of the film-constituting components, etc., taking into consideration various factors such as the coating method used and the desired film thickness.

[0179] In one embodiment of the present invention, the stripper composition contains a glycol-based solvent from the viewpoint of reproducibly obtaining a highly uniform composition, reproducibly obtaining a composition with high storage stability, reproducibly obtaining a composition that gives a highly uniform film, etc. Note that the term "glycol-based solvent" used here is a general term for glycols, glycol monoethers, glycol diethers, glycol monoesters, glycol diesters, and glycol ester ethers.

[0180] An example of a preferred glycol-based solvent is represented by formula (G).

[0181]

[0182] In formula (G), R Ｇ１ each independently represents a linear or branched alkylene group having 2 to 4 carbon atoms; R Ｇ２ and R Ｇ３ each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, or an alkylacyl group in which the alkyl moiety is a linear or branched alkyl group having 1 to 8 carbon atoms; n ｇ is an integer from 1 to 6.

[0183] Specific examples of the linear or branched alkylene group having 2 to 4 carbon atoms include, but are not limited to, an ethylene group, a trimethylene group, a 1-methylethylene group, a tetramethylene group, a 2-methylpropane-1,3-diyl group, a pentamethylene group, a hexamethylene group, etc. Among these, from the viewpoint of reproducibly obtaining a highly uniform composition, reproducibly obtaining a composition with high storage stability, and reproducibly obtaining a composition that gives a highly uniform film, linear or branched alkylene groups having 2 to 3 carbon atoms are preferred, and linear or branched alkylene groups having 3 carbon atoms are more preferred.

[0184] Specific examples of the linear or branched alkyl group having 1 to 8 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, an s-butyl group, a tertiary butyl group, an n-pentyl group, a 1-methyl-n-butyl group, a 2-methyl-n-butyl group, a 3-methyl-n-butyl group, a 1,1-dimethyl-n-propyl group, a 1,2-dimethyl-n-propyl group, a 2,2-dimethyl-n-propyl group, a 1-ethyl-n-propyl group, an n-hexyl group, a 1-methyl-n-pentyl group, a 2-methyl-n-pentyl group, a 3-methyl Examples of the alkyl group include, but are not limited to, a methyl group, a 4-methyl-n-pentyl group, a 1,1-dimethyl-n-butyl group, a 1,2-dimethyl-n-butyl group, a 1,3-dimethyl-n-butyl group, a 2,2-dimethyl-n-butyl group, a 2,3-dimethyl-n-butyl group, a 3,3-dimethyl-n-butyl group, a 1-ethyl-n-butyl group, a 2-ethyl-n-butyl group, a 1,1,2-trimethyl-n-propyl group, a 1,2,2-trimethyl-n-propyl group, a 1-ethyl-1-methyl-n-propyl group, and a 1-ethyl-2-methyl-n-propyl group. Among these, from the viewpoint of reproducibly obtaining a highly uniform composition, a highly storage stable composition, and a composition that gives a highly uniform film, a methyl group and an ethyl group are preferred, and a methyl group is more preferred.

[0185] Specific examples of the linear or branched alkyl group having 1 to 8 carbon atoms in the alkyl acyl group in which the alkyl moiety is a linear or branched alkyl group having 1 to 8 carbon atoms include the same as the specific examples described above. Among these, from the viewpoints of reproducibly obtaining a highly uniform composition, reproducibly obtaining a composition having high storage stability, and reproducibly obtaining a composition that gives a highly uniform film, a methylcarbonyl group and an ethylcarbonyl group are preferred, and a methylcarbonyl group is more preferred.

[0186] n ｇ is preferably 4 or less, more preferably 3 or less, even more preferably 2 or less, and most preferably 1, from the viewpoint of reproducibly obtaining a highly uniform composition, from the viewpoint of reproducibly obtaining a composition with high storage stability, from the viewpoint of reproducibly obtaining a composition that gives a highly uniform film, etc.

[0187] From the viewpoint of reproducibly obtaining a composition having high uniformity, a composition having high storage stability, and a composition that gives a film having high uniformity, it is preferable that R Ｇ２ and R Ｇ３ At least one of R is a linear or branched alkyl group having 1 to 8 carbon atoms, and more preferably R Ｇ２ and R Ｇ３ One of the groups is a linear or branched alkyl group having 1 to 8 carbon atoms, and the other is a hydrogen atom or an alkylacyl group in which the alkyl portion is a linear or branched alkyl group having 1 to 8 carbon atoms.

[0188] From the viewpoint of reproducibly obtaining a highly uniform composition, a highly storage stable composition, and a composition that gives a highly uniform film, the content of the glycol-based solvent is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, still more preferably 90% by mass or more, and still more preferably 95% by mass or more, relative to the solvent contained in the stripper composition. From the viewpoint of reproducibly obtaining a highly uniform composition, a highly storage stable composition, and a composition that gives a highly uniform film, the film constituent components in the stripper composition are uniformly dispersed or dissolved, preferably dissolved, in the solvent.

[0189] The release agent composition can be produced, for example, by mixing an organic resin or a polynuclear phenol derivative, a solvent, and, if necessary, a crosslinker. The order of mixing is not particularly limited, and examples of methods that can easily and reproducibly produce a release agent composition include, but are not limited to, a method in which the organic resin or polynuclear phenol derivative and the crosslinker are dissolved in a solvent at once, or a method in which a portion of the organic resin or polynuclear phenol derivative and the crosslinker are dissolved in a solvent and the remainder is separately dissolved in a solvent, and the resulting solutions are mixed. Furthermore, when preparing the release agent composition, heating may be performed as appropriate within a range that does not cause decomposition or deterioration of the components. In the present invention, in order to remove foreign matter, the solvent, solution, etc. used may be filtered using a filter or the like during the production of the release agent composition or after mixing all the components.

[0190] The method for forming a release agent layer from a release agent composition is not particularly limited, but examples include a method of forming a release agent layer by applying the release agent composition. The method for applying the release agent composition is not particularly limited, but is typically spin coating. The heating temperature of the applied release agent composition cannot be generally specified because it varies depending on the type and amount of release agent components contained in the release agent composition, the desired thickness of the release agent layer, etc., but from the perspective of reproducibly achieving a suitable release agent layer, it is 80°C or higher and 300°C or lower, and the heating time is typically determined appropriately within the range of 10 seconds to 10 minutes depending on the heating temperature. The heating temperature is preferably 100°C or higher and 280°C or lower, more preferably 150°C or higher and 250°C or lower. The heating time is preferably 30 seconds to 8 minutes, more preferably 1 minute to 5 minutes. Heating can be performed using a hot plate, oven, or the like.

[0191] An example of the configuration of a laminate will be described below with reference to the drawings. Fig. 1 shows a schematic cross-sectional view of an example of a laminate. The laminate of Fig. 1 has a compound semiconductor substrate 1, an adhesive layer 2, and a support substrate 4, in this order. That is, the adhesive layer 2 is provided between the compound semiconductor substrate 1 and the support substrate 4. The adhesive layer 2 contacts the compound semiconductor substrate 1 and the support substrate 4.

[0192] Another example of the configuration of the laminate will be described below with reference to the drawings. Fig. 2 shows a schematic cross-sectional view of another example of the laminate. The laminate of Fig. 2 has a compound semiconductor substrate 1, an adhesive layer 2, a release agent layer 3, and a support substrate 4, in this order. The adhesive layer 2 and the release agent layer 3 are provided between the compound semiconductor substrate 1 and the support substrate 4. The adhesive layer 2 is in contact with the compound semiconductor substrate 1. The release agent layer 3 is in contact with the adhesive layer 2 and the support substrate 4.

[0193] <<Example of a Method for Producing a Laminate>> A method for producing a laminate will be described below using the laminate shown in Fig. 1 as an example of a laminate. An example of the laminate of the present invention can be produced by a method including the following steps 1A to 2A. Step 1A: A step of applying an adhesive composition onto a compound semiconductor substrate to form an adhesive coating layer. Step 2A: A step of heating the adhesive coating layer to form an adhesive layer.

[0194] A method for producing a laminate will be described below using the laminate shown in Figure 2 as an example of a laminate. An example of the laminate of the present invention can be produced by a method including the following steps 1B to 3B. Step 1B: A step of applying an adhesive composition onto a compound semiconductor substrate to form an adhesive coating layer. Step 2B: A step of applying a release agent composition onto a support substrate to form a release agent layer. Step 3B: A step of heating the adhesive coating layer while the adhesive coating layer and the release agent layer are in contact with each other to form an adhesive layer.

[0195] The method for applying the adhesive composition is not particularly limited, but is typically spin coating. Alternatively, a method can be employed in which a coating film is formed separately by spin coating or the like, a sheet-like coating film is formed, and the sheet-like coating film is then applied as an adhesive coating layer. The heating temperature of the applied adhesive composition cannot be generally specified because it varies depending on the type and amount of adhesive components contained in the adhesive composition, whether or not a solvent is contained, the boiling point of the solvent used, the desired thickness of the adhesive layer, and other factors. However, it is typically 80 to 150°C, and the heating time is typically 30 seconds to 5 minutes. When the adhesive composition contains a solvent, the applied adhesive composition is typically heated. The thickness of the adhesive coating layer obtained by applying the adhesive composition and, if necessary, heating it is typically about 5 to 500 μm, and is appropriately determined so as to ultimately achieve the above-mentioned range of adhesive layer thickness.

[0196] The method for applying the release agent composition is not particularly limited, but is usually spin coating. The heating temperature of the applied release agent composition cannot be generally specified because it varies depending on the type and amount of release agent components contained in the release agent composition, the desired thickness of the release agent layer, etc., but from the viewpoint of achieving a suitable release agent layer with good reproducibility, it is 80°C or higher and 300°C or lower, and the heating time is usually appropriately determined within the range of 10 seconds to 10 minutes depending on the heating temperature. The heating temperature is preferably 100°C or higher and 280°C or lower, more preferably 150°C or higher and 250°C or lower. The heating time is preferably 30 seconds or higher and 8 minutes or lower, more preferably 1 minute or higher and 5 minutes or lower. Heating can be performed using a hot plate, oven, etc.

[0197] In the present invention, the laminate of the present invention can be obtained by applying a load in the thickness direction of the compound semiconductor substrate and the support substrate while performing a heat treatment, a decompression treatment, or both, and then performing a post-heat treatment. The treatment conditions to be adopted, whether heat treatment, decompression treatment, or a combination of both, are appropriately determined taking into consideration various factors such as the type of adhesive composition, the film thickness, and the desired adhesive strength.

[0198] The heat treatment temperature is determined appropriately from the viewpoint of removing the solvent from the composition, etc., typically within the range of 20 to 160° C. In particular, when the adhesive composition contains adhesive component (A), the heat treatment temperature is preferably 150° C. or lower, more preferably 130° C. or lower, from the viewpoint of suppressing or avoiding excessive curing or unnecessary deterioration of adhesive component (A). The heating time is determined appropriately depending on the heating temperature and the type of adhesive, but is typically 30 seconds or longer, preferably 1 minute or longer, from the viewpoint of reliably achieving suitable adhesion, and is typically 10 minutes or shorter, preferably 5 minutes or shorter, from the viewpoint of suppressing deterioration of the adhesive layer and other components.

[0199] The reduced pressure treatment can be carried out by exposing the adhesive coated layers in contact with each other to an atmospheric pressure of 10 to 10,000 Pa. The reduced pressure treatment time is usually 1 to 30 minutes.

[0200] The load in the thickness direction of the compound semiconductor substrate and the support substrate is not particularly limited as long as it does not adversely affect the compound semiconductor substrate, the support substrate, and the layers therebetween and can firmly adhere them to each other, but is usually within the range of 10 to 50,000 N.

[0201] The post-heating temperature is preferably 120°C or higher from the viewpoint of achieving a sufficient curing rate, and preferably 260°C or lower from the viewpoint of preventing deterioration of the substrate and each layer. The post-heating time is usually 1 minute or longer, preferably 5 minutes or longer, from the viewpoint of achieving suitable bonding of the substrate and layers constituting the laminate, and usually 180 minutes or shorter, preferably 120 minutes or shorter, from the viewpoint of suppressing or avoiding adverse effects on each layer due to excessive heating. Heating can be performed using a hot plate, oven, or the like. When post-heating is performed using a hot plate, either the compound semiconductor substrate or the support substrate of the laminate may be heated facing down, but from the viewpoint of achieving suitable peeling with good reproducibility, post-heating with the compound semiconductor substrate facing down is preferred. Note that one purpose of the post-heating treatment is to achieve an adhesive layer that is a more suitable free-standing film, and in particular to achieve suitable curing by a hydrosilylation reaction.

[0202] An example of a method for producing the laminate shown in FIG. 2 will be described below with reference to FIGS. 3A to 3C. FIGS. 3A to 3C are diagrams illustrating one embodiment of laminate production. First, a laminate is prepared in which an adhesive coating layer 2a is formed on a compound semiconductor substrate 1 (FIG. 3A). This laminate can be obtained, for example, by applying an adhesive composition to the compound semiconductor substrate 1 and heating the resulting laminate. Separately, a laminate is prepared in which a release agent layer 3 is formed on a support substrate 4 (FIG. 3B). This laminate can be obtained, for example, by applying a release agent composition to the support substrate 4 and heating the resulting laminate. Next, the laminate shown in FIG. 3A and the laminate shown in FIG. 3B are bonded together so that the adhesive coating layer 2a and the release agent layer 3 are in contact with each other. Then, a load is applied to the compound semiconductor substrate 1 and the support substrate 4 in the thickness direction under reduced pressure. After that, a heating device (not shown; hot plate) is placed on the surface of the compound semiconductor substrate 1 opposite the surface where the adhesive coating layer 2a is in contact. The adhesive coating layer 2a is heated and cured by the heating device, converting it into the adhesive layer 2 (FIG. 3C). A laminate is obtained by the steps shown in FIGS. 3A to 3C.

[0203] (Method for manufacturing a processed compound semiconductor substrate) By using the laminate according to the present invention, a method for manufacturing a processed compound semiconductor substrate can be provided. The method for manufacturing a processed compound semiconductor substrate according to the present invention comprises the following steps: A step of processing the compound semiconductor substrate of the laminate according to the present invention (processing step) A step of separating the processed compound semiconductor substrate from the support substrate (separation step) Furthermore, the method for manufacturing a processed compound semiconductor substrate may comprise the following steps: A step of cleaning the processed compound semiconductor substrate (cleaning step)

[0204] <Processing Step> The processing performed on the compound semiconductor substrate in the processing step is, for example, processing of the side opposite the circuit surface of the compound semiconductor substrate, such as thinning the compound semiconductor substrate by polishing the back surface of the compound semiconductor substrate. Thereafter, for example, through-hole vias (TSVs) are formed, and then the thinned compound semiconductor substrate is peeled off from the support substrate to form a stack of compound semiconductor substrates, which are then three-dimensionally mounted. Also, for example, before or after this, back electrodes of the compound semiconductor substrate are formed. During the thinning and TSV process of the compound semiconductor substrate, heat is applied at approximately 250 to 350°C or 250 to 450°C while the substrate is adhered to the support substrate. The laminate of the present invention, including the adhesive layer, typically has heat resistance to this load. Note that the processing is not limited to the above-described processing, and includes, for example, the implementation of a semiconductor component mounting process in which the substrate is temporarily adhered to a support substrate to support the substrate on which the semiconductor component is mounted.

[0205] <Separation Step> In the separation step, the method for separating (peeling) the compound semiconductor substrate and the support substrate is not particularly limited. For example, a mechanical peeling method using a device with a sharp part (a so-called debonder) can be used. Specifically, for example, a sharp part is inserted between the compound semiconductor substrate and the support substrate, and then the compound semiconductor substrate and the support substrate are separated. Furthermore, when the laminate has a release agent layer, the method for separating (peeling) the compound semiconductor substrate and the support substrate in the separation step may be, for example, a method in which the release agent layer is irradiated with light and then the compound semiconductor substrate and the support substrate are peeled off from each other. By irradiating the release agent layer with light from the support substrate side, the release agent layer is altered (e.g., separated or decomposed) as described above, and then, for example, one of the substrates can be lifted up to easily separate the compound semiconductor substrate and the support substrate.

[0206] The light irradiation of the release agent layer does not necessarily have to be performed on the entire area of ​​the release agent layer. Even if there are regions irradiated with light and regions not irradiated with light, as long as the release agent layer as a whole has sufficiently improved releasability, the compound semiconductor substrate and the support substrate can be separated by a slight external force, such as by lifting up the support substrate. The ratio and positional relationship of the light-irradiated and non-irradiated regions will vary depending on the type and specific composition of the adhesive used, the thickness of the adhesive layer, the thickness of the release agent layer, the intensity of the irradiated light, etc., but those skilled in the art will be able to set appropriate conditions without the need for excessive testing. For these reasons, the method for producing a processed compound semiconductor substrate of the present invention makes it possible to shorten the light irradiation time when peeling is performed by light irradiation from the support substrate side, for example, when the support substrate of the laminate used is optically transparent. As a result, not only can throughput be improved, but physical stresses and the like required for peeling can be avoided, and the compound semiconductor substrate and the support substrate can be easily and efficiently separated by light irradiation alone. Typically, the light irradiation dose for peeling is 50 to 3,000 mJ / cm. ２ The irradiation time is appropriately determined depending on the wavelength and the irradiation amount.

[0207] The wavelength of the light used for peeling is, for example, preferably 250 to 600 nm, and more preferably 250 to 370 nm. More preferred wavelengths are 308 nm, 343 nm, 355 nm, 365 nm, or 532 nm. The light irradiation amount required for peeling is an irradiation amount that can cause suitable alteration, for example, decomposition, of the specific compound and polymer. The light used for peeling may be laser light or non-laser light emitted from a light source such as an ultraviolet lamp.

[0208] <Cleaning Step> In the cleaning step, the substrates can be cleaned by spraying a cleaning composition onto the surface of at least one of the separated compound semiconductor substrate and the support substrate, or by immersing the separated compound semiconductor substrate or the support substrate in the cleaning composition. Alternatively, the surface of the processed compound semiconductor substrate or the like may be cleaned using a removal tape or the like. Examples of cleaning compositions used for cleaning include the following.

[0209] The cleaning agent composition usually contains a solvent. Examples of the solvent include lactones, ketones, polyhydric alcohols, compounds having an ester bond, derivatives of polyhydric alcohols, cyclic ethers, esters, and aromatic organic solvents. Examples of the lactones include γ-butyrolactone. Examples of the ketones include acetone, methyl ethyl ketone, cyclohexanone, methyl-n-pentyl ketone, methyl isopentyl ketone, and 2-heptanone. Examples of the polyhydric alcohols include ethylene glycol, diethylene glycol, propylene glycol, and dipropylene glycol. Examples of compounds having an ester bond include ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, and dipropylene glycol monoacetate. Examples of derivatives of polyhydric alcohols include compounds having an ether bond, such as monoalkyl ethers or monophenyl ethers of the above polyhydric alcohols or compounds having an ester bond, such as monomethyl ether, monoethyl ether, monopropyl ether, and monobutyl ether. Among these, propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) are preferred. Examples of cyclic ethers include dioxane. Examples of esters include methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, and ethyl ethoxypropionate. Examples of aromatic organic solvents include anisole, ethyl benzyl ether, cresyl methyl ether, diphenyl ether, dibenzyl ether, phenetole, butylphenyl ether, ethylbenzene, diethylbenzene, pentylbenzene, isopropylbenzene, toluene, xylene, cymene, mesitylene, etc. These can be used alone or in combination of two or more.Among these, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), cyclohexanone, and ethyl lactate (EL) are preferred.

[0210] Also preferred are mixed solvents containing PGMEA and a polar solvent. The blending ratio (mass ratio) can be determined appropriately taking into account the compatibility of the PGMEA and the polar solvent, but is preferably within the range of 1:9 to 9:1, and more preferably 2:8 to 8:2. For example, when EL is blended as the polar solvent, the mass ratio of PGMEA:EL is preferably 1:9 to 9:1, and more preferably 2:8 to 8:2. When PGME is blended as the polar solvent, the mass ratio of PGMEA:PGME is preferably 1:9 to 9:1, more preferably 2:8 to 8:2, and even more preferably 3:7 to 7:3. When PGME and cyclohexanone are blended as the polar solvents, the mass ratio of PGMEA:(PGME + cyclohexanone) is preferably 1:9 to 9:1, more preferably 2:8 to 8:2, and even more preferably 3:7 to 7:3.

[0211] The cleaning composition may or may not contain a salt; however, the absence of a salt is preferred in terms of increasing versatility in processing compound semiconductor substrates using the laminate and reducing costs.

[0212] An example of a detergent composition containing a salt is a detergent composition containing a quaternary ammonium salt and a solvent. The quaternary ammonium salt is composed of a quaternary ammonium cation and an anion, and is not particularly limited as long as it is used for this type of application. A typical example of such a quaternary ammonium cation is a tetra(hydrocarbon)ammonium cation. On the other hand, the anion paired with the quaternary ammonium cation is a hydroxide ion (OH － ) ; fluorine ion (F － ), chloride ions (Cl － ), bromine ion (Br － ), iodine ion (I － ) and other halogen ions; tetrafluoroborate ion (BF４ － ) ; hexafluorophosphate ion (PF ６ － ) and the like, but are not limited to these.

[0213] The quaternary ammonium salt is preferably a halogen-containing quaternary ammonium salt, more preferably a fluorine-containing quaternary ammonium salt. In the quaternary ammonium salt, the halogen atom may be contained in either the cation or the anion, but is preferably contained in the anion.

[0214] In a preferred embodiment, the fluorine-containing quaternary ammonium salt is tetra(hydrocarbon)ammonium fluoride. Specific examples of the hydrocarbon group in tetra(hydrocarbon)ammonium fluoride include alkyl groups having 1 to 20 carbon atoms, alkenyl groups having 2 to 20 carbon atoms, alkynyl groups having 2 to 20 carbon atoms, and aryl groups having 6 to 20 carbon atoms. In a more preferred embodiment, the tetra(hydrocarbon)ammonium fluoride includes tetraalkylammonium fluoride. Specific examples of tetraalkylammonium fluorides include, but are not limited to, tetramethylammonium fluoride, tetraethylammonium fluoride, tetrapropylammonium fluoride, and tetrabutylammonium fluoride (also known as tetrabutylammonium fluoride). Of these, tetrabutylammonium fluoride is preferred.

[0215] The quaternary ammonium salts such as tetra(hydrocarbon)ammonium fluoride may be used in the form of a hydrate. The quaternary ammonium salts such as tetra(hydrocarbon)ammonium fluoride may be used singly or in combination of two or more. The amount of the quaternary ammonium salt is not particularly limited as long as it dissolves in the solvent contained in the cleaning composition, but is usually 0.1 to 30 mass% based on the cleaning composition.

[0216] When the cleaning composition contains a salt, the solvent to be used in combination with the salt is not particularly limited as long as it is used for this type of application and dissolves the salt such as a quaternary ammonium salt. However, from the viewpoint of reproducibly obtaining a cleaning composition having excellent cleaning properties and from the viewpoint of satisfactorily dissolving the salt such as a quaternary ammonium salt to obtain a cleaning composition having excellent uniformity, the cleaning composition preferably contains one or two or more amide solvents.

[0217] A suitable example of the amide solvent is an acid amide derivative represented by formula (Z).

[0218] In the formula, R ０ represents an ethyl group, a propyl group, or an isopropyl group, preferably an ethyl group or an isopropyl group, and more preferably an ethyl group. Ａ and R Ｂ each independently represents an alkyl group having 1 to 4 carbon atoms. The alkyl group having 1 to 4 carbon atoms may be linear, branched, or cyclic, and specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a cyclopropyl group, an n-butyl group, an isobutyl group, an s-butyl group, a t-butyl group, and a cyclobutyl group. Of these, R Ａ and R Ｂ As the alkyl group, a methyl group or an ethyl group is preferred, and both of them are more preferably methyl groups or ethyl groups, and both of them are even more preferably methyl groups.

[0219] Examples of the acid amide derivative represented by formula (Z) include N,N-dimethylpropionamide, N,N-diethylpropionamide, N-ethyl-N-methylpropionamide, N,N-dimethylbutyric acid amide, N,N-diethylbutyric acid amide, N-ethyl-N-methylbutyric acid amide, N,N-dimethylisobutyric acid amide, N,N-diethylisobutyric acid amide, N-ethyl-N-methylisobutyric acid amide, etc. Among these, N,N-dimethylpropionamide and N,N-dimethylisobutyric acid amide are particularly preferred, and N,N-dimethylpropionamide is more preferred.

[0220] The acid amide derivative represented by formula (Z) may be synthesized by a substitution reaction between a corresponding carboxylic acid ester and an amine, or a commercially available product may be used.

[0221] Another example of a preferred amide solvent is a lactam compound represented by formula (Y).

[0222] In formula (Y), R １０１ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R １０２ represents an alkylene group having 1 to 6 carbon atoms. Specific examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, an n-propyl group, and an n-butyl group, and specific examples of the alkylene group having 1 to 6 carbon atoms include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group, but are not limited to these.

[0223] Specific examples of the lactam compound represented by formula (Y) include α-lactam compounds, β-lactam compounds, γ-lactam compounds, and δ-lactam compounds, and these can be used alone or in combination of two or more.

[0224] In a preferred embodiment, the lactam compound represented by formula (Y) includes 1-alkyl-2-pyrrolidone (N-alkyl-γ-butyrolactam), in a more preferred embodiment, it includes N-methylpyrrolidone (NMP) or N-ethylpyrrolidone (NEP), and in an even more preferred embodiment, it includes N-methylpyrrolidone (NMP).

[0225] The cleaning composition used in the present invention may contain water as a solvent, but usually only an organic solvent is used as the solvent from the viewpoint of avoiding corrosion of the substrate, etc. In this case, it is not excluded that the cleaning composition may contain water of hydration of salts or trace amounts of water contained in the organic solvent. The water content of the cleaning composition used in the present invention is usually 5 mass% or less.

[0226] The constituent elements and methodological elements of the above-described steps of the method for manufacturing a processed compound semiconductor substrate of the present invention may be modified in various ways without departing from the spirit and scope of the present invention. The method for manufacturing a processed compound semiconductor substrate of the present invention may include steps other than those described above.

[0227] In one example of the peeling method of the present invention, when the compound semiconductor substrate or the support substrate of the laminate of the present invention is optically transparent, the compound semiconductor substrate and the support substrate of the laminate are separated by irradiating the release agent layer with light from the compound semiconductor substrate side or the support substrate side. In one example of the laminate of the present invention, the compound semiconductor substrate and the support substrate are suitably and releasably temporarily bonded by the adhesive layer and the release agent layer. Therefore, for example, when the support substrate is optically transparent, the compound 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. Typically, peeling is performed after processing the compound semiconductor substrate of the laminate.

[0228] An example of a method for manufacturing a processed compound semiconductor substrate is described below with reference to FIGS. 4A to 4E. This example is an example of manufacturing a thinned compound semiconductor substrate. First, a laminate is prepared ( FIG. 4A ). This laminate is the same as the laminate shown in FIGS. 2 and 3C . Next, a polishing device (not shown) is used to polish the surface of the compound semiconductor substrate 1 opposite to the surface in contact with the adhesive layer 2, thereby thinning the compound semiconductor substrate 1 ( FIG. 4B ). The thinned compound semiconductor substrate 1 may also be subjected to the formation of through-hole electrodes. Next, light L is irradiated onto the release agent layer 3 from the support substrate 4 side ( FIG. 4C ). Next, a peeling device (not shown) is used to separate the thinned compound semiconductor substrate 1 from the support substrate 4 ( FIG. 4D ). This results in a thinned compound semiconductor substrate 1. Residues of the adhesive layer 2 and the release agent layer 3 may remain on the thinned compound semiconductor substrate 1. Therefore, it is preferable to clean the thinned compound semiconductor substrate 1 with a cleaning composition to remove the residues of the adhesive layer 2 and the release agent layer 3 from the compound semiconductor substrate 1 (FIG. 4E).

[0229] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples. The apparatus used is as follows.

[0230] [Devices] (1) Mixer: ARE-500, a planetary centrifugal mixer manufactured by Thinky Corporation (2-1) Vacuum bonding device: SUSS MicroTec Co., Ltd., a manual bonder (2-2) Vacuum bonding device: XBS300, a manufacturer of SUSS MicroTec Co., Ltd. (3) Laser peeling device: OPTOPIA Co., Ltd., a laser debonder

[0231] [1] Preparation of Adhesive Composition [Preparation Example 1] 80 g of MQ resin (manufactured by Wacker Chemie) containing a polysiloxane skeleton and vinyl groups, 2.52 g of vinyl group-containing linear polydimethylsiloxane (manufactured by Wacker Chemie) with a viscosity of 100 mPa s, 5.89 g of SiH group-containing linear polydimethylsiloxane (manufactured by Wacker Chemie) with a viscosity of 70 mPa s, and 0.22 g of 1-ethynyl-1-cyclohexanol (manufactured by Wacker Chemie) were placed in a 600 mL stirring vessel for a planetary centrifugal mixer, and the mixture was stirred for 5 minutes to obtain a mixture (I). 0.147 g of platinum catalyst (manufactured by Wacker Chemie) and 5.81 g of vinyl group-containing linear polydimethylsiloxane (manufactured by Wacker Chemie) with a viscosity of 1,000 mPa s were stirred for 5 minutes to obtain a mixture (II). 3.96 g of the obtained mixture (I) was added to the mixture (II), and the mixture was stirred for 5 minutes with a stirrer to obtain a mixture (III). Finally, the obtained mixture (III) was filtered through a 300 mesh nylon filter to obtain an adhesive composition.

[0232] [Preparation Example 2] In a 600 mL stirring vessel dedicated to the stirrer, 148.3 g of a vinyl group-containing linear polydimethylsiloxane (Wacker Chem. Co.) having a viscosity of 100 mPa s as the polyorganosiloxane (a1), 16.4 g of a SiH group-containing linear polydimethylsiloxane (Wacker Chem. Co.) having a viscosity of 70 mPa s as the polyorganosiloxane (a2), 0.45 g of 1-ethynyl-1-cyclohexanol (Wacker Chem. Co.) as a polymerization inhibitor, 0.45 g of 1,1-diphenyl-2-propyn-1-ol (Tokyo Chemical Industry Co.), 0.21 g of a platinum catalyst (Wacker Chem. Co.) as a platinum group metal catalyst, and 17.2 g of p-menthane (Tokyo Chemical Industry Co.) as a solvent were added and stirred for 5 minutes. Finally, the resulting mixture was filtered through a 300 mesh nylon filter to obtain an adhesive composition.

[0233] [2] Preparation of Release Agent Composition [Synthesis Example 1] 86.36 g of 1,4-dioxane and 86.36 g of toluene were added to a mixture of 56.02 g of 1-phenylnaphthylamine, 50.00 g of 1-pyrenecarboxaldehyde (Maruzen Chemical Co., Ltd.), 6.67 g of 4-(trifluoromethyl)benzaldehyde, and 2.46 g of methanesulfonic acid, and the mixture was refluxed and stirred for 18 hours under a nitrogen atmosphere. After completion of the reaction, the mixture was diluted with 96 g of tetrahydrofuran, and the diluted solution was added dropwise to methanol to obtain a precipitate. The obtained precipitate was filtered, washed with methanol, and dried under reduced pressure at 60°C to obtain 72.12 g of a novolak resin. The weight average molecular weight measured by GPC in terms of standard polystyrene was 1,100. 60 g of the obtained novolak resin was dissolved in 849 g of propylene glycol monomethyl ether acetate, and the solution was filtered through a polyethylene microfilter having a pore size of 0.2 μm to prepare a release agent composition.

[0234] [3] Preparation of Laminate for Evaluation [Example 1] The adhesive composition obtained in Preparation Example 1 was spin-coated onto a 100 mm silicon carbide substrate (thickness 350 μm, manufactured by SICC) so that the film thickness in the final laminate obtained was approximately 30 μm, and heated at 120 ° C. for 90 seconds to form a release agent coating layer on the sample substrate, which was a semiconductor substrate. Meanwhile, the release agent composition obtained in Synthesis Example 1 was spin-coated onto a 100 mm glass wafer (EAGLE-XG, manufactured by Corning, thickness 500 μm) so that the film thickness in the final laminate obtained was approximately 200 nm, and heated at 250 ° C. for 300 seconds to form a release agent coating layer on the glass wafer. Then, using a vacuum bonding apparatus (2-1), the silicon carbide substrate and the glass wafer were bonded together so that the release agent coating layer and the adhesive coating layer were sandwiched between them, and then the sample substrate was placed face down and post-heat-treated on a hot plate at 200 ° C. for 10 minutes to produce a laminate. The bonding was performed at a temperature of 23°C and a reduced pressure of 1,500 Pa. The silicon carbide substrate of the obtained laminate was ground to a thickness of 20 μm using a grinding device, and then the glass wafer was irradiated with 308 nm excimer laser light at an energy of 150 mJ from a direction perpendicular to the glass wafer using a laser debonder. After the laser irradiation, it was confirmed whether peeling could be performed from the interface between the adhesive coating layer on the silicon carbide substrate and the release agent coating layer on the glass wafer, and it was found that peeling was easily possible.

[0235] Example 2 The adhesive composition obtained in Preparation Example 2 was spin-coated onto a 300 mm silicon substrate (thickness: 775 μm) so that the film thickness in the final laminate would be approximately 30 μm, and the substrate was heated at 120°C for 90 seconds to form a release agent coating layer on the sample substrate, which was a semiconductor substrate. Meanwhile, the release agent composition obtained in Synthesis Example 1 was spin-coated onto a 300 mm glass wafer (EAGLE-XG, manufactured by Corning Incorporated, thickness: 700 μm) so that the film thickness in the final laminate would be approximately 200 nm, and the substrate was heated at 250°C for 300 seconds to form a release agent coating layer on the glass wafer. Note that, from the viewpoint of ease of availability, a silicon substrate was used as an alternative to a compound semiconductor substrate. Then, using a vacuum bonding apparatus (2-2), the silicon substrate and the glass wafer were bonded together so that the release agent coating layer and the adhesive coating layer were sandwiched between them, and then the sample substrate was placed face down and post-heated on a hot plate at 200°C for 10 minutes to produce a laminate. The bonding was performed at a temperature of 23°C and a reduced pressure of 1,500 Pa. The obtained laminate was placed under a reduced pressure of 10 Pa and subjected to a heat treatment at 400°C for 1 hour. After the heat treatment, the laminate was observed through a glass substrate to determine whether bubbles had been generated due to gas components generated by peeling or decomposition. No peeling occurred. Furthermore, using a laser debonder, the glass wafer was irradiated perpendicularly with 308 nm excimer laser light at an energy of 150 mJ. After the laser irradiation, it was confirmed whether peeling could be performed from the interface between the adhesive layer on the silicon substrate and the release agent layer on the glass wafer. It was found that peeling was easily possible.

[0236] REFERENCE SIGNS LIST 1 Compound semiconductor substrate 2 Adhesive layer 2a Adhesive coating layer 3 Release agent layer 4 Support substrate L Light

Claims

1. A laminate having a compound semiconductor substrate temporarily bonded when processing the compound semiconductor substrate, the laminate having the compound semiconductor substrate, a support substrate, and an adhesive layer provided between the compound semiconductor substrate and the support substrate.

2. The laminate according to claim 1, further comprising a release agent layer provided between said compound semiconductor substrate and said support substrate.

3. The compound semiconductor in the compound semiconductor substrate is SiC, GaN, GaAs, Ga ２ O ３ 2. The stack according to claim 1, comprising at least one of AlGaAs and AlGaAs.

4. The laminate according to claim 1, wherein the adhesive layer is an adhesive layer formed from an adhesive composition.

5. The laminate according to claim 1, wherein the adhesive layer is a heat-resistant adhesive layer.

6. A method for manufacturing a processed compound semiconductor substrate, comprising: a processing step in which the compound semiconductor substrate of the laminate according to any one of claims 1 to 5 is processed; and a separation step in which the processed compound semiconductor substrate is separated from the support substrate.

7. The method for producing a processed compound semiconductor substrate according to claim 6, further comprising a cleaning step of cleaning the processed compound semiconductor substrate after the separating step.

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