Laminate, method for manufacturing laminate, and method for manufacturing processed semiconductor substrate

Abstract

Provided is, for example, a laminate which comprises an adhesive layer that is for temporarily bonding a semiconductor substrate and a support substrate and that can be formed of a thin film. The laminate can be effectively used in practical use since a separation step for separating the semiconductor substrate and the support substrate and a cleaning step for removing the adhesive layer remaining on the semiconductor substrate after separation can be simply and easily performed using the laminate.　The laminate comprises a semiconductor substrate, a support substrate, and an adhesive layer that is formed so as to be in contact with the semiconductor substrate. The adhesive layer is used for the purpose of temporarily bonding the semiconductor substrate and the support substrate to each other. The adhesive layer contains an organic resin and does not contain a silicone resin. The adhesive layer has a thickness of 200 nm to 20 µm inclusive.

Description

Laminate, method for manufacturing a laminate, and method for manufacturing a processed semiconductor substrate

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

[0002] Conventionally, semiconductor wafers have been integrated in a two-dimensional planar direction. To achieve even greater integration, there is a need for semiconductor integration technology that integrates (stacks) in a three-dimensional direction as well. This three-dimensional stacking is a technology that integrates in multiple layers while connecting them with through-silicon vias (TSVs). When integrating in multiple layers, the side opposite to the circuit surface (i.e., the back surface) of each wafer to be integrated is thinned by polishing, and the thinned semiconductor wafers are stacked.

[0003] Before thinning, the semiconductor wafer (referred to simply as a wafer here) is bonded to a support in order to be polished using a polishing device. This bonding is called temporary bonding because it must be easily removed after polishing. This temporary bonding must be easily removed from the support, as applying too much force during removal can cause the thinned semiconductor wafer to cut or deform. To prevent this, it must be easily removed. However, it is undesirable for the temporary bonding to detach or shift due to polishing stress during back-side polishing of the semiconductor wafer. Therefore, the required performance of the temporary bonding is to withstand the stress during polishing and to be easily removed after polishing.

[0004] As temporary adhesives used for such temporary bonding, adhesives containing polydimethylsiloxane (Patent Document 1) and temporary adhesives containing epoxy-modified polysiloxane (Patent Document 2) have been proposed.

[0005] International Publication No. 2017 / 221772 Brochure International Publication No. 2018 / 216732 Brochure

[0006] There is a constant need for adhesive compositions that can be effectively used as temporary bonding materials, and for practical laminates containing adhesive layers formed with such adhesive compositions. However, the polysiloxane-containing adhesive layers described in Patent Documents 1 and 2 are formed to cover electrodes formed on a semiconductor substrate. Therefore, the thickness of the adhesive layer is usually several tens of micrometers or more, and for example, in the examples described in Patent Documents 1 and 2, the thickness of the adhesive layer is 50 μm. However, if a semiconductor substrate with a flat surface is used, for example, an insulating film with grooves for wiring patterns formed in it, and a copper metal film embedded in these grooves (i.e., electrodes embedded in the substrate), then there is no need to cover the electrodes on the substrate, and therefore there is no need to form a thick adhesive layer. Polysiloxane, which was used in Patent Documents 1 and 2, has been widely used because it allows for the formation of adhesive layers with a certain thickness, but if a thin adhesive layer is to be formed, the material for forming the adhesive layer is not limited to polysiloxane. However, in laminates containing an adhesive layer formed using a material other than polysiloxane as an adhesive layer for temporarily bonding a semiconductor substrate and a support substrate, no practically effective laminate is known, nor is a practically effective laminate in which the adhesive layer is formed as a thin film. Therefore, the present invention aims to provide a practically effective laminate containing an adhesive layer that can be formed as a thin film and serves as an adhesive layer for temporarily bonding a semiconductor substrate and a support substrate, wherein the peeling step for separating the semiconductor substrate and the support substrate, and the cleaning step for removing the adhesive layer remaining on the semiconductor substrate after peeling, can be carried out simply and easily. The present invention also aims to provide a method for manufacturing the laminate and a method for manufacturing a processed semiconductor substrate using the laminate.

[0007] The inventors of the present invention conducted diligent studies to solve the aforementioned problems and, as a result, found that they could solve the aforementioned problems, and completed the present invention having the following gist.

[0008] In other words, the present invention encompasses the following: [1] A laminate comprising a semiconductor substrate, a support substrate, and an adhesive layer formed in contact with the semiconductor substrate, wherein the adhesive layer is used to temporarily bond the semiconductor substrate and the support substrate, the adhesive layer contains an organic resin but does not contain a silicone resin, and the thickness of the adhesive layer is 200 nm or more and 20 μm or less. [2] The laminate according to [1], wherein the thickness of the adhesive layer is 250 nm or more and 10 μm or less. [3] The laminate according to [1] or [2], wherein the semiconductor substrate is a substrate with a flat surface, in which grooves for wiring formation patterns are formed in an insulating film and a copper metal film is embedded in the grooves. [4] The laminate according to any one of [1] to [3], wherein the organic resin contains at least one resin selected from the group consisting of novolac resin, polyacrylic acid resin, polymethyl methacrylate resin, polyarylate resin, and polyimide resin. [5] A method for manufacturing a laminate according to any one of [1] to [4], comprising the step of applying an adhesive composition for forming the adhesive layer to either the semiconductor substrate or the support substrate. [6] The method for manufacturing a laminate according to [5], wherein the semiconductor substrate is a substrate with a flat surface, obtained by a damascene manufacturing method, in which grooves for wiring formation patterns are formed in the insulating film, and copper metal films are embedded in the grooves. [7] The method for manufacturing a laminate according to [6], comprising: etching a hard mask formed on the insulating film (dielectric film) to form a wiring formation pattern; then etching the insulating film using the hard mask to form grooves in the insulating film to form a wiring formation pattern similar to that of the hard mask in the insulating film; then removing the hard mask; then forming a copper metal film in the grooves and on the surface of the insulating film by electrolytic plating; and then removing the copper metal film on the surface by chemical mechanical polishing (CMP) to expose the surface of the insulating film.[8] A method for manufacturing a processed semiconductor substrate, comprising: a step of processing the semiconductor substrate in the laminate according to any one of [1] to [4]; and a peeling step of separating the support substrate and the processed semiconductor substrate by irradiating with a laser. [9] The method for manufacturing a processed semiconductor substrate according to [8], wherein the laser used in the peeling step is an infrared (IR) laser or an ultraviolet (UV) laser.

[10] The method for manufacturing a processed semiconductor substrate according to [9], wherein the peeling step includes a step of irradiating with an infrared (IR) laser from the silicon support substrate side, or a step of irradiating with an ultraviolet (UV) laser from the glass support substrate side.

[11] The method for manufacturing a processed semiconductor substrate according to any one of [8] to

[10] , further comprising a cleaning step of removing the adhesive layer on the semiconductor substrate after separation.

[12] The cleaning step is O. ２ Using a dry etching method by ashing, plasma-generated oxygen (O ２ A method for manufacturing a processed semiconductor substrate according to

[11] , wherein the adhesive layer is removed by reacting the adhesive layer with a gas.

[0009] According to the present invention, it is possible to provide a laminate containing an adhesive layer, which can be formed as a thin film, for temporarily bonding a semiconductor substrate and a support substrate, and which can be practically and effectively used in which a peeling step for separating the semiconductor substrate and the support substrate, and a cleaning step for removing the adhesive layer remaining on the semiconductor substrate after peeling, can be carried out simply and easily. Furthermore, a method for manufacturing the laminate and a method for manufacturing a processed semiconductor substrate using the laminate can be provided.

[0010] Figure 1 is a schematic cross-sectional view of an example of a laminate in the first embodiment. Figure 2 is a schematic cross-sectional view of another example of a laminate in the first embodiment. Figure 3A is a schematic cross-sectional view illustrating a method for manufacturing a laminate in an example of the first embodiment (part 1). Figure 3B is a schematic cross-sectional view illustrating a method for manufacturing a laminate in an example of the first embodiment (part 2). Figure 4A is a schematic cross-sectional view illustrating the manufacturing of a semiconductor substrate by a damascene manufacturing method (part 1). Figure 4B is a schematic cross-sectional view illustrating the manufacturing of a semiconductor substrate by a damascene manufacturing method (part 2). Figure 4C is a schematic cross-sectional view illustrating the manufacturing of a semiconductor substrate by a damascene manufacturing method (part 3). Figure 4D is a schematic cross-sectional view illustrating the manufacturing of a semiconductor substrate by a damascene manufacturing method (part 4). Figure 4E is a schematic cross-sectional view illustrating the manufacturing of a semiconductor substrate by a damascene manufacturing method (part 5). Figure 4F is a schematic cross-sectional view illustrating the manufacturing of a semiconductor substrate by a damascene manufacturing method (part 6).

[0011] (Laminate) The laminate of the present invention comprises a semiconductor substrate, a support substrate, and an adhesive layer formed in contact with the semiconductor substrate. The adhesive layer is used to temporarily bond the semiconductor substrate and the support substrate. The adhesive layer contains an organic resin but does not contain a silicone resin. The thickness of the adhesive layer is 200 nm or more and 20 μm or less.

[0012] The laminate of the present invention may further have a release agent layer, in which case it has a configuration comprising a support substrate, a semiconductor substrate, a release agent layer, and an adhesive layer.

[0013] The laminate of the present invention is used for temporary bonding when processing a semiconductor substrate and is suitably used for processing such as thinning of the semiconductor substrate. While the semiconductor substrate is being processed such as thinning, the semiconductor substrate is supported by a support substrate. On the other hand, after the semiconductor substrate has been processed, the support substrate and the semiconductor substrate are separated. After the semiconductor substrate and the support substrate are separated, any residue of the release agent layer or adhesive layer remaining on the semiconductor substrate or the support substrate is removed by a cleaning means.

[0014] <Adhesive Layer> As described above, the adhesive layer according to the present invention is used to temporarily bond a semiconductor substrate and a support substrate. The adhesive composition material for forming the adhesive layer contains an organic resin but does not contain a silicone resin. The thickness of the adhesive layer is 200 nm or more and 20 μm or less. In the present invention, since it is expected that the demand for thinner adhesive layers will increase in the future, the thickness of the adhesive layer is preferably 15 μm or less, more preferably 10 μm or less, and even more preferably 5 μm or less. The thickness of the adhesive layer may be 200 nm or more, 250 nm or more, 300 nm or more, 500 nm or more, or 1 μm or more. For example, the thickness of the adhesive layer may be 200 nm or more and 20 μm or less, or 250 nm or more and 10 μm or less.

[0015] <<Adhesive Composition>> The adhesive composition according to the present invention is an adhesive composition for forming an adhesive layer used for temporary bonding a support substrate and a semiconductor substrate. The components contained in the adhesive composition are materials that can be easily formed even if the thickness of the adhesive layer is 20 μm or less, and it is desirable that they be selected from organic materials, for example. More specifically, for example, the adhesive composition according to the present invention contains an organic resin. The organic resin may be a thermoplastic resin or a thermosetting resin. Examples of thermoplastic resins include novolac resin, polyacrylic acid resin, polymethyl methacrylate resin, acrylic resin, polyester resin, olefin resin, and styrene resin. Examples of thermosetting resins include polyarylate resin, polyimide resin, urea resin, melamine resin, phenolic resin, resorcinol resin, epoxy resin, acrylic resin, polyester resin, polyurethane resin, polybenzimidazole resin, polyamide resin, and isocyanate resin. The organic resin contained in the adhesive composition may be at least one resin selected from the group consisting of novolac resin, polyacrylic acid resin, polymethyl methacrylate resin, polyarylate resin, and polyimide resin.

[0016] <<<Novolac Resins>>> As mentioned above, an example of an organic resin is novolac resin. Novolac resins have at least one of a hydroxyl group directly bonded to an aromatic ring and at least one of a carboxyl group directly bonded to an aromatic ring. Novolac resins are resins obtained by condensing at least one of a phenolic compound, a carbazole compound, and an aromatic amine compound with at least one of an aldehyde compound, a ketone compound, and a divinyl compound, and optionally a styrene compound, under an acid catalyst.

[0017] Examples of phenolic compounds include phenols, naphthols, antrols, and hydroxypyrenes. Examples of phenols include phenol, cresol, xylenol, resorcinol, bisphenol A, p-tert-butylphenol, p-octylphenol, 9,9-bis(4-hydroxyphenyl)fluorene, and 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane. Examples of naphthols include 1-naphthol, 2-naphthol, 1,5-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, and 9,9-bis(6-hydroxynaphthyl)fluorene. Examples of antrols include 9-antrol. Examples of hydroxypyrenes include 1-hydroxypyrene and 2-hydroxypyrene. Examples of carbazole compounds include carbazole, 1,3,6,8-tetranitrocarbazole, 3,6-diaminocarbazole, 3,6-dibromo-9-ethylcarbazole, 3,6-dibromo-9-phenylcarbazole, 3,6-dibromocarbazole, 3,6-dichlorocarbazole, 3-amino-9-ethylcarbazole, 3-bromo-9-ethylcarbazole, 4,4'bis(9H-carbazole-9-yl)biphenyl, 4-glycidylcarbazole, 4-hydroxycarbazole, and 9-(1H-benzotriazole-1-ylmethyl Examples include (9-ethylcarbazole-9H-carbazole, 9-acetyl-3,6-diiodocarbazole, 9-benzoylcarbazole, 9-benzoylcarbazole-6-dicarboxyaldehyde, 9-benzylcarbazole-3-carboxyaldehyde, 9-methylcarbazole, 9-phenylcarbazole, 9-vinylcarbazole, potassium carbazole, carbazole-N-carbonyl chloride, N-ethylcarbazole-3-carboxyaldehyde, and N-((9-ethylcarbazole-3-yl)methylene)-2-methyl-1-indolinylamine. Examples of aromatic amine compounds include diphenylamine and N-phenyl-1-naphthylamine. These can be used individually or in combination of two or more. They may also have substituents.For example, these may have substituents on the aromatic ring.

[0018] Examples of aldehyde compounds include saturated aliphatic aldehydes, unsaturated aliphatic aldehydes, heterocyclic aldehydes, and aromatic aldehydes. Examples of saturated aliphatic aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, propylaldehyde, butyraldehyde, isobutyraldehyde, varelualdehyde, caproaldehyde, 2-methylbutyraldehyde, hexylaldehyde, undecanealdehyde, 7-methoxy-3,7-dimethyloctylaldehyde, cyclohexanealdehyde, 3-methyl-2-butyraldehyde, 2-ethylhexylaldehyde, glyoxal, malonaldehyde, succinaldehyde, glutaraldehyde, and adipinaldehyde. Examples of unsaturated aliphatic aldehydes include acrolein and methacrolein. Examples of heterocyclic aldehydes include furfural and pyridine aldehyde. Examples of aromatic aldehydes include benzaldehyde, naphthyl aldehyde, anthryl aldehyde, phenanthryl aldehyde, salicyl aldehyde, phenylacetaldehyde, 3-phenylpropionaldehyde, tolyl aldehyde, (N,N-dimethylamino)benzaldehyde, and acetoxybenzaldehyde. Among these, saturated aliphatic aldehydes and aromatic aldehydes are preferred. Examples of ketone compounds include diaryl ketone compounds. Examples of diaryl ketone compounds include diphenyl ketone, phenylnaphthyl ketone, dinaphthyl ketone, phenyltolyl ketone, and ditolyl ketone. Examples of divinyl compounds include divinylbenzene, dicyclopentadiene, tetrahydroindene, 4-vinylcyclohexene, 5-vinylnorborna-2-ene, divinylpyrene, limonene, and 5-vinylnorbornadiene. These can be used individually or in combination of two or more.

[0019] Novolac resins are, for example, novolac resins that absorb light and undergo deterioration. This deterioration is, for example, photodegradation.

[0020] The novolak resin contains, for example, at least any 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). For example, at least any one of the structural units represented by the following formula (C1-1), the structural unit represented by the following formula (1-2), and the structural unit represented by the following formula (C1-3) contained in the novolak resin may be at least 1 unit.

[0021]

[0022] 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 or a quaternary 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 the side chain or represents a methylene group. 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 bisphenol. C ５ represents a single bond or a group having a structure derived from styrene. In formula (C1-1), at least any one of C １ , C ２ and C ５ has at least any one of a hydroxy group directly bonded to an aromatic ring and a carboxy group directly bonded to an aromatic ring. In formula (C1-2), at least any one of C １ , C ３ and C ５ has at least any one of a hydroxy group directly bonded to an aromatic ring and a carboxy group directly bonded to an aromatic ring. In formula (C1-3), at least any one of C ２ , C ４ and C ５ has at least any one of a hydroxy group directly bonded to an aromatic ring and a carboxy group directly bonded to an aromatic ring.

[0023] In other words, 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, a group containing a tertiary or quaternary carbon atom or a methylene group having at least one selected from the group consisting of a secondary carbon atom, a quaternary carbon atom, and an aromatic ring as a side chain, and a group optionally having a structure derived from styrene (Formula (C1-1)) • A structural unit having a bond between a group derived from an aromatic compound containing a nitrogen atom, a group derived from an aliphatic polycyclic compound, and a group optionally having a structure derived from styrene (Formula (C1-2)) • A structural unit having a bond between 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, a group containing a tertiary or quaternary carbon atom or a methylene group having at least one selected from the group consisting of a quaternary carbon atom and an aromatic ring as a side chain, and a group optionally having a structure derived from styrene (Formula (C1-3))

[0024] C １ The group derived from an aromatic compound containing a nitrogen atom can be, for example, a group derived from carbazole, a group derived from N-phenyl-1-naphthylamine, a group derived from N-phenyl-2-naphthylamine, a group derived from N,N'-diphenyl-1,4-phenylenediamine, etc., but is not limited to these. ２ The group containing a tertiary or quaternary carbon atom or a methylene group having at least one selected from the group consisting of a secondary carbon atom, a quaternary carbon atom, and an aromatic ring in its side chain can be, for example, a group derived from 1-naphthaldehyde, a group derived from 1-pyrenecarboxyaldehyde, a group derived from 4-(trifluoromethyl)benzaldehyde, a group derived from 2-ethylhexylaldehyde, a group derived from acetaldehyde, etc., but is not limited to these. ３ The group derived from the aliphatic polycyclic compound may be, but is not limited to, a group derived from dicyclopentadiene. ４This 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. ５ This group has a single bond or a structure derived from styrene.

[0025] C ５ If the group has a structure derived from styrene, then C ５ It may have at least one of a hydroxyl group directly bonded to an aromatic ring and a carboxyl group directly bonded to an aromatic ring.

[0026] In a preferred embodiment, the novolac resin includes, for example, a structural unit represented by the following formula (C1-1-1) as a structural unit represented by formula (C1-1-1).

[0027]

[0028] In formula (C1-1-1), R ９０１ and R ９０２ R represents a substituent that substitutes for the ring, and each independently represents a halogen atom, a nitro group, a cyano group, an amino group, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group. ９０３ R represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group. ９０４ R represents a hydrogen atom, an optionally substituted aryl group, or an optionally substituted heteroaryl group. ９０５ R represents an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted heteroaryl group. ９０４ The base and R ９０５ The groups may bond with each other to form a divalent group. Examples of substituents on alkyl and alkenyl groups include halogen atoms, nitro groups, cyano groups, amino groups, hydroxyl groups, carboxyl groups, aryl groups, and heteroaryl groups. Examples of substituents on aryl and heteroaryl groups include halogen atoms, nitro groups, cyano groups, amino groups, hydroxyl groups, carboxyl groups, alkyl groups, and alkenyl groups. X１ and X ２ Each of these independently represents either a hydroxyl group or a carboxyl group. １ This represents a group having a single bond or a structure derived from styrene. １ and h ２ Each of these independently represents an integer between 0 and 3. １ and k ２ Each of these independently represents an integer between 0 and 3. １ tok １ The sum is 3 or less. ２ tok ２ The sum of these is 3 or less. However, the structural unit represented by formula (C1-1-1) has at least one of a hydroxyl group directly bonded to an aromatic ring and a carboxyl group directly bonded to an aromatic ring.

[0029] For example, in equation (C1-1-1), R ９０４ , R ９０５ and Z １ If at least one of them has a hydroxyl group or a carboxyl group, k １ and k ２ R may be 0. For example, in equation (C1-1-1), ９０４ and R ９０５ At least one of them is an aryl group having a hydroxyl group or a carboxyl group, or Z １ If it has at least one of a hydroxyl group directly bonded to an aromatic ring and a carboxyl group directly bonded to an aromatic ring, then k １ and k ２ k may be 0. For example, in equation (C1-1-1), k １ and k ２ If R is 0, ９０４ , R ９０５ and Z １ Preferably, at least one of them has a hydroxyl group or a carboxyl group. For example, in formula (C1-1-1), k １ and k ２ If R is 0, ９０４ and R ９０５At least one of them is an aryl group having a hydroxyl group or a carboxyl group, or Z １ It is preferable that the compound has at least one of a hydroxyl group directly bonded to an aromatic ring and a carboxyl group directly bonded to an aromatic ring.

[0030] In this specification, the number of carbon atoms in optionally substituted alkyl groups and optionally substituted alkenyl groups is usually 40 or less, preferably 30 or less, and more preferably 20 or less, from the viewpoint of solubility. In this specification, the number of carbon atoms in optionally substituted aryl groups and heteroaryl groups is usually 40 or less, preferably 30 or less, and more preferably 20 or less, from the viewpoint of solubility.

[0031] In this specification, examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, and the like.

[0032] In this specification, examples of substituents on optionally substituted alkyl groups include halogen atoms, alkoxy groups, and halogenated alkoxy groups. In this specification, examples of substituents on optionally substituted alkenyl groups include halogen atoms, alkoxy groups, and halogenated alkoxy groups. In this specification, examples of substituents on optionally substituted aryl groups include halogen atoms, hydroxyl groups, carboxyl groups, cyano groups, alkyl groups, halogenated alkyl groups, alkoxy groups, and halogenated alkoxy groups. In this specification, examples of substituents on optionally substituted heteroaryl groups include halogen atoms, hydroxyl groups, carboxyl groups, cyano groups, alkyl groups, halogenated alkyl groups, alkoxy groups, and halogenated alkoxy groups.

[0033] Specific examples of substituted alkyl groups include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group, n-pentyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl-n-propyl group, 1,2-dimethyl-n-propyl group, 2,2-dimethyl-n-propyl group, 1-ethyl-n-propyl group, n-hexyl, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, 3-methyl-n-pentyl group, 4-methyl Examples include, but are not limited to, ethyl-n-pentyl group, 1,1-dimethyl-n-butyl group, 1,2-dimethyl-n-butyl group, 1,3-dimethyl-n-butyl group, 2,2-dimethyl-n-butyl group, 2,3-dimethyl-n-butyl group, 3,3-dimethyl-n-butyl group, 1-ethyl-n-butyl group, 2-ethyl-n-butyl group, 1,1,2-trimethyl-n-propyl group, 1,2,2-trimethyl-n-propyl group, 1-ethyl-1-methyl-n-propyl group, 1-ethyl-2-methyl-n-propyl group, and 2-ethylhexyl group.

[0034] Specific examples of alkenyl groups that may be substituted include ethenyl group, 1-propenyl group, 2-propenyl group, 1-methyl-1-ethenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 2-methyl-1-propenyl group, 2-methyl-2-propenyl group, 1-ethylethenyl group, 1-methyl-1-propenyl group, 1-methyl-2-propenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 1-n-propylethenyl group, 1-methyl-1-butenyl group, 1-methyl-2-butenyl group, and 1-methyl-3-butenyl group. Nyl group, 2-ethyl-2-propenyl group, 2-methyl-1-butenyl group, 2-methyl-2-butenyl group, 2-methyl-3-butenyl group, 3-methyl-1-butenyl group, 3-methyl-2-butenyl group, 3-methyl-3-butenyl group, 1,1-dimethyl-2-propenyl group, 1-i-propylethenyl group, 1,2-dimethyl-1-propenyl group, 1,2-dimethyl-2-propenyl group, 1-cyclopentenyl group, 2-cyclopentenyl group, 3-cyclopentenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group Xenyl group, 1-methyl-1-pentenyl group, 1-methyl-2-pentenyl group, 1-methyl-3-pentenyl group, 1-methyl-4-pentenyl group, 1-n-butylethenyl group, 2-methyl-1-pentenyl group, 2-methyl-2-pentenyl group, 2-methyl-3-pentenyl group, 2-methyl-4-pentenyl group, 2-n-propyl-2-propenyl group, 3-methyl-1-pentenyl group, 3-methyl-2-pentenyl group, 3-methyl-3-pentenyl group, 3-methyl-4-pentenyl group, 3-ethyl-3-butenyl group, 4-methyl-1-pentenyl group, 4-methyl-2-pentenyl group, 4-methyl-3-pentenyl group, 4-methyl-4-pentenyl group, 1,1-dimethyl-2-butenyl group, 1,1-dimethyl-3-butenyl group, 1,2-dimethyl-1-butenyl group, 1,2-dimethyl-2-butenyl group, 1,2-dimethyl-3-butenyl group, 1-methyl-2-ethyl-2-propenyl group, 1-s-butylethenyl group, 1,3-dimethyl-1-butenyl group, 1,3-dimethyl-2-butenyl group, 1,3-dimethyl-3-butenyl group, 1-i-butylethenyl group, 2,2-dimethyl-3-butenyl group, 2,3-dimethyl-1-butenyl group, 2,3-dimethyl-2-butenyl group, 2,3-dimethyl-3-butenyl group, 2-i-propyl-2-propenyl group, 3,3-dimethyl-1-butenyl group, 1-ethyl-1-butenyl group, 1-ethyl-2-butenyl group, 1-ethyl-3-butenyl group, 1-n-propyl-1-propenyl group, 1-n-propyl-2-propenyl group, 2-ethyl-1-butenyl group, 2-ethyl-2-butenyl group, 2-ethyl-3-butenyl group, 1,1,2-trimethyl-2-propenyl group, 1-tert-butylethenyl group, 1-methyl-1-ethyl-2-propenyl group, 1-ethyl-2-methyl-1-propenyl group, 1-ethyl-2-methyl-2-propenyl group, 1-i-propyl-1-propenyl group Examples include, but are not limited to, 1-i-propyl-2-propenyl group, 1-methyl-2-cyclopentenyl group, 1-methyl-3-cyclopentenyl group, 2-methyl-1-cyclopentenyl group, 2-methyl-2-cyclopentenyl group, 2-methyl-3-cyclopentenyl group, 2-methyl-4-cyclopentenyl group, 2-methyl-5-cyclopentenyl group, 2-methylene-cyclopentyl group, 3-methyl-1-cyclopentenyl group, 3-methyl-2-cyclopentenyl group, 3-methyl-3-cyclopentenyl group, 3-methyl-4-cyclopentenyl group, 3-methyl-5-cyclopentenyl group, 3-methylene-cyclopentyl group, 1-cyclohexenyl group, 2-cyclohexenyl group, and 3-cyclohexenyl group.

[0035] Specific examples of aryl groups that may be substituted include, but are not limited to, phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 2-chlorophenyl group, 3-chlorophenyl group, 4-chlorophenyl group, 2-fluorophenyl group, 3-fluorophenyl group, 4-fluorophenyl group, 4-methoxyphenyl group, 4-ethoxyphenyl group, 4-nitrophenyl group, 4-cyanophenyl group, 2-hydroxyphenyl group, 3-hydroxyphenyl group, 4-hydroxyphenyl group, 2-carboxyphenyl group, 3-carboxyphenyl group, 4-carboxyphenyl group, 4-amyloxyphenyl group, 1-naphthyl group, 2-naphthyl group, biphenyl-4-yl group, biphenyl-3-yl group, biphenyl-2-yl group, 1-anthryl group, 2-anthryl group, 9-anthryl group, 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group, 4-phenanthryl group, and 9-phenanthryl group.

[0036] Specific examples of heteroaryl groups that may be substituted include, but are not limited to, 2-thienyl, 3-thienyl, 2-furanyl, 3-furanyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 3-isothiazolyl, 4-isothiazolyl, and 5-isothiazolyl groups.

[0037] Z １ For example, the group represented by the following formula (Z) can be cited. In formula (Z), R ９１０ R represents a halogen atom, a nitro group, a cyano group, an amino group, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group. ９１１ X represents a hydrogen atom or a methyl group. １０ h represents a hydroxyl group or a carboxyl group. １０ and k １０ Each of these independently represents an integer between 0 and 3. １０ tok １０The total is 5 or less. * represents a linking group.

[0038] R ９１０ Specific examples of R ９０１ and R ９０２ include the specific examples given in the description of R

[0039] Hereinafter, specific examples of the structural unit represented by formula (C1-1-1) are given, but are not limited thereto. Also, the substitution positions of the hydroxy group and carboxy group on the aromatic ring are not limited.

[0040]

[0041] In a preferred embodiment, the novolak resin contains, as the structural unit represented by formula (C1-1), for example, the structural unit represented by the following formula (C1-1-2).

[0042]

[0043] In formula (C1-1-2), Ar ９０１ and Ar ９０２ each independently represents an aromatic ring, and R ９０１ to R ９０５ , X １ and X ２ , Z １ , h １ and h ２ , and k １ and k ２ represent the same meaning as above. The sum of h １ and k １ is 3 or less. The sum of h ２ and k ２ is 3 or less. n represents an integer of 1 or 2. However, the structural unit represented by formula (C1-1-2) has at least one of a hydroxy group directly bonded to an aromatic ring and a carboxy group directly bonded to an aromatic ring. Examples of the aromatic ring include a benzene ring, a naphthalene ring, etc.

[0044] For example, in formula (C1-1-2), when at least one of R ９０４ , R ９０５ and Z １ has a hydroxy group or a carboxy group, k １ and k２ may be 0. For example, in formula (C1-1-2), R ９０４ and R ９０５ is an aryl group having at least one of a hydroxy group or a carboxy group, or when Z １ has at least one of a hydroxy group directly bonded to an aromatic ring and a carboxy group directly bonded to an aromatic ring, k １ and k ２ may be 0. For example, in formula (C1-1-2), k １ and k ２ is 0, it is preferable that at least one of R ９０４ , R ９０５ and Z １ has a hydroxy group or a carboxy group. For example, in formula (C1-1-2), when k １ and k ２ is 0, at least one of R ９０４ and R ９０５ is an aryl group having a hydroxy group or a carboxy group, or it is preferable that Z １ has at least one of a hydroxy group directly bonded to an aromatic ring and a carboxy group directly bonded to an aromatic ring.

[0045] Hereinafter, specific examples of the structural unit represented by formula (C1-1-2) are given, but are not limited thereto. Also, the substitution positions of the hydroxy group and carboxy group on the aromatic ring are not limited either.

[0046]

[0047] In a preferred embodiment, the novolak resin contains, as a structural unit represented by formula (C1-2), for example, a structural unit represented by the following formula (C1-2-1) or (C1-2-2).

[0048]

[0049] In the above formula, R ９０６ to R ９０９is a substituent bonded to the ring, each independently representing a halogen atom, a nitro group, a cyano group, an amino group, a hydroxyl group, a carboxyl group, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group. Specific examples and preferred carbon number configurations of the halogen atom, optionally substituted alkyl group, optionally substituted alkenyl group, and optionally substituted aryl group are the same as those described above. ３ ~h ６ Each of these independently represents an integer between 0 and 3. ９０１ ~R ９０５ , X １ and X ２ Z １ , h １ and h ２ , and k １ and k ２ This expresses the same meaning as above. １ tok １ The sum is 3 or less. ２ tok ２ The sum of these is 3 or less. However, the structural unit represented by formula (C1-2-1) and the structural unit represented by formula (C1-2-2) each independently have at least one of a hydroxyl group directly bonded to an aromatic ring and a carboxyl group directly bonded to an aromatic ring.

[0050] The following are specific examples of structural units represented by formulas (C1-2-1) and (C1-2-2), but are not limited to these. Furthermore, the substitution positions of hydroxyl and carboxyl groups on the aromatic ring are not limited.

[0051]

[0052] In a preferred embodiment, the novolac resin includes, for example, a structural unit represented by formula (C1-3-1) below, as a structural unit represented by formula (C1-3). In formula (C1-3-1), R ８０１ R represents a substituent that substitutes for the ring, and each independently represents a halogen atom, a nitro group, a cyano group, an amino group, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group.８０２ R represents a hydrogen atom, an optionally substituted aryl group, or an optionally substituted heteroaryl group. ８０３ R represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted heteroaryl group. ８０２ The base and R ８０３ The groups may bond with each other to form a divalent group. Examples of substituents on aryl and heteroaryl groups include halogen atoms, nitro groups, cyano groups, amino groups, hydroxyl groups, carboxyl groups, alkyl groups, and alkenyl groups. ８０１ X represents a benzene ring, naphthalene ring, or biphenyl structure. １１ This represents a hydroxyl group or a carboxyl group. １ This represents a group having a single bond or a structure derived from styrene. １１ Each of these independently represents an integer between 0 and 4. １１ Each of these independently represents an integer from 0 to 4. ８０１ When h is a benzene ring １１ tok １１ The sum of is 4 or less, Ar ８０１ When h is a naphthalene ring １１ tok １１ The sum of is 6 or less, Ar ８０１ When h is a biphenyl structure １１ tok １１ The sum of these is 8 or less. However, the structural unit represented by formula (C1-3-1) has at least one of a hydroxyl group directly bonded to an aromatic ring and a carboxyl group directly bonded to an aromatic ring.

[0053] For example, in equation (C1-3-1), R ８０２ , R ８０３ and Z １ If at least one of them has a hydroxyl group or a carboxyl group, k １１ R may be 0. For example, in equation (C1-3-1), ８０２ and R ８０３ At least one of them is an aryl group having a hydroxyl group or a carboxyl group, or Z１ If it has at least one of a hydroxyl group directly bonded to an aromatic ring and a carboxyl group directly bonded to an aromatic ring, then k １１ k may be 0. For example, in equation (C1-3-1), k １１ If R is 0, ８０２ and R ８０３ At least one of these is an aryl group having a hydroxyl group or a carboxyl group, or a heteroaryl group having a hydroxyl group or a carboxyl group.

[0054] The following are specific examples of structural units represented by formula (C1-3), but are not limited to these.

[0055]

[0056] As mentioned above, novolac resin is a resin obtained by condensing, for example, a phenolic compound, a carbazole compound, and an aromatic amine compound with at least one aldehyde compound, a ketone compound, and a divinyl compound, and optionally a styrene compound, under an acid catalyst. In this condensation reaction, for example, an aldehyde compound or ketone compound is usually used in a ratio of 0.1 to 10 equivalents per 1 equivalent of the benzene ring constituting the ring of the carbazole compound. When introducing at least one of a hydroxyl group directly bonded to an aromatic ring and a carboxyl group directly bonded to an aromatic ring into the novolac resin using a styrene compound, the styrene compound used as a reaction raw material may have a protecting group. An example of a styrene compound having a protecting group is tert-leaved oxystyrene.

[0057] In the above condensation reaction, an acid catalyst is usually used. Examples of acid catalysts 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 acid catalyst is determined appropriately depending on the type of acid used and cannot be specified in general terms, but it is usually set appropriately from the range of 0.001 to 10,000 parts by mass per 100 parts by mass of the carbazole compound.

[0058] The above condensation reaction can sometimes be carried out without a solvent if either the starting compound or the acid catalyst is a liquid, but it is usually carried out with a solvent. Such solvents are not particularly limited as long as they do not inhibit the reaction, but typical examples include ether compounds and ether ester compounds. Examples of ether compounds include cyclic ether compounds such as tetrahydrofuran and dioxane. Examples of ether ester compounds include methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate, and propylene glycol monopropyl ether propionate.

[0059] The reaction temperature is usually determined appropriately within the range of 40°C to 200°C, and the reaction time cannot be specified in general terms as it varies depending on the reaction temperature, but it is usually determined appropriately within the range of 30 minutes to 50 hours.

[0060] After the reaction is complete, if necessary, the novolac resin is purified and isolated according to standard methods and used in the preparation of release agent compositions and adhesive compositions. A person skilled in the art can determine the production conditions for the novolac resin without undue burden based on the above description and common technical knowledge, and therefore can produce the novolac resin.

[0061] The weight-average molecular weight of novolac resin is typically 500 to 200,000, 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 ensuring solubility in solvents, and 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, from the viewpoint of improving film strength. In this invention, the weight-average molecular weight, number-average molecular weight, and degree of dispersion of the novolac resin can be measured, for example, using a GPC instrument (EcoSEC, HLC-8320GPC manufactured by Tosoh Corporation) and a GPC column (TSKgel SuperMultiporeHZ-N, TSKgel SuperMultiporeHZ-H manufactured by Tosoh Corporation), with a column temperature of 40°C, tetrahydrofuran as the eluent (elution solvent), a flow rate (flow rate) of 0.35 mL / min, and polystyrene (manufactured by Sigma-Aldrich) as the standard sample.

[0062] <<<Polyarylate Resin>>> Polyarylate resin is an aromatic polyester resin obtained from an aromatic dicarboxylic acid component (including its functional derivatives) and a divalent phenol component, and contains these components as monomer components. The aromatic dicarboxylic acid component for introducing aromatic dicarboxylic acid residues that constitute the polyarylate resin is an organic compound containing an aromatic ring and two carboxyl groups per molecule. The carboxyl group may also be an acid halide group. An acid halide group is a group in which the hydroxyl group of a carboxyl group is replaced by a halogen atom. Specific examples of such aromatic dicarboxylic acid components include, for example, terephthalic acid, isophthalic acid, phthalic acid, chlorophthalic acid, nitrophthalic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, methylterephthalic acid, 4,4'-biphenyldicarboxylic acid, 2,2'-biphenyldicarboxylic acid, 4,4'-diphenyletherdicarboxylic acid, 4,4'-diphenylmethanedicarboxylic acid, 4,4'-diphenylsulfondicarboxylic acid, 4,4'-diphenylisopropylidenedicarboxylic acid, 1,2-bis(4-carboxyphenoxy)ethane, 5-sodium sulfisoisophthalic acid, diphenic acid, and their derivatives (e.g., acid halides). These aromatic dicarboxylic acids can be used individually or in combination of two or more types. Among these, polyarylate resins are preferably made to contain at least one, preferably both, of terephthalic acid and isophthalic acid, from the viewpoint of further improving color tone and colorfastness. The divalent phenol component for introducing divalent phenol residues into the polyarylate resin is an organic compound containing two phenolic hydroxyl groups per molecule. A phenolic hydroxyl group is a hydroxyl group that is directly bonded to an aromatic ring.Specific examples of such divalent phenol components include, for example, 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), 2,2-bis(3-methyl-4-hydroxyphenyl)propane (bisphenol C), 1,1-bis(4-hydroxyphenyl)cyclohexane (bisphenol Z), 1,1-bis(4-hydroxyphenyl)-1-phenylethane (bisphenol AP), 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, and 2,2-bis(4-hydroxy-3,5-dibromophenyl). Examples include propane, 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl ketone, 4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxybiphenyl [4,4'-biphenol], 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (bisphenol TMC), 4,4'-(1,3-dimethylbutylidene)diphenol, resorcinol, etc. These compounds may be used individually or in combination of two or more. From the viewpoint of further improving color tone and colorfastness, the polyarylate resin preferably contains one or more divalent phenol components selected from the group consisting of bisphenol A, bisphenol C, bisphenol Z, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, and bisphenol TMC, and more preferably contains bisphenol A.

[0063] The polyarylate resin may be a commercially available product. Examples of commercially available products include M-2000H (manufactured by Unitika Ltd.).

[0064] <<<Solvent>>> The adhesive composition preferably contains a solvent. As such a solvent, for example, a highly polar solvent that can dissolve the film components of the organic resin mentioned above well can be used, and if necessary, a low-polarity solvent may be used for the purpose of adjusting viscosity, surface tension, etc. In this invention, a low-polarity solvent is defined as one with a relative permittivity of less than 7 at a frequency of 100 kHz, and a highly polar solvent is defined as one with a relative permittivity of 7 or more at a frequency of 100 kHz. The solvent can be used alone or in combination of two or more types.

[0065] Examples of highly polar solvents include amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylisobutylamide, N-methylpyrrolidone, and 1,3-dimethyl-2-imidazolidinone; ketone solvents such as ethyl methyl ketone, isophorone, and cyclohexanone; cyano solvents such as acetonitrile and 3-methoxypropionitrile; polyhydric alcohol solvents such as ethylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, 1,3-butanediol, and 2,3-butanediol; monohydric alcohol solvents other than aliphatic alcohols such as propylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monophenyl ether, triethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, benzyl alcohol, 2-phenoxyethanol, 2-benzyloxyethanol, 3-phenoxybenzyl alcohol, and tetrahydrofurfuryl alcohol; and sulfoxide solvents such as dimethyl sulfoxide.

[0066] Examples of low-polarity solvents include chlorine-based solvents such as chloroform and chlorobenzene; aromatic hydrocarbon solvents such as alkylbenzenes such as toluene, xylene, tetralin, cyclohexylbenzene, and decylbenzene; aliphatic alcohol solvents such as 1-octanol, 1-nonanol, and 1-decanol; ether-based solvents such as tetrahydrofuran, dioxane, anisole, 4-methoxytoluene, 3-phenoxytoluene, dibenzyl ether, diethylene glycol dimethyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, and triethylene glycol butyl methyl ether; and ester-based solvents such as methyl benzoate, ethyl benzoate, butyl benzoate, isoamyl benzoate, bis(2-ethylhexyl) phthalate, dibutyl maleate, dibutyl oxalate, hexyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, and diethylene glycol monobutyl ether acetate.

[0067] The solvent content is determined appropriately considering the viscosity of the desired composition, the coating method used, the thickness of the film to be produced, etc., but is 99% by mass or less of the total composition, preferably 70 to 99% by mass of the total composition, that is, the amount of film components in that case is 1 to 30% by mass of the total composition.

[0068] The viscosity and surface tension of the adhesive composition are appropriately adjusted by changing the type and ratio of solvents used, the concentration of film components, etc., taking into consideration various factors such as the application method used and the desired film thickness.

[0069] Adhesive compositions can be manufactured, for example, by mixing an organic resin with a solvent. The mixing order is not particularly limited, but examples of methods that can easily and reproducibly manufacture adhesive compositions include, but are not limited to, a method in which the organic resin is dissolved in the solvent all at once, or a method in which a portion of the organic resin is dissolved in the solvent, the remainder is dissolved in the solvent separately, and the resulting solutions are mixed. Furthermore, when preparing the adhesive composition, heating may be used as appropriate, within a range that does not cause the components to decompose or deteriorate. In the present invention, for the purpose of removing foreign matter, the solvent or solution used may be filtered using a filter or the like during the manufacturing of the adhesive composition or after all components have been mixed.

[0070] The content of organic resin in the adhesive composition is not particularly limited, but it is preferably 50% to 100% by mass, more preferably 60% to 99% by mass, and particularly preferably 70% to 95% by mass, relative to the film components of the adhesive composition. In this invention, film components refer to components other than the solvent contained in the composition.

[0071] A specific embodiment of the laminate will be described below in <First Embodiment>.

[0072] <First Embodiment> A laminate having a semiconductor substrate is used for processing the semiconductor substrate. While the semiconductor substrate is being processed, the semiconductor substrate is bonded to a support substrate. After processing the semiconductor substrate, the semiconductor substrate is separated from the support substrate.

[0073] <<Semiconductor Substrate>> The main material constituting the entire semiconductor substrate is not particularly limited as long as it is used for this type of application, but examples include silicon, silicon carbide, compound semiconductors, and glass substrates with organic resin. The shape of the semiconductor substrate is not particularly limited, but for example it is disc-shaped. Note that the surface shape of the disc-shaped semiconductor substrate does not need to be a perfect circle; for example the outer edge of the semiconductor substrate may have a straight section called an orientation flat or a notch. The thickness of the disc-shaped semiconductor substrate is not particularly limited and can be appropriately determined according to the intended use of the semiconductor substrate, but for example it is 500 to 1,000 μm. The diameter of the disc-shaped semiconductor substrate is not particularly limited and can be appropriately determined according to the intended use of the semiconductor substrate, but for example it is 100 to 1,000 mm.

[0074] An example of a semiconductor substrate is a silicon wafer with a diameter of approximately 300 mm and a thickness of approximately 770 μm.

[0075] The semiconductor substrate used in the present invention is a semiconductor substrate with a flat surface in which grooves for wiring formation patterns are formed in an insulating film, and a copper metal film is embedded in the grooves. If the semiconductor substrate has a structure in which electrodes are formed on the substrate, there may be irregularities on the substrate surface due to the height of the electrodes. However, if the semiconductor substrate has a structure in which electrodes are embedded in the substrate, the surface is flat, so when an adhesive layer is provided in contact with such a semiconductor substrate, it is not necessary to cover the electrodes on the semiconductor substrate, and therefore the thickness of the adhesive layer can be made thin. A semiconductor substrate with a flat surface as described above can be manufactured, for example, by a damascene manufacturing method.

[0076] <<<Manufacturing of Semiconductor Substrates by Damascene Manufacturing Method>>> Semiconductor substrates can be manufactured by using a damascene manufacturing method that includes the following steps: A mask (hard mask (HM)) is formed on an insulating film (dielectric film). The layer of the hard mask is etched to form a wiring pattern. The insulating film is etched using the hard mask to form grooves in the insulating film, thereby forming a wiring pattern similar to that of the hard mask in the insulating film. The hard mask is removed. A copper metal film is formed on the inside and surface of the insulating film by electrolytic plating. The copper metal film on the surface is removed by chemical mechanical polishing (CMP) to expose the surface of the insulating film.

[0077] The manufacturing of a semiconductor substrate by the damascene manufacturing method will be explained using the schematic cross-sectional views in Figures 4A to 4F. Figure 4 (Figures 4A to 4F are collectively referred to as Figure 4) shows a schematic cross-sectional view of a semiconductor substrate 20. In Figure 4A, a passivation film 12, an insulating film 11b, and a hard mask 13 are stacked on the insulating film 11a in this order. In Figure 4A, the hard mask layer is etched to form a wiring pattern. In Figure 4B, the insulating film 11b and the passivation film 12 are etched using the hard mask, and grooves are formed in the insulating film 11b, creating a wiring pattern on the insulating film 11b similar to that of the hard mask. In Figure 4C, the hard mask is removed. In Figure 4D, a copper metal film 14 is formed in the grooves and on the surface of the insulating film 11b by electroplating (the copper metal film is embedded in the grooves). In Figure 4E, the copper metal film 14 on the surface is removed by chemical mechanical polishing (CMP), exposing the surface of the insulating film 11b (the surface of the copper metal film 14 is removed until the surface of the insulating film 11b is exposed, making the surfaces of the insulating film 11b and the copper metal film 14 flat). As shown in Figure 4E, the damascene manufacturing method allows for the creation of a semiconductor substrate with a flat surface in which grooves for wiring patterns are formed in the insulating film and copper metal films are embedded in these grooves. Furthermore, as shown in Figure 4F, an etching stop layer 15 may be provided on the surface.

[0078] In this invention, a semiconductor substrate with a flat surface can be obtained by a damascene manufacturing method, and therefore a semiconductor substrate with a flat surface can be used. Since an adhesive layer is laminated on a flat semiconductor substrate, the thickness of the adhesive layer according to this invention can be formed as a thin film of 20 μm or less. In this invention, a semiconductor substrate is considered flat if no protrusions or recesses are formed on the surface of the semiconductor substrate by electrodes or the like, and if the height of the protrusions or recesses relative to the substrate surface is 5 μm or less, it can be said to be substantially flat.

[0079] <<Support Substrate>> The support substrate is not particularly limited as long as it is a material that can support the semiconductor substrate when the semiconductor substrate is being processed, but examples include glass support substrates and silicon support substrates.

[0080] The shape of the support substrate is not particularly limited, but for example, it can be disc-shaped. The disc-shaped support substrate does not need to have a perfectly circular surface; for example, the outer circumference of the support substrate may have a straight section called an orientation flat, or a notch. The thickness of the disc-shaped support substrate can be appropriately determined according to the size of the semiconductor substrate, etc., and is not particularly limited, but for example, it is 500 to 1,000 μm. The diameter of the disc-shaped support substrate can be appropriately determined according to the size of the semiconductor substrate, etc., and is not particularly limited, but for example, it is 100 to 1,000 mm.

[0081] An example of a support substrate is a glass wafer with a diameter of approximately 300 mm and a thickness of approximately 700 μm.

[0082] In this invention, peeling of the laminate is preferably performed by light irradiation, taking into consideration that the adhesive layer is a thin film. Therefore, as the support substrate, for example, a substrate that is light-transmitting to the light used is used. As will be explained in detail below, for silicon support substrates, the laser used in the peeling process is preferably an infrared (IR) laser, and for glass support substrates, the laser used in the peeling process is preferably an ultraviolet (UV) laser.

[0083] <<Adhesive Layer>> The adhesive layer is provided between the support substrate and the semiconductor substrate. The adhesive layer is in contact with the semiconductor substrate, for example. The adhesive layer may also be in contact with the support substrate, for example. The adhesive layer is an adhesive layer formed from the adhesive composition described above.

[0084] As described above, the thickness of the adhesive layer in the laminate of the present invention is 20 μm or less, preferably 15 μm or less, more preferably 10 μm or less, and even more preferably 5 μm or less. The film thickness of the adhesive layer may be 200 nm or more, 250 nm or more, 300 nm or more, 500 nm or more, or 1 μm or more. For example, the film thickness of the adhesive layer may be 200 nm or more and 20 μm or less, or 250 nm or more and 10 μm or less.

[0085] The method for forming an adhesive layer from the adhesive composition will be described in detail below in the section titled "<>".

[0086] Furthermore, in this invention, the adhesive composition for forming the adhesive layer does not contain polysiloxane materials, and the material can be selected from organic materials that can suitably undergo the necessary alteration, such as decomposition, upon light irradiation to improve peelability. Therefore, depending on the type of organic material selected, the adhesive layer according to the present invention will not only function as a temporary adhesive layer, but also as a release agent layer when separating the support substrate and the semiconductor substrate by light irradiation.

[0087] <<Release Agent Layer>> The laminate may have a release agent layer. In a laminate having a release agent layer, for example, separation of the semiconductor substrate and the support substrate is performed by light irradiation of the release agent layer. In the present invention, as described above, the laminate may be configured in a way in which no release agent layer is provided, and the adhesive layer according to the present invention also functions as a release agent layer, or the laminate may be configured in a way in which a release agent layer is formed separately from the adhesive layer, and both an adhesive layer and a release agent layer are present. The release agent layer may be formed, for example, from a release agent composition.

[0088] <<<Release Agent Composition>>> The release agent composition contains, for example, at least an organic resin or a polynuclear phenol derivative, and optionally other components. The organic resin is preferably one that can exhibit suitable release ability, and when the semiconductor substrate and the support substrate are separated by light irradiation of the release agent layer, the organic resin preferably absorbs light and undergoes a change, such as decomposition, necessary to improve the release ability.

[0089] A laminate having a release agent layer formed from a release agent composition can be peeled off without applying excessive load for peeling by, for example, irradiating the release agent layer with a laser. The release agent layer of the laminate has a reduced adhesive strength compared to before irradiation, for example, when irradiated with a laser. That is, in the laminate, for example, while a semiconductor substrate is being processed such as thinning, the semiconductor substrate is suitably supported on a laser-transmitting support substrate via an adhesive layer and a release agent layer. After processing is complete, by irradiating a laser from the support substrate side, the laser that has passed through the support substrate is absorbed by the release agent layer, causing alteration (e.g., separation) of the release agent layer at the interface between the release agent layer and the adhesive layer, at the interface between the release agent layer and the support substrate, or within the release agent layer itself. As a result, suitable peeling (separation) can be achieved without applying excessive load for peeling.

[0090] <<<<<Novolac resin>>>> Examples of organic resins include novolac resin. The description of novolac resin is as explained in the <<Novolac resin>> section of the <Adhesive composition> above.

[0091] The organic resin contained in the above-mentioned release agent composition is preferably novolac resin. Therefore, the above-mentioned release agent composition preferably contains novolac resin alone as the organic resin. However, other polymers may be included together with the novolac resin for purposes such as adjusting the film properties. Examples of such other polymers include polyacrylic acid ester compounds, polymethacrylic acid ester compounds, polyacrylamide compounds, polymethacrylamide compounds, polyvinyl compounds, polystyrene compounds, polymaleimide compounds, polymaleic anhydride, and polyacrylonitrile compounds.

[0092] The content of novolac resin in the release agent composition is not particularly limited, but it is preferably 70% by mass or more relative to the total amount of polymer contained in the release agent composition. The content of novolac resin in the release agent composition is not particularly limited, but it is preferably 50 to 100% by mass relative to the film constituent components. In this invention, film constituent components refer to components other than the solvent contained in the composition.

[0093] <<<<<Polynuclear phenol derivatives>>>> A polynuclear phenol derivative is represented, for example, by the following formula (P).

[0094] In formula (P), Ar represents an arylene group, and its carbon number is not particularly limited, but is usually 6 to 60. From the viewpoint of preparing a release agent composition with excellent uniformity and obtaining a release agent layer with higher flatness with good reproducibility, it is preferably 30 or less, more preferably 20 or less, even more preferably 18 or less, and still more preferably 12 or less.

[0095] Specific examples of such arylene groups include 1,2-phenylene, 1,3-phenylene, 1,4-phenylene; 1,5-naphthalenediyl, 1,8-naphthalenediyl, 2,6-naphthalenediyl, 2,7-naphthalenediyl, 1,2-anthracenediyl, 1,3-anthracenediyl, 1,4-anthracenediyl, 1,5-anthracenediyl, 1,6-anthracenediyl, 1,7-anthracenediyl, 1,8-anthracenediyl, and 2,3-anthracenediyl. Examples include, but are not limited to, groups derived by removing two hydrogen atoms from the aromatic ring of fused ring aromatic hydrocarbon compounds such as diyl, 2,6-anthracenediyl, 2,7-anthracenediyl, 2,9-anthracenediyl, 2,10-anthracenediyl, and 9,10-anthracenediyl groups; and groups derived by removing two hydrogen atoms from the aromatic ring of ring-linked ring aromatic hydrocarbon compounds such as biphenyl-4,4'-diyl group and paraterphenyl-4,4''-diyl group.

[0096] From the viewpoint of obtaining a laminate that exhibits good peelability as a release agent layer and allows for good separation of the support substrate with good reproducibility, the polynuclear phenol derivative represented by formula (P) is preferably a polynuclear phenol derivative represented by formula (P-1), more preferably a polynuclear phenol derivative represented by formula (P-1-1), and even more preferably a polynuclear phenol derivative represented by formula (P1).

[0097]

[0098] The content of the polynuclear phenol derivative in the release agent composition is not particularly limited, but it is preferably 50 to 100% by mass relative to the film components.

[0099] <<

[0100] In a preferred embodiment, the release agent composition contains at least a novolac resin and optionally other components such as a crosslinking agent, an acid generator, an acid, a surfactant, or a solvent. In another preferred embodiment, the release agent composition contains at least a polynuclear phenol derivative and a crosslinking agent, and optionally other components such as an acid generator, an acid, a surfactant, or a solvent. In yet another preferred embodiment, the release agent composition contains at least an organic resin and a branched polysilane, and optionally other components such as a crosslinking agent, an acid generator, an acid, a surfactant, or a solvent.

[0101] <<<<Solvent>>>> The release agent composition preferably contains a solvent. The solvent is as described in the <<Solvent>> section of the <Adhesive Composition> above.

[0102] The solvent content is determined appropriately considering the viscosity of the desired composition, the coating method used, the thickness of the film to be produced, etc., but is 99% by mass or less of the total composition, preferably 70 to 99% by mass of the total composition, that is, the amount of film components in that case is 1 to 30% by mass of the total composition.

[0103] The viscosity and surface tension of the release agent composition are appropriately adjusted by changing the type of solvent used, their ratios, and the concentration of film components, taking into consideration various factors such as the application method used and the desired film thickness.

[0104] A release agent composition can be produced, for example, by mixing an organic resin or a polynuclear phenol derivative with a solvent and, if necessary, a crosslinking agent. The mixing order is not particularly limited, but examples of methods that can easily and reproducibly produce a release agent composition include, but are not limited to, a method in which the organic resin or polynuclear phenol derivative and the crosslinking agent are dissolved in the solvent at once, or a method in which a portion of the organic resin or polynuclear phenol derivative and the crosslinking agent are dissolved in the solvent, the remainder is dissolved separately in the solvent, and the resulting solutions are mixed. Furthermore, when preparing the release agent composition, heating may be appropriately applied, as long as the components do not decompose or deteriorate. In the present invention, for the purpose of removing foreign matter, the solvent or solution used may be filtered using a filter or the like during the production of the release agent composition or after all components have been mixed.

[0105] The thickness of the release agent layer is not particularly limited, but is usually 5 nm to 100 μm, 10 nm to 10 μm in one embodiment, 50 nm to 1 μm in another embodiment, and 100 nm to 700 nm in yet another embodiment.

[0106] There are no particular limitations on the method for forming a release agent layer from a release agent composition, but one example is a method of forming a release agent layer by coating the release agent composition. There are no particular limitations on the method of coating the release agent composition, but it is usually a spin coating method. The heating temperature of the coated release agent composition cannot be specified in general terms as it varies depending on the type and amount of release agent components contained in the release agent composition, the desired thickness of the release agent layer, etc. However, from the viewpoint of reproducibly achieving a suitable release agent layer, it is 80°C to 300°C, and the heating time is usually appropriately determined in the range of 10 seconds to 10 minutes depending on the heating temperature. The heating temperature is preferably 100°C to 280°C, and more preferably 150°C to 250°C. The heating time is preferably 30 seconds to 8 minutes, and more preferably 1 minute to 5 minutes. Heating can be carried out using a hot plate, oven, etc.

[0107] The following describes an example of the configuration of the laminate according to the first embodiment, using the figures. Figure 1 shows a schematic cross-sectional view of an example of the laminate according to the first embodiment. The laminate in Figure 1 has a semiconductor substrate 1, an adhesive layer 2, and a support substrate 4 in this order. That is, the adhesive layer 2 is provided between the semiconductor substrate 1 and the support substrate 4. The adhesive layer 2 is in contact with the semiconductor substrate 1 and the support substrate 4.

[0108] The following describes another example of the configuration of the laminate according to the first embodiment, using the figures. Figure 2 shows a schematic cross-sectional view of another example of the laminate according to the first embodiment. The laminate in Figure 2 has a semiconductor substrate 1, an adhesive layer 2, a release agent layer 3, and a support substrate 4 in this order. The adhesive layer 2 and the release agent layer 3 are provided between the semiconductor substrate 1 and the support substrate 4. The adhesive layer 2 is in contact with the semiconductor substrate 1. The release agent layer 3 is in contact with the adhesive layer 2 and the support substrate 4.

[0109] <<Example of Manufacturing Method for a Laminate in the First Embodiment>> The manufacturing method for a laminate will be described below, using the laminate shown in Figure 1 as an example from the laminates in the first embodiment. An example of the laminate of the present invention can be manufactured by a method including the following first and second steps. First step: A step of applying an adhesive composition onto a semiconductor substrate to form an adhesive coating layer. Second step: A step of heating the adhesive coating layer to form an adhesive layer.

[0110] The method of applying the adhesive composition is not particularly limited, but is usually done by spin coating. Alternatively, a method can be adopted in which a sheet-like coating film is formed separately by spin coating or the like, and this sheet-like coating film is then applied as the adhesive coating layer. The heating temperature of the applied adhesive composition cannot be specified in general terms, as it varies depending on the type and amount of adhesive components contained in the adhesive composition, whether or not a solvent is included, the boiling point of the solvent used, and the desired thickness of the adhesive layer, but is usually 80 to 150°C, and the heating time is usually 30 seconds to 5 minutes. If the adhesive composition contains a solvent, the applied adhesive composition is usually heated. The thickness of the adhesive coating layer obtained by applying the adhesive composition and heating it if necessary is usually about 200 nm to 20 μm, and is ultimately determined as appropriate so that it falls within the aforementioned range of adhesive layer thickness.

[0111] In this invention, the laminate can be obtained by applying a load in the thickness direction of the semiconductor substrate and the support substrate while performing heat treatment, vacuum treatment, or both, and then performing post-heat treatment. The choice of which treatment conditions to adopt—heat treatment, vacuum treatment, or a combination of both—is determined appropriately after considering various factors such as the type of adhesive composition, film thickness, and desired adhesive strength.

[0112] The heat treatment is usually determined appropriately from the range of 20 to 160°C, from the viewpoint of removing the solvent from the composition. Preferably it is 150°C or lower, more preferably 130°C or lower. The heating time is appropriately determined depending on the heating temperature and the type of adhesive, but from the viewpoint of ensuring suitable adhesion, it is usually 30 seconds or more, preferably 1 minute or more, but from the viewpoint of suppressing deterioration of the adhesive layer and other components, it is usually 10 minutes or less, preferably 5 minutes or less.

[0113] The vacuum treatment can be performed by exposing the adhesive coating layers that are in contact with each other to a pressure of 10 to 10,000 Pa. The vacuum treatment time is usually 1 to 30 minutes.

[0114] The load in the thickness direction of the semiconductor substrate and the support substrate is not particularly limited as long as it does not adversely affect the semiconductor substrate, the support substrate and the layers between them, and can firmly adhere them together, but it is usually in the range of 10 to 50,000 N.

[0115] The post-heating temperature is preferably 120°C or higher from the viewpoint of achieving a sufficient curing speed, and preferably 260°C or lower from the viewpoint of preventing deterioration of the substrate and each layer. The post-heating time is usually 1 minute or more, preferably 5 minutes or more, from the viewpoint of achieving suitable bonding of the substrate and layers constituting the laminate, and is usually 180 minutes or less, preferably 120 minutes or less, from the viewpoint of suppressing or avoiding adverse effects on each layer due to excessive heating. Heating can be carried out using a hot plate, oven, etc. When post-heating using a hot plate, the semiconductor substrate and the support substrate of the laminate may be placed facing downwards during heating, but it is preferable to post-heat with the semiconductor substrate facing downwards from the viewpoint of achieving suitable delamination with good reproducibility.

[0116] Figures 3A to 3C illustrate one method of manufacturing a laminate. First, a laminate is prepared in which an adhesive coating layer 2a is formed on a semiconductor substrate 1 (Figure 3A). This laminate can be obtained, for example, by applying an adhesive composition to the semiconductor substrate 1 and heating it. Next, the laminate shown in Figure 3A and the support substrate 4 are bonded together so that the adhesive coating layer 2a and the support substrate 4 are in contact. Then, after applying a load in the thickness direction of the semiconductor substrate 1 and the support substrate 4 under reduced pressure, a heating device (not shown; hot plate) is placed on the side of the semiconductor substrate 1 opposite to the side where the adhesive coating layer 2a is in contact, and the adhesive coating layer 2a is heated by the heating device and converted into an adhesive layer 2 (Figure 3B). The laminate shown in Figure 1 is obtained by the process shown in Figures 3A to 3B.

[0117] (Method for manufacturing a processed semiconductor substrate) By using the laminate according to the present invention, a method for manufacturing a processed semiconductor substrate can be provided. The method for manufacturing a processed semiconductor substrate according to the present invention is characterized by comprising: a step of processing the semiconductor substrate in the laminate according to the present invention; and a peeling step of separating the processed semiconductor substrate from the support substrate. Thus, the method for manufacturing a processed semiconductor substrate according to the present invention may include the following processing step and the following peeling step, and may further include the following cleaning step. - A step of processing the semiconductor substrate in the laminate according to the present invention - A peeling step of separating the processed semiconductor substrate from the support substrate - A step of cleaning the processed semiconductor substrate after the peeling step

[0118] The processing applied to the semiconductor substrate includes, for example, processing the side opposite the circuit surface of the wafer, such as thinning the wafer by polishing the back surface. Subsequently, for example, through-silicon electrodes (TSVs) are formed, and then the thinned wafer is peeled off the support substrate to form a wafer laminate for three-dimensional mounting. Alternatively, for example, back-side electrodes may be formed before or after this process. During the wafer thinning and TSV processes, heat of approximately 250 to 350°C is applied while the wafer is bonded to the support substrate. The laminate of the present invention typically includes an adhesive layer and possesses heat resistance to this load. It should be noted that the processing is not limited to those described above, and also includes, for example, the implementation of a semiconductor component mounting process when the substrate is temporarily bonded to the support substrate to support the substrate for mounting semiconductor components.

[0119] As a method for separating (delaminating) the semiconductor substrate from the support substrate, it is desirable to use light irradiation, taking into consideration that the adhesive layer is a thin film. If the laminate contains an adhesive layer or a release agent layer, irradiating the release agent layer with light will alter (e.g., separate or decompose) the adhesive layer or release agent layer that absorbs the light, making it easier to separate the semiconductor substrate from the support substrate. Examples of lasers used in the delamination process include infrared (IR) lasers and ultraviolet (UV) lasers. In particular, it is preferable to use an infrared (IR) laser for silicon support substrates and an ultraviolet (UV) laser for glass support substrates.

[0120] If an adhesive layer remains on at least one of the surfaces of the separated semiconductor substrate and support substrate, in the cleaning step to remove the adhesive layer, the present invention is performed by O ２ It is preferable to use a dry etching method by ashing. In the present invention, since the adhesive layer is formed as a thin film, ２ The adhesive layer can be removed simply and effectively by dry etching using ashing. In the cleaning process according to the present invention, the adhesive layer can be removed by a dry process that does not use solvents. If the adhesive layer is formed of polysiloxane or if the thickness of the adhesive layer is thick, ２ Removing the adhesive layer by ashing is difficult, but in the present invention, ２ The adhesive layer can be removed simply and easily by ashing. Here, O ２ Dry etching by ashing is a method that uses plasma-induced oxygen (O). ２ This method removes the adhesive layer by reacting it with CO2 gas. More specifically, high-energy oxygen plasma is irradiated onto the resin surface of the adhesive layer, causing it to bond with the carbon that makes up the resin. ２ The adhesive layer is removed by using a chemical reaction that involves vaporization and decomposition (ashing).

[0121] The components and method elements relating to the above-described steps of the method for manufacturing a processed semiconductor substrate of the present invention may be modified in various ways, as long as they do not depart from the spirit of the present invention. The method for manufacturing a processed semiconductor substrate of the present invention may also include steps other than those described above.

[0122] 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.

[0123] [Equipment] (1) Rotation and revolving mixer: ARE-500, manufactured by Thinky Co., Ltd. (2) Bonding machine: VJ-300, manufactured by Ayumi Kogyo Co., Ltd. (3) Infrared laser delamination machine: AFS-MCTI-FX, manufactured by Aflair Inc. (4) UV laser delamination machine: Laser debonder, manufactured by Optopia Co., Ltd. (5) Etching machine: RIE-200NL, manufactured by Samco Co., Ltd.

[0124] [1] Synthesis of Novolac Resin [Synthesis Example 1] 7.4 g of tert-leaf oxystyrene, 7.38 g of 4-amyloxybenzaldehyde, and 10.0 g of propylene glycol monomethyl ether as a solvent were placed in a flask and stirred. After stirring, 10.0 g of N,N'-diphenyl-1,4-phenylenediamine, 1.1 g of methanesulfonic acid, and 31.1 g of propylene glycol monomethyl ether as a solvent were added, and the mixture was heated and stirred overnight at 110°C under a nitrogen atmosphere to obtain a reaction solution. Propylene glycol monomethyl ether acetate and pure water were added to the reaction solution and stirred. Subsequently, liquid-liquid extraction was performed, and the organic layer was recovered and concentrated to obtain novolac resin. The weight-average molecular weight of the polymer novolac resin was measured by the following method and found to be 1,200. The weight-average molecular weight was measured using a GPC instrument (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 that order), with a column temperature of 40°C, tetrahydrofuran as the eluent (elution solvent), and a flow rate of 1.00 mL / min. Polystyrene (manufactured by Sigma-Aldrich) was used as the standard sample. The obtained novolac resin has the following repeating units.

[0125]

[0126] [2] Preparation of adhesive compositions having a release function [Preparation Example 1] Preparation of adhesive compositions having a release function 30 g of novolac resin obtained in Synthesis Example 1 was dissolved in 70 g of propylene glycol monomethyl ether acetate to make a solution. Finally, the obtained mixture was filtered through a 300 mesh nylon filter to obtain adhesive composition-1.

[0127] [Preparation Example 2] Preparation of an adhesive composition with release function 15 g of novolac resin obtained in Synthesis Example 1 was dissolved in 85 g of propylene glycol monomethyl ether acetate to make a solution. Finally, the obtained mixture was filtered through a 300 mesh nylon filter to obtain adhesive composition 2.

[0128] [Preparation Example 3] Preparation of an adhesive composition with release function 10 g of novolac resin obtained in Synthesis Example 1 was dissolved in 30 g of propylene glycol monomethyl ether acetate to make a solution. Finally, the obtained mixture was filtered through a 300 mesh nylon filter to obtain adhesive composition 3.

[0129] [Preparation Example 4] Preparation of an adhesive composition with release function 15 g of polyacrylic acid resin (manufactured by Sigma-Aldrich, number average molecular weight 450,000) was dissolved in 85 g of propylene glycol monomethyl ether to prepare a solution. Finally, the obtained mixture was filtered through a 300 mesh nylon filter to obtain adhesive composition 4.

[0130] [Preparation Example 5] Preparation of an adhesive composition with release function 10 g of polymethyl methacrylate resin (manufactured by Sigma-Aldrich, number average molecular weight 155,800) was dissolved in 90 g of propylene glycol monomethyl ether acetate to prepare a solution. Finally, the obtained mixture was filtered through a 300 mesh nylon filter to obtain adhesive composition-5.

[0131] [Preparation Example 6] Preparation of an adhesive composition with release function 20 g of polyarylate resin (M-2000H, manufactured by Unitika Ltd.) was dissolved in 80 g of cyclohexanone to prepare a solution. Finally, the obtained mixture was filtered through a 300 mesh nylon filter to obtain adhesive composition-6.

[0132] [Preparation Example 7] Preparation of an adhesive composition with release function 15 g of polyarylate resin (M-2000H, manufactured by Unitika Ltd.) was dissolved in 85 g of cyclohexanone to prepare a solution. Finally, the obtained mixture was filtered through a 300 mesh nylon filter to obtain adhesive composition-7.

[0133] [Preparation Example 8] Preparation of an adhesive composition for use as a release layer In a 600 mL stirring container for a stirrer, 64.5 g of vinyl group-containing MQ resin (manufactured by Wacker Chem Co., Ltd.), 10.94 g of vinyl group-containing linear polydimethylsiloxane (Wacker Chem Co., Ltd.) with a viscosity of 100 mPa·s as polyorganosiloxane (a1), and SiH group-containing linear polydimethylsiloxane (a2) with a viscosity of 70 mPa·s 6.82 g of roxane (manufactured by Wacker Chem Co., Ltd.), 0.09 g of 1-ethynyl-1-cyclohexanol (manufactured by Wacker Chem Co., Ltd.) and 0.09 g of 1,1-diphenyl-2-propyne-1-ol (manufactured by Tokyo Chemical Industry Co., Ltd.) as polymerization inhibitors (a3), 0.01 g of platinum catalyst (manufactured by Wacker Chem Co., Ltd.) as a platinum group metal catalyst (a4), and 319.44 g of p-menthane (manufactured by Tokyo Chemical Industry Co., Ltd.) as a solvent were added and stirred with a stirrer for 5 minutes. Finally, the resulting mixture was filtered through a 300 mesh nylon filter to obtain adhesive composition-8.

[0134] [1] Manufacturing of Laminates [Example 1: Examples 1-1 to 1-3] The obtained adhesive compositions 1 to 3 were spin-coated onto a 100 mm silicon wafer (thickness 750 μm) as the device-side substrate, and then heated at 100°C for 1 minute to form an adhesive coating layer on the silicon wafer, which is a semiconductor substrate. A 100 mm glass wafer (thickness 500 μm) was used as the carrier-side substrate. Then, using a bonding apparatus, the glass wafer and the silicon wafer were bonded together so that the adhesive coating layer was sandwiched between them, and then a laminate was fabricated by post-heat treatment at 200°C for 10 minutes. The bonding was performed at a temperature of 250°C, a load of 20 kN, and a reduced pressure of 1,500 Pa. The thickness of the adhesive layer formed on the silicon wafer using each adhesive composition is shown in Table 1 below.

[0135]

[0136] [2] Manufacturing of Laminates [Example 2: Examples 2-1 to 2-6] The obtained adhesive compositions 4 to 7 were spin-coated onto a 100 mm silicon wafer (thickness 750 μm) as the device-side substrate, and then heated at 100°C for 1 minute to form an adhesive coating layer on the silicon wafer, which is the semiconductor substrate. A 100 mm silicon wafer (thickness 750 μm) was used as the carrier-side substrate. Then, using a bonding apparatus, the silicon wafers were bonded together so that the adhesive coating layer was sandwiched between them, and then a laminate was fabricated by post-heating at 200°C for 10 minutes. The bonding was performed at a temperature of 250°C, a load of 20 kN, and a reduced pressure of 1,500 Pa. The thickness of the adhesive layer formed on the silicon wafer using each adhesive composition is shown in Table 2 below.

[0137]

[0138] [3] Manufacturing of Laminates [Comparative Example 1] The obtained adhesive composition-8 was spin-coated onto a 100 mm silicon wafer (thickness 750 μm) as the device-side substrate, so that the final film thickness in the laminate would be 3000 nm, and then heated at 120°C for 1 minute to form an adhesive coating layer on the silicon wafer, which is the semiconductor substrate. A 100 mm glass wafer (thickness 500 μm) was used as the carrier-side substrate. Then, using a bonding apparatus, the glass wafer and the silicon wafer were bonded together so that the adhesive coating layer was sandwiched between them, and then a laminate was manufactured by post-heat treatment at 200°C for 10 minutes. The bonding was performed at a temperature of 50°C, a load of 20 kN, and a reduced pressure of 1,500 Pa.

[0139] [4] Manufacturing of Laminates [Comparative Example 2] The obtained adhesive composition-8 was spin-coated onto a 100 mm silicon wafer (thickness 750 μm) as the device-side substrate so that the final film thickness in the laminate would be 3000 nm, and then heated at 120°C for 1 minute to form an adhesive coating layer on the silicon wafer, which is the semiconductor substrate. A 100 mm silicon wafer (thickness 750 μm) was used as the carrier-side substrate. Then, using a bonding apparatus, the silicon wafers were bonded together so that the adhesive coating layer was sandwiched between them, and then a laminate was manufactured by post-heat treatment at 200°C for 10 minutes. The bonding was performed at a temperature of 50°C, a load of 20 kN, and a reduced pressure of 1,500 Pa.

[0140] [5] Fabrication and evaluation of laminates for evaluation. The laminated substrates obtained in Example 1 (Examples 1-1 to 1-3) and Comparative Example 1 were irradiated with a 308 nm laser beam at 300 mJ perpendicular to the carrier-side glass wafer using a UV laser peeling apparatus. After laser irradiation, the feasibility of peeling was checked at the interface between the carrier-side glass wafer and the device-side silicon wafer. ○ was used to indicate easy peeling without load, and × was used to indicate that peeling was not possible. The results are shown in Table 3 below.

[0141] [6] Fabrication and evaluation of laminates for evaluation The laminated substrates obtained in Example 2 (Examples 2-1 to 2-6) and Comparative Example 2 were irradiated with a 9.3 μm laser beam perpendicular to the carrier-side silicon wafer using an infrared laser delamination apparatus. The laser irradiation conditions were as follows: Scan speed: 1000 nm / sec Laser power: 90 W Frequency: 20 Hz After laser irradiation, the feasibility of delamination was checked at the interface between the carrier-side silicon wafer and the device-side silicon wafer. ○ was used if delamination was easy without load, and × was used if delamination was not possible. The results are shown in Table 3 below.

[0142] [7] Evaluation of Residue Removal from Substrate After Peeling The laminates obtained in Example 1 (Examples 1-1 to 1-3) and Comparative Example 1, and in Example 2 (Examples 2-1 to 2-6) and Comparative Example 2 were peeled using an infrared or UV laser peeling device, and the device-side substrate was etched under the following conditions: Pressure: 8.7 Pa Time: 20 minutes Flow rate: 50 sccm(O ２ RF power: 200W The surface of the silicon wafer on the device side after processing was observed with an optical microscope, and samples where the residue had been removed were marked with ○, and samples where it had not been removed were marked with ×. The results are shown in Table 3 below.

[0143]

[0144] All laminates prepared in Examples 1 and 2 showed good laser peelability and residue removal properties. In Comparative Example 1, laser peelability was not possible, so residue removal was not evaluated. In Comparative Example 2, laser peelability was possible, but residue removal by etching was difficult.

[0145] 1. Semiconductor substrate 2. Adhesive layer 2a. Adhesive coating layer 3. Release agent layer 4. Support substrate 11a. Insulating film 12. Passivation film 11b. Insulating film 13. Hard mask 14. Copper metal film 15. Etching stop layer 20. Semiconductor substrate

Claims

1. A laminate comprising a semiconductor substrate, a support substrate, and an adhesive layer formed in contact with the semiconductor substrate, wherein the adhesive layer is used to temporarily bond the semiconductor substrate and the support substrate, the adhesive layer contains an organic resin but does not contain a silicone resin, and the thickness of the adhesive layer is 200 nm or more and 20 μm or less.

2. The laminate according to claim 1, wherein the thickness of the adhesive layer is 250 nm or more and 10 μm or less.

3. The laminate according to claim 1, wherein the semiconductor substrate is a substrate with a flat surface, in which grooves for wiring formation patterns are formed in an insulating film, and a copper metal film is embedded in the grooves.

4. The laminate according to claim 1, wherein the organic resin contains at least one resin selected from the group consisting of novolac resin, polyacrylic acid resin, polymethyl methacrylate resin, polyarylate resin, and polyimide resin.

5. A method for manufacturing a laminate according to claim 1, comprising the step of applying an adhesive composition for forming the adhesive layer to either the semiconductor substrate or the support substrate.

6. The method for manufacturing a laminate according to claim 5, wherein the semiconductor substrate is a substrate with a flat surface, obtained by a damascene manufacturing method, in which grooves for wiring formation patterns are formed in an insulating film and copper metal films are embedded in the grooves.

7. The method for manufacturing a damascene film, comprising: etching a hard mask formed on the insulating film (dielectric film) to form a wiring pattern; then etching the insulating film using the hard mask to form grooves in the insulating film to form a wiring pattern similar to that of the hard mask in the insulating film; then removing the hard mask; then forming a copper metal film in the grooves and on the surface of the insulating film by electroplating; and then removing the copper metal film on the surface by chemical mechanical polishing (CMP) to expose the surface of the insulating film.

8. A method for manufacturing a processed semiconductor substrate, comprising: a step of processing the semiconductor substrate in a laminate according to any one of claims 1 to 4; and a peeling step of separating the support substrate and the processed semiconductor substrate by irradiating them with a laser.

9. The method for manufacturing a processed semiconductor substrate according to claim 8, wherein the laser used in the peeling step is an infrared (IR) laser or an ultraviolet (UV) laser.

10. The method for manufacturing a processed semiconductor substrate according to claim 9, wherein the peeling step includes a step of irradiating with an infrared (IR) laser from the silicon support substrate side, or a step of irradiating with an ultraviolet (UV) laser from the glass support substrate side.

11. The method for manufacturing a processed semiconductor substrate according to claim 8, further comprising a cleaning step of removing the adhesive layer on the semiconductor substrate after separation.

12. The cleaning process is O ２ Using a dry etching method by ashing, plasma-generated oxygen (O ２ A method for manufacturing a processed semiconductor substrate according to claim 11, comprising removing the adhesive layer by reacting the adhesive layer with a gas.

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