Method for manufacturing a laminate, a release agent composition, and a processed semiconductor substrate

Abstract

A multilayer body which is characterized by comprising a semiconductor substrate, a supporting substrate, and a bonding layer and a release layer that are provided between the semiconductor substrate and the supporting substrate, and which is also characterized in that the release layer is a film that is obtained from a release agent composition that contains an organic resin, a branched chain polysilane and a solvent.

Description

Technical Field

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

Background Art

[0002] Conventionally, semiconductor wafers that have been integrated in a two-dimensional planar direction require semiconductor integration technology that further integrates (laminates) the plane in the three-dimensional direction for the purpose of further integration. This three-dimensional lamination is a technology in which multiple layers are integrated while being connected by silicon through vias (TSV: through silicon via). When integrating multiple layers, each wafer to be integrated is thinned by polishing the side opposite to the formed circuit surface (i.e., the back surface), and the thinned semiconductor wafers are laminated.

[0003] Before thinning, a semiconductor wafer (hereafter also simply referred to as a wafer) is adhered to a support for polishing with a polishing device. The adhesion at this time is called temporary adhesion because it must be easily peeled off after polishing. This temporary adhesion must be easily removed from the support, and if a large force is applied for removal, the thinned semiconductor wafer may be cut or deformed. It should be easily removed so that such a situation does not occur. However, it is not preferable for the temporary adhesion to come off or shift due to polishing stress during the back surface polishing of the semiconductor wafer. Therefore, the performance required for temporary adhesion is to withstand the stress during polishing and be easily removed after polishing.

[0004] For example, performance is required to have high stress (strong adhesive force) in the planar direction during polishing and low stress (weak adhesive force) in the vertical direction during removal. Although a method using laser irradiation has been disclosed for such an adhesion and separation process (see, for example, Patent Documents 1 and 2), with the further progress in the semiconductor field in recent years, new technologies related to peeling by irradiation with light such as lasers are constantly in demand.

Prior Art Documents

Patent Documents

[0005] Patent Document 1 Japanese Patent Application Laid-Open No. 2004-64040 Patent Document 2 Japanese Patent Application Laid-Open No. 2012-106486 SUMMARY OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION

[0006] The present invention has been made in view of the above circumstances, and is excellent in heat resistance during bonding of a support substrate and a semiconductor substrate, processing of the back surface of the semiconductor substrate, component mounting, etc., and can be easily peeled off when the support substrate or the semiconductor substrate is peeled off. Further, it cannot be suitably removed by any of chemical solutions such as an organic solvent, an acid, an alkaline developer, and hydrogen peroxide solution used in the manufacture of semiconductor elements, but can be suitably removed by a cleaning agent composition. An object of the present invention is to provide a laminate including a release layer, a release agent composition that provides a film suitable as such a release layer, and a method for manufacturing a processed semiconductor substrate using such a laminate. MEANS FOR SOLVING THE PROBLEMS

[0007] As a result of intensive studies by the present inventors to solve the above problems, as a release layer of a laminate including a semiconductor substrate, a support substrate, and an adhesive layer and a release layer provided between the semiconductor substrate and the support substrate, By using a film obtained from a release agent composition containing an organic resin, a branched polysilane, and a solvent, it has been found that the above problems can be solved, and the present invention has been completed.

[0008] That is, the present invention is 1. A semiconductor substrate, A support substrate, An adhesive layer and a release layer provided between the semiconductor substrate and the support substrate, A laminate, characterized in that the release layer is a film obtained from a release agent composition containing an organic resin, a branched polysilane, and a solvent, 2. The laminate according to any one of 1, wherein the branched-chain polysilane contains a structural unit represented by formula (B). [Chemical formula] (In the formula, R B represents a hydrogen atom, a hydroxyl group, a silyl group or an organic group.) 3. The laminate according to 2, wherein the above R B is an aryl group. 4. The laminate according to 3, wherein the above R B is a phenyl group. 5. The laminate according to any one of 1 to 4, wherein the weight average molecular weight of the branched-chain polysilane is 50 to 30,000. 6. The laminate according to any one of 1 to 5, wherein the 5% weight loss temperature of the branched-chain polysilane is 300 °C or higher. 7. The laminate according to any one of 1 to 6, wherein the organic resin is a novolak resin. 8. The laminate according to 7, wherein the novolak resin is a polymer containing one or more selected from the group consisting of a unit represented by formula (C1-1), a unit represented by formula (C1-2), and a unit represented by formula (C1-3). [Chemical formula] (In the formula, C 1 represents a group derived from an aromatic compound containing a nitrogen atom, C 2 represents a group containing a tertiary carbon atom having at least one selected from the group consisting of a secondary carbon atom, a quaternary carbon atom, and an aromatic ring in the side chain, 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.) 9. The laminate according to any one of 1 to 8, wherein the release agent composition contains a crosslinking agent. 10. The laminate according to any one of 1 to 9, wherein the adhesive layer is a film obtained by using an adhesive composition containing an adhesive component (S) containing at least one selected from a polysiloxane-based adhesive, an acrylic resin-based adhesive, an epoxy resin-based adhesive, a polyamide-based adhesive, a polystyrene-based adhesive, a polyimide adhesive, and a phenol resin-based adhesive. 11. The laminate according to 10, wherein the adhesive component (S) contains a polysiloxane-based adhesive. 12. The laminate according to 11, wherein the polysiloxane-based adhesive contains a polysiloxane component (A) that cures by a hydrosilylation reaction. 13. A release agent composition for forming the release layer of a laminate including a semiconductor substrate, a support substrate, and an adhesive layer and a release layer provided between the semiconductor substrate and the support substrate, The release agent composition contains an organic resin, a branched polysilane, and a solvent. 14. The release agent composition according to 13, wherein the branched polysilane contains a structural unit represented by formula (B).

Chemical formula

Chemical formula

Advantages of the Invention

[0009] The laminate of the present invention includes a semiconductor substrate, a support substrate, and an adhesive layer and a release layer provided between the semiconductor substrate and the support substrate. Since the release layer is a film obtained from a release agent composition containing an organic resin, a branched polysilane, and a solvent, the semiconductor substrate and the support substrate can be separated without applying an excessive load for peeling to the semiconductor substrate, and the separated semiconductor substrate can be washed with a cleaning agent composition to achieve suitable cleaning of the substrate without leaving residues of the release layer on its surface. In particular, when the support substrate of the laminate of the present invention has light transmissivity, by irradiating light from the support substrate side to the release layer, in the release layer, the organic resin absorbs the light and suitable alteration occurs, thereby exhibiting good peelability. As a result, the semiconductor substrate and the support substrate can be separated without applying an excessive physical load for peeling to the semiconductor substrate, and the separated semiconductor substrate can be washed with a cleaning agent composition to achieve suitable cleaning of the substrate without leaving residues of the release layer on its surface.

[0010] Further, the release layer provided in the laminate of the present invention cannot be suitably removed by any of an organic solvent, an acid, and a chemical solution (such as an alkaline developer, hydrogen peroxide solution, etc.) used in the manufacture of semiconductor elements.

[0011] By using the laminate of the present invention having such characteristics, for example, when separating a glass substrate as a support substrate and a processed silicon wafer after processing the back surface of the silicon wafer which is a semiconductor substrate, the processed silicon wafer can be easily separated without applying an excessive load for peeling. In particular, when the support substrate has light transmissivity, by irradiating light from the support substrate side, the processed silicon wafer can be more easily separated without applying an excessive load for peeling even more. As a result, mechanical stress on the silicon wafer can be avoided, and thus damage such as warping and deformation of the silicon wafer can be avoided. In addition, since the release layer provided in the laminate of the present invention cannot be suitably removed by an organic solvent, an acid, or a chemical solution (such as an alkaline developer or hydrogen peroxide solution) used in the manufacture of semiconductor elements, even if the laminate is exposed to any of an organic solvent, an acid, and a chemical solution used in the manufacture of semiconductor elements before the semiconductor substrate and the support substrate are finally separated and the release layer comes into contact with it, the possibility of unintentional peeling occurring is sufficiently reduced. On the other hand, since the release layer can be suitably removed by a cleaning agent composition, by cleaning the separated semiconductor substrate with the cleaning agent composition after separating the semiconductor substrate and the support substrate, good cleaning can be achieved without leaving residues of the release layer on its surface.

[0012] Since the release agent composition of the present invention contains a branched polysilane together with an organic resin and a solvent, it can easily and reproducibly provide a film with excellent uniformity by a wet method such as spin coating. Further, when the organic resin contained in the release agent composition absorbs light and is altered, when the film obtained from the release agent composition is irradiated with light, the organic resin in the film absorbs light and suitable alteration occurs, thereby exhibiting good release ability. As a result, the releasability is improved. In addition, since the release agent composition contains a branched polysilane, the film obtained from the release agent composition cannot be suitably removed by any of an organic solvent, an acid, and a chemical solution used in the manufacture of semiconductor elements, but can be suitably removed by a cleaning agent composition. By providing, as a release layer, a film obtained from the release agent composition of the present invention having such characteristics, together with an adhesive layer, between a semiconductor substrate and a support substrate, a laminate can be obtained that can be separated without applying an excessive load for release to a workpiece such as a support substrate or a semiconductor substrate. In particular, when the support substrate has light transmissivity, by irradiating light from the support substrate side, a laminate can be obtained that can be separated without applying an even greater excessive load for release to a workpiece such as a support substrate or a semiconductor substrate. Moreover, even if such a laminate is exposed to any one of an organic solvent, an acid, and a chemical solution used in the manufacture of a semiconductor element in the manufacturing process of a semiconductor element, the possibility of unintentional peeling occurring is sufficiently reduced. On the other hand, since the release layer can be suitably removed by a cleaning agent composition, after separating the semiconductor substrate and the support substrate, by cleaning the separated semiconductor substrate with the cleaning agent composition, good cleaning can be achieved without leaving residues of the release layer on its surface.

[0013] By using the laminate and the release agent composition of the present invention having the above characteristics, a method for manufacturing a well-processed semiconductor substrate can be realized, and the manufacture of a more reliable semiconductor element can be expected.

Embodiments for Carrying Out the Invention

[0014] The laminate of the present invention includes a semiconductor substrate, a support substrate, and an adhesive layer and a release layer provided between the semiconductor substrate and the support substrate, and the release layer is a film obtained from a release agent composition containing an organic resin, a branched polysilane, and a solvent.

[0015] The semiconductor substrate is, for example, a wafer, and specific examples thereof include, but are not limited to, a silicon wafer having a diameter of 300 mm and a thickness of about 770 μm.

[0016] The support substrate is a support (carrier) to which the semiconductor substrate is bonded to support it. The support substrate is not particularly limited as long as it can support the semiconductor substrate via functional layers such as an adhesive layer and a release layer. However, when performing separation by irradiating the release layer with light from the support substrate side, the support substrate needs to have light transmissivity. When performing separation by light irradiation, the light transmittance of the support substrate is usually 50% or more, preferably 60% or more, more preferably 70% or more, even more preferably 80% or more, and still more preferably 90% or more.

[0017] The wavelength of the light used for separation is not particularly limited as long as it is absorbed by the organic resin, but it is usually light in the range of 100 nm to 600 nm. For example, suitable wavelengths are 308 nm, 343 nm, 355 nm, or 365 nm. The irradiation amount of light required for separation is the irradiation amount that can cause suitable alterations described later, such as decomposition. The light used for separation may be laser light or non-laser light emitted from a light source such as a lamp.

[0018] Specific examples of the support substrate include a glass wafer with a diameter of 300 mm and a thickness of about 700 μm, but it is not limited thereto.

[0019] In one aspect, the laminate of the present invention has only two layers between the semiconductor substrate and the support substrate, one of these two layers being an adhesive layer and the other layer being a release layer. In a preferred aspect, the laminate of the present invention includes a semiconductor substrate, a support substrate, an adhesive layer provided in contact with the semiconductor substrate, and a release layer provided in contact with the support substrate and the adhesive layer. Further, in one aspect, since the support substrate has light transmissivity and the organic resin absorbs light irradiation and undergoes alteration, separation can be achieved by irradiating the release layer of the laminate of the present invention with light.

[0020] When the support substrate of the laminate of the present invention has light transmissivity, by irradiating light from the support substrate side to the release layer, peeling can be performed without applying an excessive load for peeling. As a result, the semiconductor substrate and the support substrate can be easily separated. That is, when the support substrate of the laminate of the present invention has light transmissivity, the release layer provided in the laminate of the present invention is irradiated with light from the support substrate side, and the peelability is improved compared to before irradiation. In the laminate of the present invention, for example, a silicon wafer as a semiconductor substrate is suitably supported via functional layers such as an adhesive layer and a release layer while the silicon wafer is being processed such as thinning on a glass wafer as a support substrate that transmits light. After the processing is completed, by irradiating light from the support substrate side, the light transmitted through the support substrate is absorbed by the release layer, so that separation or decomposition of the release layer occurs at the interface between the release layer and the adhesive layer, at the interface between the release layer and the support substrate or the semiconductor substrate, or inside the release layer. As a result, suitable peeling can be realized without applying an excessive load for peeling. And, as described later, by cleaning the separated semiconductor substrate with a cleaning agent composition, suitable cleaning of the substrate can be realized without leaving residues of the release layer on the substrate.

[0021] As described above, the release layer provided in the laminate of the present invention is a film obtained from a release agent composition containing an organic resin, a branched polysilane, and a solvent. In one aspect, the film is a cured film obtained by curing the film constituent components in the release agent composition.

[0022] The release agent composition contains an organic resin. Such an organic resin preferably exhibits suitable peelability. When separating the semiconductor substrate and the support substrate by irradiating light to the release layer, the organic resin preferably absorbs light and undergoes suitable alteration such as decomposition necessary for improving the peelability.

[0023] As a preferable example of the organic resin, a novolak resin can be mentioned. When irradiating light to the release layer included in the laminate of the present invention to cause release, a novolak resin that absorbs and alters light with a wavelength of 190 nm to 600 nm is preferable, and a novolak resin that is altered by irradiation with light such as a laser having a wavelength of 308 nm, 343 nm, 355 nm, or 365 nm is more preferable.

[0024] Specifically, for example, the novolak resin is a polymer containing one or more selected from the group consisting of a unit represented by formula (C1-1), a unit represented by formula (C1-2), and a unit represented by formula (C1-3).

[0025]

Chemical formula

[0026] C 1 represents a group derived from an aromatic compound containing a nitrogen atom, and C 2 represents a group containing a tertiary carbon atom having at least one selected from the group consisting of a secondary carbon atom, a quaternary carbon atom, and an aromatic ring in its side chain, and C 3 represents a group derived from an aliphatic polycyclic compound, and 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.

[0027] That is, a unit having a bond between a group derived from an aromatic compound containing a nitrogen atom and a group containing a tertiary carbon atom having at least one selected from the group consisting of a secondary carbon atom, a quaternary carbon atom, and an aromatic ring in its side chain (formula (C1-1)), a unit having a bond between a group derived from an aromatic compound containing a nitrogen atom and a group derived from an aliphatic polycyclic compound (formula (C1-2)), and a 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 bisphenol and a group containing a tertiary carbon atom having at least one selected from the group consisting of a quaternary carbon atom and an aromatic ring in its side chain ((formula (C1-3))), one or more selected from the group consisting of these are included in the polymer which is the novolak resin.

[0028] In a preferred embodiment, the polymer that is a novolak resin has a unit having a bond between a group derived from an aromatic compound containing a nitrogen atom and a group containing a tertiary carbon atom having at least one selected from the group consisting of a secondary carbon atom, a quaternary carbon atom, and an aromatic ring in a side chain (formula (C1-1)) and / or a unit having a bond between a group derived from an aromatic compound containing a nitrogen atom and a group derived from an aliphatic polycyclic compound (formula (C1-2)).

[0029] C 1 The group derived from an aromatic compound containing a nitrogen atom of C 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-1-naphthylamine, etc., but is not limited thereto.

[0030] C 2 The group containing a tertiary carbon atom having at least one selected from the group consisting of a secondary carbon atom, a quaternary carbon atom, and an aromatic ring in a side chain of C can be, for example, a group derived from 1-naphthaldehyde, a group derived from 1-pyrenecarboxaldehyde, a group derived from 4-(trifluoromethyl)benzaldehyde, a group derived from acetaldehyde, etc., but is not limited thereto.

[0031] C 3 The group derived from an aliphatic polycyclic compound of C can be a group derived from dicyclopentadiene, but is not limited thereto.

[0032] C 4 is a group derived from phenol, a group derived from bisphenol, a group derived from naphthol, a group derived from biphenyl, or a group derived from bisphenol.

[0033] In a preferred embodiment, the above polymer contains, as a unit represented by formula (C1-1), for example, a unit represented by formula (C1-1-1).

[0034] [Chemical formula]

[0035] In formula (C1-1-1), R 901 and R 902 represent substituents that substitute on the ring, and each independently represents a halogen atom, a nitro group, a cyano group, an amino group, a hydroxy group, a carboxyl group, an optionally substituted alkyl group, an optionally substituted alkenyl group or an optionally substituted aryl group. R 903 represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group or an optionally substituted aryl group. R 904 represents a hydrogen atom, an optionally substituted aryl group or an optionally substituted heteroaryl group. R 905 represents an optionally substituted alkyl group, an optionally substituted aryl group or an optionally substituted heteroaryl group. The group of R 904 and the group of R 905 may be bonded to each other to form a divalent group. Examples of the substituents of the alkyl group and the alkenyl group include a halogen atom, a nitro group, a cyano group, an amino group, a hydroxy group, a carboxyl group, an aryl group, a heteroaryl group, etc. Examples of the substituents of the aryl group and the heteroaryl group include a halogen atom, a nitro group, a cyano group, an amino group, a hydroxy group, a carboxyl group, an alkyl group, an alkenyl group, etc. h 1 and h 2 each independently represents an integer from 0 to 3.

[0036] The carbon number of the optionally substituted alkyl group and the optionally substituted alkenyl group is usually 40 or less, and from the viewpoint of solubility, it is preferably 30 or less, more preferably 20 or less. The carbon number of the optionally substituted aryl group and the heteroaryl group is usually 40 or less, and from the viewpoint of solubility, it is preferably 30 or less, more preferably 20 or less.

[0037] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like.

[0038] Specific examples of the optionally substituted alkyl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, an s-butyl group, a t-butyl group, an n-pentyl group, a 1-methyl-n-butyl group, a 2-methyl-n-butyl group, a 3-methyl-n-butyl group, a 1,1-dimethyl-n-propyl group, a 1,2-dimethyl-n-propyl group, a 2,2-dimethyl-n-propyl group, a 1-ethyl-n-propyl group, an n-hexyl, a 1-methyl-n-pentyl group, a 2-methyl-n-pentyl group, a 3-methyl-n-pentyl group, a 4-methyl-n-pentyl group, a 1,1-dimethyl-n-butyl group, a 1,2-dimethyl-n-butyl group, a 1,3-dimethyl-n-butyl group, a 2,2-dimethyl-n-butyl group, a 2,3-dimethyl-n-butyl group, a 3,3-dimethyl-n-butyl group, a 1-ethyl-n-butyl group, a 2-ethyl-n-butyl group, a 1,1,2-trimethyl-n-propyl group, a 1,2,2-trimethyl-n-propyl group, a 1-ethyl-1-methyl-n-propyl group, a 1-ethyl-2-methyl-n-propyl group, and the like, but are not limited thereto.

[0039] Specific examples of the alkenyl group 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, 1-methyl-3-butenyl 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, 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-tertiary 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, 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, 3-cyclohexenyl group and the like can be mentioned, but are not limited thereto.,

[0040] Specific examples of the aryl group that may be substituted include a 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, 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, 9-phenanthryl group, etc., but are not limited thereto.

[0041] Specific examples of the heteroaryl group that may be substituted include a 2-thienyl group, 3-thienyl group, 2-furanyl group, 3-furanyl group, 2-oxazolyl group, 4-oxazolyl group, 5-oxazolyl group, 3-isoxazolyl group, 4-isoxazolyl group, 5-isoxazolyl group, 2-thiazolyl group, 4-thiazolyl group, 5-thiazolyl group, 3-isothiazolyl group, 4-isothiazolyl group, 5-isothiazolyl group, etc., but are not limited thereto.

[0042] Hereinafter, specific examples of the unit represented by the formula (C1-1-1) are given, but are not limited thereto.

[0043]

Chemical formula

[0044] In a preferred embodiment, the above polymer contains, as a unit represented by the formula (C1-1), for example, a unit represented by the formula (C1-1-2).

[0045]

Chemical formula

[0046] In the formula (C1-1-2), Ar901 and Ar 902 each independently represents an aromatic ring such as a benzene ring or a naphthalene ring, and R 901 ~R 905 as well as h 1 and h 2 represent the same meaning as described above.

[0047] Hereinafter, specific examples of the unit represented by the formula (C1-1-2) will be given, but it is not limited thereto.

[0048]

Chemical formula

[0049] In a preferred embodiment, the above polymer includes, as the unit represented by the formula (C1-2), for example, the unit represented by the formula (C1-2-1) or (1-2-2).

[0050]

Chemical formula

[0051] In the above formula, R 906 ~R 909 are substituents bonded to the ring, and each independently represents a halogen atom, a nitro group, a cyano group, an amino group, a hydroxy 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 numbers of the halogen atom, the optionally substituted alkyl group, the optionally substituted alkenyl group and the optionally substituted aryl group are the same as those described above. h 3 ~h 6 each independently represents an integer from 0 to 3, and R 901 ~R 903 as well as h 1 and h 2 represent the same meaning as described above.

[0052] Hereinafter, specific examples of the units represented by the formulas (C1-2-1) and (C1-2-2) will be given, but it is not limited thereto.

[0053] [Chem.]

[0054] Examples of the unit represented by the formula (C1-3) are given below, but are not limited thereto.

[0055] [Chem.]

[0056] The novolak resin, which is the polymer used in the present invention, can be obtained by condensing a carbazole compound and an aldehyde compound or a ketone compound.

[0057] Specific examples of the carbazole compound include carbazole, 1,3,6,8-tetranitrocarbazole, 3,6-diaminocarbazole, 3,6-dibromo-9-ethylcarbazole, 3,6-dibromo-9-phenylcarbazole, 3,6-dibromocarbazole, 3,6-dichlorocarbazole, 3-amino-9-ethylcarbazole, 3-bromo-9-ethylcarbazole, 4,4'-bis(9H-carbazol-9-yl)biphenyl, 4-glycidylcarbazole, 4-hydroxycarbazole, 9-(1H-benzotriazol-1-ylmethyl)-9H-carbazole, 9-acetyl-3,6-diiodocarbazole, 9-benzoylcarbazole, 9-benzoylcarbazole-6-dicarboxaldehyde, 9-benzylcarbazole-3-carboxaldehyde, 9-methylcarbazole, 9-phenylcarbazole, 9-vinylcarbazole, potassium carbazole, carbazole-N-carbonyl chloride, N-ethylcarbazole-3-carboxaldehyde, N-((9-ethylcarbazol-3-yl)methylene)-2-methyl-1-indolinylamine, and the like, but are not limited thereto. The carbazole compound can be used alone or in combination of two or more.

[0058] Specific examples of the aldehyde compound include saturated aliphatic aldehydes such as formaldehyde, paraformaldehyde, acetaldehyde, propyl aldehyde, butyl aldehyde, isobutyl aldehyde, valeraldehyde, caproaldehyde, 2-methylbutyl aldehyde, hexyl aldehyde, undecanal, 7-methoxy-3,7-dimethyloctyl aldehyde, cyclohexane aldehyde, 3-methyl-2-butyl aldehyde, glyoxal, malonaldehyde, succinaldehyde, glutaraldehyde, adipinaldehyde, etc.; unsaturated aliphatic aldehydes such as acrolein, methacrolein, etc.; heterocyclic aldehydes such as furfural, pyridine aldehyde, etc.; aromatic aldehydes such as benzaldehyde, naphthyl aldehyde, anthryl aldehyde, phenanthryl aldehyde, salicylaldehyde, phenylacetaldehyde, 3-phenylpropionaldehyde, tolyl aldehyde, (N,N-dimethylamino)benzaldehyde, acetoxybenzaldehyde, etc., but are not limited thereto. Among them, aromatic aldehydes are preferred. The aldehyde compound can be used alone or in combination of two or more.

[0059] Specific examples of the ketone compound include diaryl ketone compounds such as diphenyl ketone, phenylnaphthyl ketone, dinaphthyl ketone, phenyltolyl ketone, ditolyl ketone, etc., but are not limited thereto. The ketone compound can be used alone or in combination of two or more.

[0060] In the condensation reaction for obtaining the above polymer, the aldehyde compound or the ketone compound is usually used in a ratio of 0.1 to 10 equivalents with respect to 1 equivalent of the benzene ring constituting the carbazole compound ring.

[0061] In the condensation reaction for obtaining the above polymer, an acid catalyst is usually used. Examples of the acid catalyst include, but are not limited to, mineral acids such as sulfuric acid, phosphoric acid, and perchloric acid; organic sulfonic acids such as p-toluenesulfonic acid and p-toluenesulfonic acid monohydrate; and carboxylic acids such as formic acid and oxalic acid. The amount of the acid catalyst cannot be generally specified as it is appropriately determined according to the type of the acid used, etc., but it is usually appropriately determined from the range of 0.001 to 10,000 parts by mass with respect to 100 parts by mass of the carbazole compound.

[0062] The condensation reaction for obtaining the above polymer can sometimes be carried out without using a solvent when either the raw material compound or the acid catalyst used is liquid, but it is usually carried out using a solvent. Such a solvent is not particularly limited as long as it does not inhibit the reaction, but typically includes ether compounds such as cyclic ether compounds like tetrahydrofuran and dioxane.

[0063] The reaction temperature is usually appropriately determined from the range of 40°C to 200°C, and the reaction time cannot be generally specified as it varies depending on the reaction temperature, but it is usually appropriately determined from the range of 30 minutes to 50 hours.

[0064] After completion of the reaction, if necessary, purification and isolation are carried out according to a conventional method, and the obtained novolak resin is used for the preparation of the release agent composition. A person skilled in the art can determine the production conditions of the novolak resin without undue burden based on the above description and common general knowledge, and thus can produce the novolak resin.

[0065] The weight average molecular weight of an organic resin such as a novolak resin, which is a polymer, is usually 500 to 200,000. From the viewpoint of ensuring solubility in a solvent and of being able to mix well with branched-chain polysilane when forming a film to obtain a uniform film, etc., it is preferably 100,000 or less, more preferably 50,000 or less, even more preferably 10,000 or less, still more preferably 5,000 or less, and even still more preferably 3,000 or less. From the viewpoint of improving the strength of the film, etc., it is preferably 600 or more, more preferably 700 or more, even more preferably 800 or more, still more preferably 900 or more, and even still more preferably 1,000 or more. In the present invention, the weight average molecular weight, number average molecular weight, and dispersity of an organic resin such as a novolak resin, which is a polymer, can be measured, for example, using a GPC apparatus (EcoSEC, HLC-8320GPC manufactured by Tosoh Corporation) and GPC columns (TSKgel SuperMultipore HZ-N, TSKgel SuperMultipore HZ-H manufactured by Tosoh Corporation), setting the column temperature at 40°C, using tetrahydrofuran as the eluent (elution solvent), setting the flow rate at 0.35 mL / min, and using polystyrene (manufactured by Sigma-Aldrich) as the standard sample.

[0066] As the resin contained in the release agent composition, a novolak resin is preferred. Therefore, the release agent composition preferably contains a novolak resin alone as the organic resin. However, for the purpose of adjusting film physical properties, etc., it may contain other polymers together with the novolak resin. Examples of such other polymers include polyacrylate ester compounds, polymethacrylate ester compounds, polyacrylamide compounds, polymethacrylamide compounds, polyvinyl compounds, polystyrene compounds, polymaleimide compounds, polymaleic anhydride, polyacrylonitrile compounds, and the like.

[0067] The above-described release agent composition may contain a crosslinking agent. By including a crosslinking agent, crosslinking between resins can proceed favorably, enabling the achievement of suitable curing. As a result, it is not possible to be favorably removed by an organic solvent, an acid, or chemical solutions (such as an alkaline developer and hydrogen peroxide solution) used in the manufacture of semiconductor elements, but a film that can be favorably removed by a cleaning agent composition can be obtained with good reproducibility. Specific examples of such a crosslinking agent are not particularly limited as long as it can crosslink with the above-described organic resin. Typically, phenolic crosslinking agents, melamine crosslinking agents, urea crosslinking agents, thiourea crosslinking agents, etc. having a crosslinking-forming group such as an alkoxymethyl group (such as a hydroxymethyl group, a methoxymethyl group, a butoxymethyl group) in the molecule can be mentioned. These may be low molecular weight compounds or high molecular weight compounds. The crosslinking agent contained in the above-described release agent composition usually has two or more crosslinking-forming groups. From the viewpoint of achieving more suitable curing with good reproducibility, the number of crosslinking-forming groups contained in the compound that is the crosslinking agent is preferably 2 to 10, more preferably 2 to 6. From the viewpoint of achieving higher heat resistance, the crosslinking agent contained in the above-described release agent composition preferably has an aromatic ring (for example, a benzene ring, a naphthalene ring) in the molecule. Typical examples of such a crosslinking agent include, but are not limited to, phenolic crosslinking agents.

[0068] A phenolic crosslinking agent having a crosslinking-forming group is a compound having a crosslinking-forming group bonded to an aromatic ring and having at least one of a phenolic hydroxyl group and an alkoxy group derived from the phenolic hydroxyl group. Examples of such an alkoxy group derived from the phenolic hydroxyl group include, but are not limited to, a methoxy group and a butoxy group. Neither the aromatic ring to which the crosslinking-forming group is bonded nor the aromatic ring to which the phenolic hydroxyl group and / or the alkoxy group derived from the phenolic hydroxyl group is bonded is limited to a non-condensed aromatic ring such as a benzene ring, and may be a condensed aromatic ring such as a naphthalene ring or anthracene. When there are multiple aromatic rings in the molecule of a phenolic crosslinking agent, the crosslinking-forming group, the phenolic hydroxyl group, and the alkoxy group derived from the phenolic hydroxyl group may be bonded to the same aromatic ring in the molecule or to different aromatic rings. The aromatic ring to which the crosslinking-forming group, the phenolic hydroxyl group, and the alkoxy group derived from the phenolic hydroxyl group are bonded may be further substituted with a hydrocarbon group such as an alkyl group (such as a methyl group, an ethyl group, or a butyl group), an aryl group (such as a phenyl group), or a halogen atom (such as a fluorine atom).

[0069] For example, specific examples of the phenolic crosslinking agent having a crosslinking-forming group include compounds represented by any of the formulas (L1) to (L4).

Chemical formula

[0070] In each formula, each R' independently represents a fluorine atom, an aryl group, or an alkyl group, each R" independently represents a hydrogen atom or an alkyl group, and L 1 and L 2 each independently represents a single bond, a methylene group, or a propane-2,2-diyl group, and L 3is determined according to q1 and represents a single bond, a methylene group, a propane-2,2-diyl group, a methanetriyl group, or an ethane-1,1,1-triyl group; t11, t12, and t13 are integers satisfying 2 ≤ t11 ≤ 5, 1 ≤ t12 ≤ 4, 0 ≤ t13 ≤ 3, and t11 + t12 + t13 ≤ 6; t21, t22, and t23 are integers satisfying 2 ≤ t21 ≤ 4, 1 ≤ t22 ≤ 3, 0 ≤ t23 ≤ 2, and t21 + t22 + t23 ≤ 5; t24, t25, and t26 are integers satisfying 2 ≤ t24 ≤ 4, 1 ≤ t25 ≤ 3, 0 ≤ t26 ≤ 2, and t24 + t25 + t26 ≤ 5; t27, t28, and t29 are integers satisfying 0 ≤ t27 ≤ 4, 0 ≤ t28 ≤ 4, 0 ≤ t29 ≤ 4, and t24 + t25 + t26 ≤ 4; t31, t32, and t33 are integers satisfying 2 ≤ t31 ≤ 4, 1 ≤ t32 ≤ 3, 0 ≤ t33 ≤ 2, and t31 + t32 + t33 ≤ 5; t41, t42, and t43 are integers satisfying 2 ≤ t41 ≤ 3, 1 ≤ t42 ≤ 2, 0 ≤ t43 ≤ 1, and t41 + t42 + t43 ≤ 4; q1 is 2 or 3; q2 represents the number of repetitions and is an integer of 0 or more. Specific examples of the above aryl group and alkyl group are the same as the following specific examples, but as the aryl group, a phenyl group is preferable, and as the alkyl group, a methyl group and a t-butyl group are preferable.

[0071] Hereinafter, specific examples of the compounds represented by formula (L1) to (L22) and formula (L1M) to (L22M) are given, but are not limited thereto. These compounds may be synthesized by known methods, and can also be obtained, for example, as products of Asahi Organic Chemical Industry Co., Ltd. and Honshu Chemical Industry Co., Ltd.

[0072]

Chemical formula

[0073]

Chemical formula

[0074]

Chemical formula

[0075] [Chemistry]

[0076] The melamine-based crosslinking agent having a crosslink-forming group is a melamine derivative, 2,4-diamino-1,3,5-triazine derivative or 2-amino-1,3,5-triazine derivative in which at least one of the hydrogen atoms of the amino group bonded to the triazine ring is substituted with a crosslink-forming group, and the triazine ring may further have a substituent such as an aryl group such as a phenyl group. Specific examples of the melamine-based crosslinking agent having a crosslink-forming group include, but are not limited to, mono-, bis-, tris-, tetrakis-, pentakis- or hexakisalkoxymethylmelamines such as N,N,N’,N’,N”,N”-hexakis(methoxymethyl)melamine and N,N,N’,N’,N”,N”-hexakis(butoxymethyl)melamine, and mono-, bis-, tris- or tetrakisalkoxymethylbenzoguanamines such as N,N,N’,N’-tetrakis(methoxymethyl)benzoguanamine and N,N,N’,N’-tetrakis(butoxymethyl)benzoguanamine.

[0077] The urea-based crosslinking agent having a crosslink-forming group is a derivative of a urea bond-containing compound and has a structure in which at least one of the hydrogen atoms of the NH group constituting the urea bond is substituted with a crosslink-forming group. Specific examples of the urea-based crosslinking agent having a crosslink-forming group include, but are not limited to, mono-, bis-, tris- or tetrakisalkoxymethyl glycolurils such as 1,3,4,6-tetrakis(methoxymethyl)glycoluril and 1,3,4,6-tetrakis(butoxymethyl)glycoluril, and mono-, bis-, tris- or tetrakisalkoxymethyl ureas such as 1,3-bis(methoxymethyl)urea and 1,1,3,3-tetrakis(methoxymethyl)urea.

[0078] A thiourea-based crosslinking agent having a crosslink-forming group is a derivative of a thiourea bond-containing compound and has a structure in which at least one of the hydrogen atoms of the NH group constituting the thiourea bond is substituted with a crosslink-forming group. Specific examples of the thiourea-based crosslinking agent having a crosslink-forming group include, but are not limited to, mono-, bis-, tris- or tetrakisalkoxymethylthioureas such as 1,3-bis(methoxymethyl)thiourea and 1,1,3,3-tetrakis(methoxymethyl)thiourea.

[0079] The amount of the crosslinking agent contained in the above-described release agent composition varies depending on the coating method employed, the desired film thickness, etc., and thus cannot be generally specified. However, with respect to the film constituent components, it is usually 0.001 to 80% by mass, and from the viewpoint of achieving suitable curing and reproducibly obtaining a laminate in which the semiconductor substrate and the support substrate can be satisfactorily separated, it is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, still more preferably 0.5% by mass or more, and still more preferably 1.0% by mass or more, and is preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably 20% by mass or less, and still more preferably 10% by mass or less.

[0080] For the purpose of promoting the crosslinking reaction or the like, the above-described release agent composition may contain an acid generator or an acid. However, from the viewpoint of reproducibly obtaining a film suitable as a release layer, which has the characteristic that it cannot be suitably removed by an organic solvent, an acid, or a chemical solution (alkali developer, hydrogen peroxide solution, etc.) used in the manufacture of semiconductor elements, but can be suitably removed by a cleaning agent composition, the above-described release agent composition usually does not contain an acid generator or an acid.

[0081] Examples of the acid generator include a thermal acid generator and a photoacid generator. The thermal acid generator is not particularly limited as long as it generates an acid by heat. Specific examples thereof include 2,4,4,6-tetrabromocyclohexadienone, benzoin tosylate, 2-nitrobenzyl tosylate, K-PURE [registered trademark] CXC-1612, CXC-1614, TAG-2172, TAG-2179, TAG-2678, TAG-2689, TAG-2700 (manufactured by King Industries), and SI-45, SI-60, SI-80, SI-100, SI-110, SI-150 (manufactured by Sanshin Chemical Industry Co., Ltd.), and other alkyl esters of organic sulfonic acids, etc., but are not limited thereto.

[0082] Examples of the photoacid generator include, for example, onium salt compounds, sulfonimide compounds, and disulfonyldiazomethane compounds, etc.

[0083] Specific examples of the onium salt compounds include iodonium salt compounds such as diphenyliodonium hexafluorophosphate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoronormalbutanesulfonate, diphenyliodonium perfluoronormaloctanesulfonate, diphenyliodonium camphorsulfonate, bis(4-tert-butylphenyl)iodonium camphorsulfonate, bis(4-tert-butylphenyl)iodonium trifluoromethanesulfonate, etc., and sulfonium salt compounds such as triphenylsulfonium hexafluoroantimonate, triphenylsulfonium nonafluoronormalbutanesulfonate, triphenylsulfonium camphorsulfonate, triphenylsulfonium trifluoromethanesulfonate, etc., but are not limited thereto.

[0084] Specific examples of the sulfonimide compounds include N-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluoronormalbutanesulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, N-(trifluoromethanesulfonyloxy)naphthalimide, etc., but are not limited thereto.

[0085] Specific examples of the disulfonyldiazomethane compound include, but are not limited to, bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(2,4-dimethylbenzenesulfonyl)diazomethane, methylsulfonyl-p-toluenesulfonyldiazomethane, and the like.

[0086] Specific examples of the acid include arylsulfonic acids such as p-toluenesulfonic acid, pyridinium p-toluenesulfonic acid (pyridinium paratoluenesulfonate), pyridinium phenolsulfonic acid, 5-sulfosalicylic acid, 4-phenolsulfonic acid, 4-chlorobenzenesulfonic acid, benzenedisulfonic acid, 1-naphthalenesulfonic acid, and pyridinium salts and their salts; arylcarboxylic acids such as salicylic acid, benzoic acid, hydroxybenzoic acid, naphthalenecarboxylic acid, and their salts; chain or cyclic alkylsulfonic acids such as trifluoromethanesulfonic acid, camphorsulfonic acid, and their salts; and chain or cyclic alkylcarboxylic acids such as citric acid and their salts, but are not limited thereto.

[0087] Since the amounts of the acid generator and the acid contained in the above-described release agent composition vary depending on the type of the crosslinking agent used, the heating temperature during film formation, etc., they cannot be generally defined, but are usually 0.01% by mass to 5% by mass based on the film constituent components.

[0088] The above-described release agent composition may contain a surfactant for the purpose of adjusting the liquid physical properties of the composition itself and the film physical properties of the resulting film, or for reproducibly preparing a highly uniform release agent composition. Examples of the surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether; polyoxyethylene alkyl allyl ethers such as polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether; polyoxyethylene-polyoxypropylene block copolymers; sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, and sorbitan tristearate; polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate; nonionic surfactants; fluorosurfactants such as Ftop EF301, EF303, and EF352 (trade names, manufactured by Tocem Products Co., Ltd.), Megafac F171, F173, R-30, and R-30N (trade names, manufactured by DIC Corporation), Fluorad FC430 and FC431 (trade names, manufactured by Sumitomo 3M Limited), Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, and SC106 (trade names, manufactured by Asahi Glass Co., Ltd.); and organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.). The surfactant can be used alone or in combination of two or more kinds. The amount of the surfactant is usually 2% by mass or less based on the film constituent components of the release agent composition.

[0089] The release agent composition contains a branched polysilane. Branched-chain polysilane has an Si-Si bond and a branched structure. When the release agent composition contains branched-chain polysilane, the resulting release layer made of a film cannot be suitably removed by any of an organic solvent, an acid, and a chemical solution (such as an alkaline developer and hydrogen peroxide solution) used in the manufacture of semiconductor devices, but can be suitably removed by a cleaning agent composition. As a result, after separating the semiconductor substrate and the support substrate of the laminate of the present invention, by cleaning each substrate with the cleaning agent composition, the residue of the release layer on the substrate can be suitably removed. Although the reason for this is not clear, depending on the type of terminal group (terminal substituent (atom)) of polysilane, polysilane can react with an organic resin and crosslink, and since branched-chain polysilane has more terminal groups (terminal substituents (atoms)) than linear polysilane, it is considered that branched-chain polysilane has more crosslinking points than linear polysilane. By appropriate and suitable curing through such more crosslinking points in the branched-chain polysilane, it is presumed that it is possible to achieve both the property of not being suitably removed by an organic solvent, an acid, and a chemical solution (such as an alkaline developer and hydrogen peroxide solution) used in the manufacture of semiconductor devices, and the property of being suitably removed by a cleaning agent composition.

[0090] The branched-chain polysilane preferably contains a structural unit represented by formula (B).

Chemical formula

[0091] R Brepresents a hydrogen atom, a hydroxyl group, a silyl group or an organic group. Specific examples of such organic groups include hydrocarbon groups (an alkyl group which may be substituted, an alkenyl group which may be substituted, an aryl group which may be substituted, an aralkyl group which may be substituted), ether groups corresponding to these hydrocarbon groups (an alkoxy group which may be substituted, an aryloxy group which may be substituted, an aralkyloxy group which may be substituted, etc.), and the like. Usually, the organic group is often a hydrocarbon group such as an alkyl group, an alkenyl group, an aryl group, an aralkyl group, etc. Further, a hydrogen atom, a hydroxyl group, an alkoxy group, a silyl group, etc. are often substituted at the terminal.

[0092] The alkyl group which may be substituted may be linear, branched or cyclic. Specific examples of the linear or branched alkyl group which may be substituted include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, an s-butyl group, a tertiary butyl group, an n-pentyl group, a 1-methyl-n-butyl group, a 2-methyl-n-butyl group, a 3-methyl-n-butyl group, a 1,1-dimethyl-n-propyl group, a 1,2-dimethyl-n-propyl group, a 2,2-dimethyl-n-propyl group, a 1-ethyl-n-propyl group, an n-hexyl group, a 1-methyl-n-pentyl group, a 2-methyl-n-pentyl group, a 3-methyl-n-pentyl group, a 4-methyl-n-pentyl group, a 1,1-dimethyl-n-butyl group, a 1,2-dimethyl-n-butyl group, a 1,3-dimethyl-n-butyl group, a 2,2-dimethyl-n-butyl group, a 2,3-dimethyl-n-butyl group, a 3,3-dimethyl-n-butyl group, a 1-ethyl-n-butyl group, a 2-ethyl-n-butyl group, a 1,1,2-trimethyl-n-propyl group, a 1,2,2-trimethyl-n-propyl group, a 1-ethyl-1-methyl-n-propyl group, a 1-ethyl-2-methyl-n-propyl group, etc., but are not limited thereto, and the number of carbon atoms thereof is usually 1 to 14, preferably 1 to 10, more preferably 1 to 6. Specific examples of the cyclic alkyl group which may be substituted include cycloalkyl groups such as cyclopropyl group, cyclobutyl group, 1-methyl-cyclopropyl group, 2-methyl-cyclopropyl group, cyclopentyl group, 1-methyl-cyclobutyl group, 2-methyl-cyclobutyl group, 3-methyl-cyclobutyl group, 1,2-dimethyl-cyclopropyl group, 2,3-dimethyl-cyclopropyl group, 1-ethyl-cyclopropyl group, 2-ethyl-cyclopropyl group, cyclohexyl group, 1-methyl-cyclopentyl group, 2-methyl-cyclopentyl group, 3-methyl-cyclopentyl group, 1-ethyl-cyclobutyl group, 2-ethyl-cyclobutyl group, 3-ethyl-cyclobutyl group, 1,2-dimethyl-cyclobutyl group, 1,3-dimethyl-cyclobutyl group, 2,2-dimethyl-cyclobutyl group, 2,3-dimethyl-cyclobutyl group, 2,4-dimethyl-cyclobutyl group, 3,3-dimethyl-cyclobutyl group, 1-n-propyl-cyclopropyl group, 2-n-propyl-cyclopropyl group, 1-i-propyl-cyclopropyl group, 2-i-propyl-cyclopropyl group, 1,2,2-trimethyl-cyclopropyl group, 1,2,3-trimethyl-cyclopropyl group, 2,2,3-trimethyl-cyclopropyl group, 1-ethyl-2-methyl-cyclopropyl group, 2-ethyl-1-methyl-cyclopropyl group, 2-ethyl-2-methyl-cyclopropyl group, 2-ethyl-3-methyl-cyclopropyl group, bicyclobutyl group, bicyclopentyl group, bicyclohexyl group, bicycloheptyl group, bicyclooctyl group, bicyclononyl group, bicyclodecyl group, etc., but are not limited thereto, and the number of carbon atoms thereof is usually 3 to 14, preferably 4 to 10, more preferably 5 to 6.

[0093] The alkenyl group may be linear, branched or cyclic. Specific examples of the linear or branched alkenyl group which may be substituted include vinyl group, allyl group, butenyl group, pentenyl group, etc., but are not limited thereto, and the number of carbon atoms thereof is usually 2 to 14, preferably 2 to 10, more preferably 1 to 6. Specific examples of the optionally substituted cyclic alkenyl group include, but are not limited to, cyclopentenyl, cyclohexenyl, etc. The number of carbon atoms thereof is usually 4 to 14, preferably 5 to 10, more preferably 5 to 6.

[0094] Specific examples of the optionally substituted aryl group include, but are not limited to, phenyl group, 4-methylphenyl group, 3-methylphenyl group, 2-methylphenyl group, 3,5-dimethylphenyl group, 1-naphthyl group, 2-naphthyl group, etc. The number of carbon atoms thereof is usually 6 to 20, preferably 6 to 14, more preferably 6 to 12.

[0095] Specific examples of the optionally substituted aralkyl group include, but are not limited to, benzyl group, phenethyl group, phenylpropyl group, etc. The optionally substituted aralkyl group is preferably a group in which one hydrogen atom of an alkyl group having 1 to 4 carbon atoms is substituted with an aryl group having 6 to 20 carbon atoms.

[0096] The optionally substituted alkoxy group may have a linear, branched or cyclic alkyl moiety.

[0097] Specific examples of the optionally substituted linear or branched alkoxy group include, but are not limited to, methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, t-butoxy group, pentyloxy group, etc. The number of carbon atoms thereof is usually 1 to 14, preferably 1 to 10, more preferably 1 to 6.

[0098] Specific examples of the optionally substituted cyclic alkoxy group include, but are not limited to, cyclopentyloxy, cyclohexyloxy, etc. The number of carbon atoms thereof is usually 3 to 14, preferably 4 to 10, more preferably 5 to 6.

[0099] Specific examples of the aryl oxy group which may be substituted include phenoxy, 1-naphthyloxy, 2-naphthyloxy and the like, but are not limited thereto, and the number of carbon atoms thereof is usually 6 to 20, preferably 6 to 14, more preferably 6 to 10.

[0100] Specific examples of the aralkyl oxy group which may be substituted include benzyloxy, phenethyloxy, phenylpropyloxy and the like, but are not limited thereto. The aralkyl oxy group which may be substituted is preferably a group in which one hydrogen atom of an alkyloxy group having 1 to 4 carbon atoms is substituted with an aryl group having 6 to 20 carbon atoms.

[0101] Specific examples of the silyl group include a silyl group, a disilanyl group, a trisilanyl group and the like, but are not limited thereto, and the number of silicon atoms thereof is usually 1 to 10, preferably 1 to 6.

[0102] R B When R is the above organic group or silyl group, at least one of its hydrogen atoms may be substituted by a substituent. Specific examples of such a substituent include a hydroxyl group, an alkyl group, an aryl group, an alkoxy group and the like.

[0103] From the viewpoint of suppressing unintentional peeling when the laminate of the present invention is brought into contact with any of an organic solvent, an acid, and a chemical solution (alkali developer, hydrogen peroxide solution, etc.) used in the manufacture of semiconductor devices, and from the viewpoint of preferably removing the residue of the peeling layer on the substrate when each substrate is washed with a detergent composition after separating the semiconductor substrate and the support substrate of the laminate of the present invention, R B is preferably an alkyl group or an aryl group, more preferably an aryl group, even more preferably a phenyl group, a 1-naphthyl group or a 2-naphthyl group, and still more preferably a phenyl group.

[0104] The branched polysilane used in the present invention may contain a structural unit represented by formula (S) or a structural unit represented by formula (N) together with the structural unit represented by formula (B). However, from the viewpoint of suppressing unintentional peeling when the laminate of the present invention is brought into contact with any of an organic solvent, an acid, and a chemical solution (such as an alkaline developer and hydrogen peroxide solution) used in the manufacture of semiconductor elements, and from the viewpoint of preferably removing the residue of the peeling layer on the substrate when each substrate is washed with a cleaning agent composition after separating the semiconductor substrate and the support substrate of the laminate of the present invention, the content of the structural unit represented by formula (B) in the branched polysilane is usually 50 mol% or more, preferably 60 mol% or more, more preferably 70 mol% or more, even more preferably 80 mol% or more, still more preferably 90% or more, and even still more preferably 95 mol% or more in all the structural units.

[0105]

Chemical formula

[0106] The terminal group (terminal substituent (atom)) of the branched polysilane may usually be a hydrogen atom, a hydroxyl group, a halogen atom (such as a chlorine atom), an alkyl group, an aryl group, an alkoxy group, a silyl group, etc. Among them, the hydroxyl group, methyl group, and phenyl group are often the case, and among them, the methyl group is preferable, and the terminal group may be a trimethylsilyl group.

[0107] In a certain aspect, the average degree of polymerization of the branched polysilane, in terms of silicon atoms (that is, the average number of silicon atoms per molecule), is usually 2 to 100, preferably 3 to 80, more preferably 5 to 50, and even more preferably 10 to 30. In one aspect, the upper limit of the weight-average molecular weight of the branched polysilane is usually 30,000, preferably 20,000, more preferably 10,000, even more preferably 5,000, still more preferably 2,000, and even more preferably 1,500, and the lower limit thereof is usually 50, preferably 100, more preferably 150, even more preferably 200, still more preferably 300, and even more preferably 500. The number-average degree of polymerization and the weight-average molecular weight of the polysilane used in the present invention can be measured, for example, using a GPC apparatus (EcoSEC, HLC-8220GPC manufactured by Tosoh Corporation) and GPC columns (Shodex KF-803L, KF-802, and KF-801 manufactured by Showa Denko K.K. used in this order), setting the column temperature at 40°C, using tetrahydrofuran as the eluent (elution solvent), setting the flow rate at 1.00 mL / min, and using polystyrene (manufactured by Sigma-Aldrich) as the standard sample. If the degree of polymerization and the weight-average molecular weight of the branched polysilane used are too small, the polysilane may vaporize due to heating when forming a film as the release layer or when processing the laminate provided with the obtained release layer, or problems may occur due to poor film strength. If the degree of polymerization and the molecular weight of the branched polysilane used are too large, precipitation may occur in the composition without ensuring sufficient solubility depending on the type of solvent used for preparing the release agent composition, or the mixing with the resin may be insufficient and it may not be possible to obtain a highly uniform film with good reproducibility. Therefore, from the viewpoint of obtaining a laminate provided with a release layer that contributes more favorably to the production of semiconductor elements with better reproducibility, it is desirable that the degree of polymerization and the weight-average molecular weight of the branched polysilane satisfy the above ranges.

[0108] The 5% weight loss temperature of the branched polysilane used in the present invention is usually 300°C or higher, preferably 350°C or higher, more preferably 365°C or higher, even more preferably 380°C or higher, still more preferably 395°C or higher, and even more preferably 400°C or higher, from the viewpoint of obtaining a release layer with excellent heat resistance with good reproducibility. The 5% weight loss temperature of the polysilane used in the present invention can be measured, for example, by using a NETZSCH 2010SR, heating from room temperature (25 °C) to 400 °C at a rate of 10 °C / min under air.

[0109] When the semiconductor substrate and the support substrate of the laminate of the present invention are separated and then each substrate is washed with a cleaning agent composition, from the viewpoint of preferably removing the residue of the release layer on the substrate and from the viewpoint of reproducibly preparing a release agent composition excellent in uniformity, the branched polysilane used in the present invention is an ether compound such as tetrahydrofuran, an aromatic compound such as toluene, a glycol ether ester compound such as propylene glycol monomethyl ether acetate, a ketone compound such as cyclohexanone or methyl ethyl ketone, or a glycol ether compound such as propylene glycol monomethyl ether. Those that dissolve in any of these are preferred. In this case, dissolution means that when an attempt is made to dissolve using a shaker at room temperature (25 °C) so as to obtain a 10% by mass solution, it can be visually confirmed that dissolution has occurred within 1 hour.

[0110] The branched polysilane may be in a solid state or a liquid state at room temperature.

[0111] The branched polysilane used in the present invention can be produced, for example, with reference to known methods described in JP-A-2011-208054, JP-A-2007-106894, JP-A-2007-145879, WO2005 / 113648, etc., or can also be obtained as a commercial product. Specific examples of commercial products include, but are not limited to, silicon materials polysilane OGSOL SI-20-10, SI-20-14 manufactured by Osaka Gas Chemical Co., Ltd.

[0112] A preferred example of the branched polysilane is as follows, but is not limited thereto.

Chemical formula

[0113] The content of the branched polysilane in the above-described release agent composition is usually 10 to 90% by mass with respect to the film constituent components. However, depending on the organic solvent, acid, or chemical solution (alkali developer, hydrogen peroxide solution, etc.) used in the manufacture of semiconductor devices, it cannot be preferably removed. From the viewpoint of reproducibly realizing a film that can be preferably removed by a cleaning agent composition, it is preferably 15 to 80% by mass, more preferably 20 to 70% by mass, even more preferably 25 to 60% by mass, and still more preferably 30 to 50% by mass.

[0114] The above-described release agent composition contains a solvent. As such a solvent, for example, a highly polar solvent that can dissolve film constituent components such as organic resins and branched polysilanes well can be used. If necessary, a low polar solvent may be used for the purpose of adjusting viscosity, surface tension, etc. In the present invention, a low polar solvent is defined as having a relative dielectric constant of less than 7 at a frequency of 100 kHz, and a high polar solvent is defined as having a relative dielectric constant of 7 or more at a frequency of 100 kHz. The solvents can be used alone or in combination of two or more.

[0115] Further, as the highly polar solvent, for example, amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylisobutyramide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone; ketone solvents such as ethyl methyl ketone, isophorone, cyclohexanone; cyano solvents such as acetonitrile, 3-methoxypropionitrile; polyhydric alcohol solvents such as ethylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, 1,3-butanediol, 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, tetrahydrofurfuryl alcohol, etc.; sulfoxide solvents such as dimethyl sulfoxide, etc. are mentioned.

[0116] Examples of low-polarity solvents include, for example, 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 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; ester 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, etc.

[0117] The content of the solvent is appropriately set in consideration of the viscosity of the desired composition, the coating method to be employed, the thickness of the film to be produced, etc., but it is 99% by mass or less of the whole composition, and preferably, with respect to the whole composition, it is 70 to 99% by mass, that is, in that case, the amount of the film constituent components is 1 to 30% by mass with respect to the whole composition. In the present invention, the film constituent components mean components other than the solvent contained in the composition.

[0118] The viscosity and surface tension of the above-described release agent composition are appropriately adjusted by changing the type of solvent used, their ratios, the concentration of film constituent components, etc., in consideration of various factors such as the coating method to be used and the desired film thickness.

[0119] In certain embodiments of the present invention, from the viewpoints of reproducibly obtaining a composition with high uniformity, reproducibly obtaining a composition with high storage stability, reproducibly obtaining a composition that gives a film with high uniformity, etc., the above-described release agent composition contains a glycol-based solvent. Here, the “glycol-based solvent” as used herein is a general term for glycols, glycol monoethers, glycol diethers, glycol monoesters, glycol diesters, and glycol ester ethers.

[0120] An example of a preferred glycol-based solvent is represented by formula (G).

Chemical formula

[0121] In formula (G), R G1 each independently represents a linear or branched alkylene group having 2 to 4 carbon atoms, and R G2 and R G3 each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, or an alkylacyl group in which the alkyl part is a linear or branched alkyl group having 1 to 8 carbon atoms, and n g is an integer from 1 to 6.

[0122] Specific examples of the linear or branched alkylene group having 2 to 4 carbon atoms include, but are not limited to, an ethylene group, a trimethylene group, a 1-methylethylene group, a tetramethylene group, a 2-methylpropane-1,3-diyl group, a pentamethylene group, a hexamethylene group, etc. Among them, from the viewpoints of reproducibly obtaining a composition with high uniformity, reproducibly obtaining a composition with high storage stability, reproducibly obtaining a composition that gives a film with high uniformity, etc., a linear or branched alkylene group having 2 to 3 carbon atoms is preferable, and a linear or branched alkylene group having 3 carbon atoms is more preferable.

[0123] Specific examples of the linear or branched alkyl group having 1 to 8 carbon atoms include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, tertiary 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-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, etc., but are not limited thereto. Among them, from the viewpoints of reproducibly obtaining a composition with high uniformity, reproducibly obtaining a composition with high storage stability, reproducibly obtaining a composition that gives a film with high uniformity, etc., a methyl group and an ethyl group are preferable, and a methyl group is more preferable.

[0124] Specific examples of the linear or branched alkyl group having 1 to 8 carbon atoms in the alkylacyl group in which the alkyl moiety is a linear or branched alkyl group having 1 to 8 carbon atoms are the same as the above specific examples. Among these, from the viewpoints of reproducibly obtaining a composition with high uniformity, reproducibly obtaining a composition with high storage stability, reproducibly obtaining a composition that provides a film with high uniformity, etc., a methylcarbonyl group and an ethylcarbonyl group are preferred, and a methylcarbonyl group is more preferred.

[0125] n g From the viewpoints of reproducibly obtaining a composition with high uniformity, reproducibly obtaining a composition with high storage stability, reproducibly obtaining a composition that provides a film with high uniformity, etc., n is preferably 4 or less, more preferably 3 or less, even more preferably 2 or less, and most preferably 1.

[0126] From the viewpoints of reproducibly obtaining a composition with high uniformity, reproducibly obtaining a composition with high storage stability, reproducibly obtaining a composition that provides a film with high uniformity, etc., in formula (G), preferably, R G2 and R G3 at least one of them is a linear or branched alkyl group having 1 to 8 carbon atoms. More preferably, one of R G2 and R G3 is a linear or branched alkyl group having 1 to 8 carbon atoms, and the other is a hydrogen atom or an alkylacyl group in which the alkyl part is a linear or branched alkyl group having 1 to 8 carbon atoms.

[0127] From the viewpoints of reproducibly obtaining a composition with high uniformity, reproducibly obtaining a composition with high storage stability, reproducibly obtaining a composition that provides a film with high uniformity, etc., the content of the glycol-based solvent is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, still more preferably 90% by mass or more, and even more preferably 95% by mass or more with respect to the solvent contained in the above-described release agent composition. From the viewpoints of reproducibly obtaining a composition with high uniformity, reproducibly obtaining a composition with high storage stability, reproducibly obtaining a composition that provides a film with high uniformity, etc., in the above-described release agent composition, the film constituent components are uniformly dispersed or dissolved in the solvent, and are preferably dissolved.

[0128] The above-described release agent composition can be produced by mixing an organic resin, a branched polysilane, and a solvent. The mixing order is not particularly limited. However, as an example of a method capable of easily and reproducibly producing the release agent composition, there are a method of dissolving an organic resin and a branched polysilane in a solvent at once, a method of dissolving a part of the organic resin and the branched polysilane in a solvent and separately dissolving the remainder in the solvent, and then mixing the obtained respective solutions, but the method is not limited thereto. At this time, as the solution of the organic resin, the reaction solution obtained in the synthesis of the organic resin can be used as it is, or can be concentrated or diluted. Further, when preparing the release agent composition, it may be appropriately heated within a range where the components are not decomposed or deteriorated. In the present invention, for the purpose of removing foreign matters, the solvent, solution, etc. to be used may be filtered using a filter on the submicrometer order or the like during the production of the release agent composition or after all the components are mixed.

[0129] The thickness of the release layer provided in the laminate of the present invention is usually 5 nm to 100 μm, but in one aspect it is 10 nm to 1 μm, and in other aspects it is 50 nm to 500 nm.

[0130] The above-described release agent composition is also an object of the present invention, and the related various conditions (preferred conditions, production conditions, etc.) are as described above. By using the release agent composition of the present invention, for example, a film suitable as a release layer used in the production of semiconductor elements can be produced with good reproducibility. In particular, the release agent composition of the present invention can be suitably used for forming the above-mentioned release layer of a laminate including a semiconductor substrate, a support substrate, an adhesive layer provided in contact with the semiconductor substrate between the semiconductor substrate and the support substrate, and a release layer provided in contact with the support substrate and the adhesive layer. When the support substrate of such a laminate has light transmissivity, by irradiating light from the support substrate side to the release layer, the separation or decomposition of the release layer proceeds preferably as described above. As a result, the semiconductor substrate can be separated from the support substrate without applying an excessive load for separation any further, and by washing the separated semiconductor substrate with a cleaning agent composition, suitable cleaning of the substrate can be achieved without leaving residues of the release layer on the substrate. One of the characteristics of the release layer obtained from the release agent composition of the present invention is that it cannot be preferably removed by an organic solvent, an acid, or a chemical solution (alkali developer, hydrogen peroxide solution, etc.) used in the manufacture of semiconductor elements, but can be preferably removed by a cleaning agent composition. Such specific and selective removability is contributed by the branched polysilane contained in the release agent composition of the present invention. The branched polysilane can function as a solubility improver or removability improver for the release layer with respect to the cleaning agent composition, and can also function as a solubility reducer or removability reducer for the release layer with respect to an organic solvent, an acid, or a chemical solution (alkali developer, hydrogen peroxide solution, etc.) used in the manufacture of semiconductor elements.

[0131] As described above, the release layer obtained from the release agent composition of the present invention cannot be preferably removed by an organic solvent, an acid, or a chemical solution (alkali developer, hydrogen peroxide solution, etc.) used in the manufacture of semiconductor elements. Specific examples of such organic solvents typically include linear or branched aliphatic hydrocarbons such as hexane, heptane, octane, nonane, decane, undecane, dodecane, isododecane, etc.; cyclic aliphatic hydrocarbons such as cyclohexane, cycloheptane, cyclooctane, isopropylcyclohexane, p-menthane, etc., and cyclic aliphatic unsaturated hydrocarbons such as limonene, etc.; aromatic hydrocarbons such as benzene, toluene, o-xylene, m-xylene, p-xylene, mesitylene, 1,2,4-trimethylbenzene, cumene, 1,4-diisopropylbenzene, p-cymene, etc.; ketones such as dialkyl ketones like MIBK (methyl isobutyl ketone), ethyl methyl ketone, acetone, diisobutyl ketone, 2-octanone, 2-nonanone, 5-nonanone, etc., and cycloalkyl ketones such as cyclohexanone, etc., aliphatic saturated hydrocarbon ketones, and alkenyl ketones such as isophorone, etc., aliphatic unsaturated hydrocarbon ketones; ethers such as dialkyl ethers like diethyl ether, di(n-propyl) ether, di(n-butyl) ether, di(n-pentyl) ether, etc., and cyclic alkyl ethers such as tetrahydrofuran, dioxane, etc.; sulfides such as dialkyl sulfides like diethyl sulfide, di(n-propyl) sulfide, di(n-butyl) sulfide, etc.; amides such as N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylisobutylamide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, etc.; nitriles such as acetonitrile, 3-methoxypropionitrile, etc.; polyhydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, 1,3-butanediol, 2,3-butanediol, etc.; glycol monohydrocarbon ethers such as glycol monoalkyl ethers like propylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, etc., and glycol monoaryl ethers such as diethylene glycol monophenyl ether, etc.Linear or branched alkyl monohydric alcohols such as methanol, ethanol, and propanol, cyclic alkyl alcohols such as cyclohexanol, and other alkyl alcohols; monohydric alcohols other than alkyl alcohols such as diacetone alcohol, benzyl alcohol, 2-phenoxyethanol, 2-benzyloxyethanol, 3-phenoxybenzyl alcohol, and tetrahydrofurfuryl alcohol; glycols such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, tripropylene glycol, hexylene glycol, triethylene glycol, 1,2-butanediol, 2,3-butanediol, 1,3-butanediol, 1,4-butanediol, and 1,5-pentanediol; glycol monoalkyl ethers such as ethylene glycol monohexyl ether, propylene glycol monobutyl ether, diethylene glycol monoethyl ether, dipropylene glycol monobutyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, diethylene glycol monoisobutyl ether, dipropylene glycol monomethyl ether, diethylene glycol monopropyl ether (propyl carbitol), diethylene glycol monohexyl ether, 2-ethylhexyl carbitol, dipropylene glycol monopropyl ether, tripropylene glycol monomethyl ether, diethylene glycol monomethyl ether, and tripropylene glycol monobutyl ether; glycol monoethers such as glycol monoaryl ethers such as 2-phenoxyethanol; glycol dialkyl ethers such as ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol dibutyl ether, dipropylene glycol methyl-n-propyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol dibutyl ether, triethylene glycol dimethyl ether, triethylene glycol butyl methyl ether, and tetraethylene glycol dimethyl ether;Glycol ether acetates such as dipropylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, etc.; cyclic carbonates such as ethylene carbonate, propylene carbonate, vinylene carbonate, etc.; esters such as butyl acetate, pentyl acetate, etc. are exemplified. ;

[0132] Examples of such acids include mineral acids such as phosphoric acid, hydrochloric acid, perchloric acid, nitric acid, sulfuric acid and their salts, arylsulfonic acids such as p-toluenesulfonic acid, pyridinium p-toluenesulfonic acid (pyridinium paratoluenesulfonate), pyridinium phenolsulfonic acid, 5-sulfosalicylic acid, 4-phenolsulfonic acid, 4-chlorobenzenesulfonic acid, benzenedisulfonic acid, 1-naphthalenesulfonic acid and their salts such as pyridinium salts, arylcarboxylic acids such as salicylic acid, benzoic acid, hydroxybenzoic acid, naphthalenecarboxylic acid and their salts, chain or cyclic alkylsulfonic acids such as trifluoromethanesulfonic acid, camphorsulfonic acid and their salts, chain or cyclic alkylcarboxylic acids such as citric acid and their salts, etc., but are not limited thereto.

[0133] Examples of such alkaline developers include aqueous solutions of alkali metal hydroxides such as potassium hydroxide and sodium hydroxide, aqueous solutions of quaternary ammonium hydroxides such as tetramethylammonium hydroxide (tetramethylammonium hydroxide), tetraethylammonium hydroxide, choline, etc., and alkaline aqueous solutions such as aqueous solutions of amines such as ethanolamine, propylamine, ethylenediamine, etc., but are not limited thereto.

[0134] The property that the release layer obtained from the release agent composition of the present invention is not preferably removed by an organic solvent, an acid or a chemical solution (alkaline developer, hydrogen peroxide solution, etc.) used in the manufacture of semiconductor elements can be evaluated by the following method. That is, it can be evaluated by the film reduction rate (%) of the film thickness after immersion with respect to the film thickness before immersion when a film with a thickness of 200 nm formed on a 4 cm square silicon wafer is immersed in 7 mL of the evaluation liquid together with the silicon wafer and the film thickness before and after immersion is compared. The release layer obtained from the release agent composition of the present invention shows a low film reduction rate, usually 6% or less, preferably 5% or less, more preferably 4% or less, even more preferably 3% or less, still more preferably 2% or less, even more preferably 1% or less, and most preferably 0%, even after being immersed in an organic solvent, an acid, or a chemical solution (such as an alkaline developer or hydrogen peroxide solution) used in the manufacture of semiconductor devices according to such a method. The film reduction rate can be calculated by the formula: film thickness after immersion (nm) / film thickness before immersion (nm) × 100.

[0135] As described above, the release layer obtained from the release agent composition of the present invention can be preferably removed by the cleaning agent composition, and such a cleaning agent composition usually contains a salt and a solvent. A preferred example of the cleaning agent composition includes a cleaning agent composition containing a quaternary ammonium salt and a solvent. The quaternary ammonium salt is composed of a quaternary ammonium cation and an anion, and is not particularly limited as long as it is used for this kind of application. Typical examples of such quaternary ammonium cations include tetra(hydrocarbon)ammonium cations. On the other hand, examples of the anion paired with it include hydroxide ions (OH - ); halogen ions such as fluoride ions (F - ), chloride ions (Cl - ), bromide ions (Br - ), and iodide ions (I - ); tetrafluoroborate ions (BF4 - ); hexafluorophosphate ions (PF6 - ), etc., but are not limited thereto.

[0136] In the present invention, the quaternary ammonium salt is preferably a halogen-containing quaternary ammonium salt, more preferably a fluorine-containing quaternary ammonium salt. In the quaternary ammonium salt, the halogen atom may be contained in the cation or the anion, but is preferably contained in the anion.

[0137] In a preferred embodiment, the fluorine-containing quaternary ammonium salt is tetra(hydrocarbon)ammonium fluoride. Specific examples of the hydrocarbon group in tetra(hydrocarbon)ammonium fluoride include an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and the like. In a more preferred embodiment, tetra(hydrocarbon)ammonium fluoride contains tetraalkylammonium fluoride. Specific examples of tetraalkylammonium fluoride include tetraethylammonium fluoride, tetrapropylammonium fluoride, tetrabutylammonium fluoride (also referred to as tetrabutylammonium fluoride), etc., but are not limited thereto. Among them, tetrabutylammonium fluoride is preferred.

[0138] Quaternary ammonium salts such as tetra(hydrocarbon)ammonium fluoride may use hydrates. Also, quaternary ammonium salts such as tetra(hydrocarbon)ammonium fluoride may be used alone or in combination of two or more. The amount of the quaternary ammonium salt is not particularly limited as long as it dissolves in the solvent contained in the detergent composition, but is usually 0.1 to 30% by mass based on the detergent composition.

[0139] The solvent contained in the cleaning composition used in the present invention is not particularly limited as long as it is used for this kind of application and can dissolve salts such as the above-mentioned quaternary ammonium salts. However, from the viewpoint of reproducibly obtaining a cleaning composition having excellent detergency, and from the viewpoint of dissolving salts such as quaternary ammonium salts well to obtain a cleaning composition with excellent uniformity, preferably, the cleaning composition used in the present invention contains one or more amide solvents.

[0140] A preferred example of the amide solvent includes an acid amide derivative represented by formula (Z).

Chemical formula

[0141] In the formula, R 0 represents an ethyl group, a propyl group or an isopropyl group, and an ethyl group or an isopropyl group is preferred, and an ethyl group is more preferred. R A and R B each independently represents an alkyl group having 1 to 4 carbon atoms. The alkyl group having 1 to 4 carbon atoms may be linear, branched or cyclic, and specifically includes a methyl group, an ethyl group, a propyl group, an isopropyl group, a cyclopropyl group, an n-butyl group, an isobutyl group, an s-butyl group, a t-butyl group, a cyclobutyl group, etc. Among these, as R A and R B , a methyl group or an ethyl group is preferred.

[0142] Examples of the acid amide derivative represented by formula (Z) include N,N-dimethylpropionamide, N,N-diethylpropionamide, N-ethyl-N-methylpropionamide, N,N-dimethylbutyramide, N,N-diethylbutyramide, N-ethyl-N-methylbutyramide, N,N-dimethylisobutyramide, N,N-diethylisobutyramide, N-ethyl-N-methylisobutyramide, etc. Among these, N,N-dimethylpropionamide is particularly preferred.

[0143] The acid amide derivative represented by formula (Z) may be synthesized by a substitution reaction between the corresponding carboxylic acid ester and an amine, or a commercially available product may be used.

[0144] Another example of a preferred amide-based solvent includes a lactam compound represented by formula (Y).

Chemical formula

[0145] In the above formula (Y), specific examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, etc., and specific examples of the alkylene group having 1 to 6 carbon atoms include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, etc., but are not limited thereto.

[0146] Specific examples of the lactam compound represented by the above formula (Y) include an α-lactam compound, a β-lactam compound, a γ-lactam compound, a δ-lactam compound, etc., and these can be used alone or in combination of two or more.

[0147] In a preferred embodiment of the present invention, the lactam compound represented by the above formula (Y) includes 1-alkyl-2-pyrrolidone (N-alkyl-γ-butyrolactam), and in a more preferred embodiment, it includes N-methylpyrrolidone (NMP) or N-ethylpyrrolidone (NEP), and in an even more preferred embodiment, it includes N-methylpyrrolidone (NMP).

[0148] The detergent composition used in the present invention may contain one or more other organic solvents different from the above-mentioned amide compounds. Such other organic solvents are those used for this type of application, and are not particularly limited as long as they are organic solvents compatible with the above-mentioned amide compounds. Preferred other solvents include, but are not limited to, alkylene glycol dialkyl ethers, aromatic hydrocarbon compounds, cyclic structure-containing ether compounds, etc. The amount of other organic solvents different from the above amide compounds is usually determined as appropriate up to 95% by mass or less in the solvent contained in the cleaning composition, as long as the quaternary ammonium salt contained in the cleaning composition does not precipitate or separate and is uniformly mixed with the above amide compounds. The cleaning composition used in the present invention may contain water as a solvent, but usually only an organic solvent is intentionally used as the solvent from the viewpoint of avoiding corrosion of the substrate, etc. In this case, it is not to deny that even the water of hydration of the salt and the water contained in trace amounts in the organic solvent may be contained in the cleaning composition. The water content of the cleaning composition used in the present invention is usually 5% by mass or less.

[0149] The property that the release layer obtained from the release agent composition of the present invention is preferably removed by the cleaning composition can be similarly evaluated by the film reduction rate (%) according to the above method. The release layer obtained from the release agent composition of the present invention usually has a film reduction rate of 94% or more after being immersed in the cleaning composition according to the above method, but in a preferred embodiment it is 95% or more, in a more preferred embodiment it is 96% or more, in an even more preferred embodiment it is 97% or more, in a further preferred embodiment it is 98% or more, in an even further preferred embodiment it is 99% or more, and in the most preferred embodiment it is 100%, showing a high film reduction rate.

[0150] The adhesive layer provided in the laminate of the present invention can be, for example, a film obtained from an adhesive composition containing an adhesive component (S). Such an adhesive component (S) is not particularly limited as long as it is used for this kind of application, and examples include, but are not limited to, polysiloxane-based adhesives, acrylic resin-based adhesives, epoxy resin-based adhesives, polyamide-based adhesives, polystyrene-based adhesives, polyimide adhesives, phenol resin-based adhesives, etc. Among these, during the processing of wafers and the like, it exhibits suitable adhesion, can be suitably peeled off after processing, has excellent heat resistance, and can be suitably removed by the above-described cleaning composition. Therefore, as the adhesive component (S), a polysiloxane-based adhesive is preferable.

[0151] In a preferred embodiment, the adhesive composition used in the present invention contains, as an adhesive component, a polyorganosiloxane component (A) that cures by a hydrosilylation reaction. In a more preferred example, the polyorganosiloxane component (A) that cures by a hydrosilylation reaction is a siloxane unit (Q unit) represented by SiO2, R 1 R 2 R 3 SiO 1 / 2 a siloxane unit (M unit) represented by, R 4 R 5 SiO 2 / 2 a siloxane unit (D unit) represented by, and R 6 SiO 3 / 2 a siloxane unit (T unit) represented by. It contains one or more units selected from the group consisting of a polysiloxane (A1) and a platinum group metal-based catalyst (A2). The above polysiloxane (A1) is a siloxane unit (Q' unit) represented by SiO2, R 1 ’R 2 ’R 3 ’SiO 1 / 2 a siloxane unit (M' unit) represented by, R 4 ’R 5 ’SiO 2 / 2 a siloxane unit (D' unit) represented by, and R 6 ’SiO 3 / 2 a siloxane unit (T' unit) represented by. It contains one or more units selected from the group consisting of, and at least one selected from the group consisting of the above M' unit, D' unit, and T' unit. A polyorganosiloxane (a1) and a siloxane unit (Q” unit) represented by SiO2, R 1 ”R 2 ”R 3 ”SiO 1 / 2 a siloxane unit (M” unit) represented by, R 4 ”R 5 ”SiO 2 / 2The siloxane unit (D” unit) represented by and R 6 ”SiO 3 / 2 It contains one or more units selected from the group consisting of siloxane units (T” units) represented by , and also contains a polyorganosiloxane (a2) containing at least one selected from the group consisting of the above M” units, D” units and T” units.

[0152] R 1 ~R 6 are groups or atoms bonded to silicon atoms, and each independently represents an alkyl group, an alkenyl group or a hydrogen atom.

[0153] R 1 ’~R 6 ’ are groups bonded to silicon atoms, and each independently represents an alkyl group or an alkenyl group, provided that at least one of R 1 ’~R 6 ’ is an alkenyl group.

[0154] R 1 ”~R 6 ” are groups or atoms bonded to silicon atoms, and each independently represents an alkyl group or a hydrogen atom, provided that at least one of R 1 ”~R 6 ” is a hydrogen atom.

[0155] The alkyl group may be linear, branched or cyclic, but a linear or branched alkyl group is preferred. Its carbon number is not particularly limited, but is usually 1 to 40, preferably 30 or less, more preferably 20 or less, and even more preferably 10 or less.

[0156] Specific examples of the linear or branched alkyl group include the same as the specific examples of the linear or branched alkyl group which may be substituted as described above for R 901 and R 902 . Among them, a methyl group is preferred.

[0157] Specific examples of the cyclic alkyl group include R 901 and R902 The same specific examples of the cyclic alkyl group which may be substituted as described above can be mentioned.

[0158] The alkenyl group may be linear or branched, and its carbon number is not particularly limited, but is usually 2 to 40, preferably 30 or less, more preferably 20 or less, and even more preferably 10 or less.

[0159] Specific examples of the alkenyl group include R 901 and R 902 The same specific examples of the alkenyl group which may be substituted as described above can be mentioned. Among them, an ethenyl group and a 2-propenyl group are preferable.

[0160] As described above, the polysiloxane (A1) contains the polyorganosiloxane (a1) and the polyorganosiloxane (a2), and the alkenyl group contained in the polyorganosiloxane (a1) and the hydrogen atom (Si-H group) contained in the polyorganosiloxane (a2) form a crosslinked structure and cure by a hydrosilylation reaction with the platinum group metal-based catalyst (A2). As a result, a cured film is formed.

[0161] The polyorganosiloxane (a1) contains one or more units selected from the group consisting of Q' units, M' units, D' units, and T' units, and contains at least one selected from the group consisting of the above M' units, D' units, and T' units. As the polyorganosiloxane (a1), two or more polyorganosiloxanes satisfying such conditions may be used in combination.

[0162] Preferable combinations of two or more selected from the group consisting of Q' units, M' units, D' units, and T' units include (Q' unit and M' unit), (D' unit and M' unit), (T' unit and M' unit), (Q' unit, T' unit, and M' unit), but are not limited thereto.

[0163] When two or more polyorganosiloxanes are included in the polyorganosiloxane (a1), the combinations of (Q' unit and M' unit) and (D' unit and M' unit), the combination of (T' unit and M' unit) and (D' unit and M' unit), and the combination of (Q' unit, T' unit and M' unit) and (T' unit and M' unit) are preferred, but not limited thereto.

[0164] The polyorganosiloxane (a2) contains one or more units selected from the group consisting of Q'' unit, M'' unit, D'' unit and T'' unit, and contains at least one selected from the group consisting of the above M'' unit, D'' unit and T'' unit. As the polyorganosiloxane (a2), two or more polyorganosiloxanes satisfying such conditions may be used in combination.

[0165] Preferred combinations of two or more selected from the group consisting of Q'' unit, M'' unit, D'' unit and T'' unit include (M'' unit and D'' unit), (Q'' unit and M'' unit), and (Q'' unit, T'' unit and M'' unit), but are not limited thereto.

[0166] The polyorganosiloxane (a1) is composed of siloxane units in which an alkyl group and / or an alkenyl group is bonded to the silicon atom. However, R 1 ’~R 6 ’ The proportion of the alkenyl group in all substituents represented by is preferably 0.1 mol% to 50.0 mol%, more preferably 0.5 mol% to 30.0 mol%, and the remaining R 1 ’~R 6 ’ can be an alkyl group.

[0167] The polyorganosiloxane (a2) is composed of siloxane units in which an alkyl group and / or a hydrogen atom is bonded to the silicon atom. However, R 1 ”~R 6 ” The proportion of the hydrogen atom in all substituents and substituted atoms represented by is preferably 0.1 mol% to 50.0 mol%, more preferably 10.0 mol% to 40.0 mol%, and the remaining R1 ”~R 6 ” can be an alkyl group.

[0168] The polysiloxane (A1) contains a polyorganosiloxane (a1) and a polyorganosiloxane (a2). In a preferred embodiment of the present invention, the molar ratio of the alkenyl group contained in the polyorganosiloxane (a1) to the hydrogen atom constituting the Si-H bond contained in the polyorganosiloxane (a2) is in the range of 1.0:0.5 to 1.0:0.66.

[0169] The weight average molecular weights of polysiloxanes such as the polyorganosiloxane (a1) and the polyorganosiloxane (a2) are usually 500 to 1,000,000 respectively. From the viewpoint of reproducibly realizing the effects of the present invention, they are preferably 5,000 to 50,000. In the present invention, the weight average molecular weight, number average molecular weight and dispersity of the polyorganosiloxane can be measured, for example, using a GPC device (EcoSEC, HLC-8320GPC manufactured by Tosoh Corporation) and GPC columns (TSKgel SuperMultipore HZ-N, TSKgel SuperMultipore HZ-H manufactured by Tosoh Corporation), setting the column temperature at 40 °C, using tetrahydrofuran as the eluent (elution solvent), setting the flow rate at 0.35 mL / min, and using polystyrene (manufactured by Sigma-Aldrich) as the standard sample.

[0170] The viscosities of the polyorganosiloxane (a1) and the polyorganosiloxane (a2) are usually 10 to 1,000,000 (mPa·s) respectively. From the viewpoint of reproducibly realizing the effects of the present invention, they are preferably 50 to 10,000 (mPa·s). The viscosities of the polyorganosiloxane (a1) and the polyorganosiloxane (a2) are the values measured with an E-type rotational viscometer at 25 °C.

[0171] The polyorganosiloxane (a1) and the polyorganosiloxane (a2) react with each other to form a film by a hydrosilylation reaction. Therefore, the curing mechanism is different from that via, for example, a silanol group. Thus, neither siloxane needs to contain a silanol group or a functional group that forms a silanol group by hydrolysis such as an alkyloxy group.

[0172] In a preferred embodiment of the present invention, the adhesive component (S) contains a platinum group metal-based catalyst (A2) together with the above-described polysiloxane (A1). Such a platinum-based metal catalyst is a catalyst for promoting the hydrosilylation reaction between the alkenyl group of the polyorganosiloxane (a1) and the Si-H group of the polyorganosiloxane (a2).

[0173] Specific examples of the platinum-based metal catalyst include, but are not limited to, platinum black, platinum dichloride, chloroplatinic acid, a reaction product of chloroplatinic acid and a monohydric alcohol, a complex of chloroplatinic acid and olefins, and platinum-based catalysts such as platinum bis(acetoacetate). Examples of the complex of platinum and olefins include, but are not limited to, a complex of divinyltetramethyldisiloxane and platinum. The amount of the platinum group metal-based catalyst (A2) is usually in the range of 1.0 to 50.0 ppm with respect to the total amount of the polyorganosiloxane (a1) and the polyorganosiloxane (a2).

[0174] The polyorganosiloxane component (A) may contain a polymerization inhibitor (A3) for the purpose of suppressing the progress of the hydrosilylation reaction. The polymerization inhibitor is not particularly limited as long as it can suppress the progress of the hydrosilylation reaction. Specific examples thereof include alkynyl alcohols such as 1-ethynyl-1-cyclohexanol and 1,1-diphenyl-2-propion-1-ol. The amount of the coincidence inhibitor is usually 1000.0 ppm or more and 10000.0 ppm or less from the viewpoint of preventing excessive inhibition of the hydrosilylation reaction, based on the total amount of the polyorganosiloxane (a1) and the polyorganosiloxane (a2) from the viewpoint of obtaining the effect.

[0175] The adhesive composition used in the present invention may contain a release agent component (B). By including such a release agent component (B) in the adhesive composition, the obtained adhesive layer can be suitably peeled off with good reproducibility. Typical examples of such a release agent component (B) include polyorganosiloxanes, and specific examples thereof include, but are not limited to, epoxy group-containing polyorganosiloxanes, methyl group-containing polyorganosiloxanes, phenyl group-containing polyorganosiloxanes, and the like.

[0176] Preferred examples of the polyorganosiloxane as the release agent component (B) include, but are not limited to, epoxy group-containing polyorganosiloxanes, methyl group-containing polyorganosiloxanes, phenyl group-containing polyorganosiloxanes, and the like.

[0177] The weight average molecular weight of the polyorganosiloxane as the release agent component (B) is usually from 100,000 to 2,000,000, but from the viewpoint of realizing the effects of the present invention with good reproducibility, it is preferably from 200,000 to 1,200,000, more preferably from 300,000 to 900,000, and its dispersity is usually from 1.0 to 10.0, but from the viewpoints such as realizing suitable peeling with good reproducibility, it is preferably from 1.5 to 5.0, more preferably from 2.0 to 3.0. The weight average molecular weight and the dispersity can be measured by the above-mentioned methods for polysiloxanes. The viscosity of the polyorganosiloxane as the release agent component (B) is usually from 1,000 to 2,000,000 mm 2 / s. The value of the viscosity of the polyorganosiloxane as the release agent component (B) is indicated by kinematic viscosity, and centistokes (cSt) = mm 2 / s. Viscosity (mPa·s) divided by density (g / cm 3) It can also be obtained by dividing. That is, the value can be obtained from the viscosity and density measured with an E-type rotational viscometer measured at 25°C, and the kinematic viscosity (mm 2 / s) = viscosity (mPa·s) / density (g / cm 3 ), and can be calculated from the formula.

[0178] Examples of the epoxy group-containing polyorganosiloxane include, for example, R 11 R 12 SiO 2 / 2 Those containing siloxane units (D 10 units) represented by are mentioned.

[0179] R 11 is a group bonded to a silicon atom, represents an alkyl group, and R 12 is a group bonded to a silicon atom, represents an epoxy group or an organic group containing an epoxy group, and specific examples of the alkyl group can include the above examples. The epoxy group in the organic group containing an epoxy group may be an independent epoxy group without condensing with other rings, or may be an epoxy group forming a condensed ring with other rings, such as a 1,2-epoxycyclohexyl group. Specific examples of the organic group containing an epoxy group include, but are not limited to, 3-glycidoxypropyl and 2-(3,4-epoxycyclohexyl)ethyl. In the present invention, as a preferred example of the epoxy group-containing polyorganosiloxane, epoxy group-containing polydimethylsiloxane can be mentioned, but it is not limited thereto.

[0180] The epoxy group-containing polyorganosiloxane contains the above-mentioned siloxane units (D 10 units), but in addition to the D 10 units, it may also contain the above Q units, M units and / or T units. In a preferred embodiment of the present invention, specific examples of the epoxy group-containing polyorganosiloxane include polyorganosiloxane composed only of D 10 units, D 10Polyorganosiloxanes containing D units and Q units 10 Polyorganosiloxanes containing D units and M units 10 Polyorganosiloxanes containing D units and T units 10 Polyorganosiloxanes containing D units, Q units and M units 10 Polyorganosiloxanes containing D units, M units and T units 10 Examples thereof include polyorganosiloxanes containing D units, Q units, M units and T units, etc.

[0181] The epoxy group-containing polyorganosiloxane is preferably an epoxy group-containing polydimethylsiloxane having an epoxy value of 0.1 to 5, and its weight average molecular weight is usually 1,500 to 500,000, but from the viewpoint of suppressing precipitation in the adhesive, it is preferably 100,000 or less.

[0182] Specific examples of the epoxy group-containing polyorganosiloxane include, but are not limited to, those represented by formulas (E1) to (E3).

[0183]

Chemical formula

[0184]

Chemical formula

[0185]

Chemical formula

[0186] Examples of the methyl group-containing polyorganosiloxane include, for example, R 210 R 220SiO 2 / 2 The siloxane unit (D 200 unit) represented by, preferably R 21 R 21 SiO 2 / 2 The siloxane unit (D 20 unit) represented by is included.

[0187] R 210 and R 220 are groups bonded to the silicon atom and each independently represents an alkyl group, at least one of which is a methyl group. Specific examples of the alkyl group can include the above-mentioned examples. R 21 is a group bonded to the silicon atom and represents an alkyl group. Specific examples of the alkyl group can include the above-mentioned examples. Among them, R 21 is preferably a methyl group. In the present invention, as a preferred example of the methyl group-containing polyorganosiloxane, polydimethylsiloxane can be mentioned, but it is not limited thereto.

[0188] The methyl group-containing polyorganosiloxane contains the above-mentioned siloxane unit (D 200 unit or D 20 unit), but in addition to the D 200 unit and D 20 unit, it may also contain the above Q unit, M unit and / or T unit.

[0189] In a certain aspect of the present invention, specific examples of the methyl group-containing polyorganosiloxane include polyorganosiloxane consisting only of D 200 units, polyorganosiloxane containing D 200 units and Q units, polyorganosiloxane containing D 200 units and M units, polyorganosiloxane containing D 200 units and T units, polyorganosiloxane containing D 200 units, Q units and M units, polyorganosiloxane containing D 200 units, M units and T units, polyorganosiloxane containing D 200Examples include polyorganosiloxanes containing unit, Q unit, M unit, and T unit.

[0190] In a preferred embodiment of the present invention, specific examples of methyl group-containing polyorganosiloxanes include polyorganosiloxanes consisting of only D 20 units, polyorganosiloxanes containing D 20 units and Q units, polyorganosiloxanes containing D 20 units and M units, polyorganosiloxanes containing D 20 units and T units, polyorganosiloxanes containing D 20 units, Q units and M units, polyorganosiloxanes containing D 20 units, M units and T units, polyorganosiloxanes containing D 20 units, Q units, M units and T units.

[0191] Specific examples of methyl group-containing polyorganosiloxanes include, but are not limited to, those represented by formula (M1).

[0192]

Chemical formula

[0193] Examples of phenyl group-containing polyorganosiloxanes include, for example, R 31 R 32 SiO 2 / 2 represented siloxane units (D 30 units).

[0194] R 31 is a group bonded to a silicon atom and represents a phenyl group or an alkyl group, and R 32 is a group bonded to a silicon atom and represents a phenyl group. Specific examples of the alkyl group can include the above examples, but a methyl group is preferred.

[0195] Phenyl group-containing polyorganosiloxanes are the above-mentioned siloxane units (D30 although it includes the D unit 30 In addition to the D unit, it may also include the above Q unit, M unit and / or T unit.

[0196] In a preferred embodiment of the present invention, specific examples of the phenyl group-containing polyorganosiloxane include D 30 a polyorganosiloxane consisting only of the D unit, D 30 a polyorganosiloxane containing the D unit and the Q unit, D 30 a polyorganosiloxane containing the D unit and the M unit, D 30 a polyorganosiloxane containing the D unit and the T unit, D 30 a polyorganosiloxane containing the D unit, the Q unit and the M unit, D 30 a polyorganosiloxane containing the D unit, the M unit and the T unit, D 30 a polyorganosiloxane containing the D unit, the Q unit, the M unit and the T unit can be mentioned.

[0197] Specific examples of the methyl group-containing polyorganosiloxane include, but are not limited to, those represented by formula (P1) or (P2).

[0198]

Chemical formula

[0199]

Chemical formula

[0200] In a preferred embodiment, the adhesive composition used in the present invention includes a polyorganosiloxane component (A) that cures by a hydrosilylation reaction and, in a preferred embodiment, includes a release agent component (B). As the release agent component (B), a polyorganosiloxane is included.

[0201] The adhesive composition used in the present invention can contain an adhesive component (S) and a release agent component (B) in any ratio. However, considering the balance between adhesiveness and releasability, the ratio of component (S) to component (B) is preferably 99.995:0.005 to 30:70, more preferably 99.9:0.1 to 75:25, by mass ratio. That is, when a polyorganosiloxane component (A) that cures by a hydrosilylation reaction is included, the ratio of component (A) to component (B) is preferably 99.995:0.005 to 30:70, more preferably 99.9:0.1 to 75:25, by mass ratio.

[0202] The adhesive composition used in the present invention may contain a solvent for the purpose of adjusting viscosity and the like. Specific examples thereof include, but are not limited to, aliphatic hydrocarbons, aromatic hydrocarbons, ketones, and the like.

[0203] More specifically, hexane, heptane, octane, nonane, decane, undecane, dodecane, isododecane, menthane, limonene, toluene, xylene, mesitylene, cumene, MIBK (methyl isobutyl ketone), butyl acetate, diisobutyl ketone, 2-octanone, 2-nonanone, 5-nonanone, etc. can be mentioned, but are not limited thereto. Such solvents can be used alone or in combination of two or more.

[0204] When the adhesive composition used in the present invention contains a solvent, its content is appropriately set in consideration of various factors such as the viscosity of the desired composition, the coating method employed, and the thickness of the film to be produced. However, it is in the range of about 10 to 90% by mass with respect to the whole composition.

[0205] The viscosity of the adhesive composition used in the present invention is usually 500 to 20,000 mPa·s, preferably 1,000 to 5,000 mPa·s at 25°C. The viscosity of the adhesive composition used in the present invention can be adjusted by changing the type of solvent used, their ratios, the concentration of film constituent components, etc., in consideration of various factors such as the coating method used and the desired film thickness.

[0206] The adhesive composition used in the present invention can be produced by mixing an adhesive component (S), and, when used, a release agent component (B) and a solvent. The mixing order is not particularly limited. As an example of a method that can easily and reproducibly produce the adhesive composition, for example, there are a method of dissolving the adhesive component (S) and the release agent component (B) in a solvent, a method of dissolving a part of the adhesive component (S) and the release agent component (B) in a solvent and dissolving the remainder in the solvent, and then mixing the obtained solutions, but it is not limited thereto. When preparing the adhesive composition, heating may be appropriately performed within a range where the components do not decompose or deteriorate. In the present invention, for the purpose of removing foreign matters, the solvent, solution, etc. used may be filtered using a filter on the submicrometer order or the like during the production of the adhesive composition or after all the components are mixed.

[0207] The thickness of the adhesive layer provided in the laminate of the present invention is usually 5 to 500 μm. From the viewpoint of maintaining film strength, it is preferably 10 μm or more, more preferably 20 μm or more, still more preferably 30 μm or more. From the viewpoint of avoiding non-uniformity caused by a thick film, it is preferably 200 μm or less, more preferably 150 μm or less, still more preferably 120 μm or less, and even more preferably 70 μm or less.

[0208] The laminate of the present invention can be produced, for example, by a method including: a first step of applying an adhesive composition to the surface of a semiconductor substrate and, if necessary, heating it to form an adhesive coating layer; a second step of applying a release agent composition to the surface of a support substrate and, if necessary, heating it to form a release agent coating layer; and a third step of bringing the adhesive coating layer of the semiconductor substrate and the release agent coating layer of the support substrate into close contact with each other by applying a load in the thickness direction of the semiconductor substrate and the support substrate while performing at least one of heat treatment and reduced pressure treatment, and then performing post-heat treatment to obtain a laminate.

[0209] Further, the laminate of the present invention can be manufactured by a method including: a first step of applying a release agent composition onto the surface of a semiconductor substrate and heating it if necessary to form a release agent coating layer; a second step of applying an adhesive composition onto the surface of a support substrate and heating it if necessary to form an adhesive coating layer; and a third step of bringing the release agent coating layer of the semiconductor substrate into close contact with the adhesive coating layer of the support substrate while applying a load in the thickness direction of the semiconductor substrate and the support substrate while performing at least one of heat treatment and reduced pressure treatment, and then performing post-heat treatment to obtain a laminate. Note that, as long as the effects of the present invention are not impaired, the application and heating of each composition may be sequentially performed on either one of the substrates.

[0210] The coating method is not particularly limited, but is usually the spin coating method. Note that a method of separately forming a coating film by the spin coating method or the like and attaching the sheet-like coating film as an adhesive coating layer or a release agent coating layer may be employed.

[0211] The heating temperature of the applied adhesive composition varies depending on the type and amount of the adhesive component contained in the adhesive composition, whether a solvent is contained, the boiling point of the solvent used, the desired thickness of the adhesive layer, etc., and thus cannot be generally specified. However, it is usually 80°C to 150°C, and the heating time is usually 30 seconds to 5 minutes. When the adhesive composition contains a solvent, the applied adhesive composition is usually heated.

[0212] The heating temperature of the applied release agent composition varies depending on the type and amount of the acid generator, the boiling point of the solvent used, the desired thickness of the release layer, etc., and thus cannot be generally specified. However, from the viewpoint of reproducibly realizing a suitable release layer, it is 80°C or higher, and from the viewpoint of suppressing the decomposition of the acid generator, it is 300°C or lower. The heating time is appropriately determined usually in the range of 10 seconds to 10 minutes according to the heating temperature. When the release agent composition contains a solvent, the applied release agent composition is usually heated.

[0213] Heating can be performed using a hot plate, an oven, or the like.

[0214] The film thickness of the adhesive coating layer obtained by applying the adhesive composition and heating it is usually about 5 to 500 μm, and finally it is appropriately determined so as to be within the range of the thickness of the above-described adhesive layer.

[0215] The film thickness of the release agent coating layer obtained by applying the release agent composition and heating it is usually about 10 nm to 10 μm, and finally it is appropriately determined so as to be within the range of the thickness of the above-described release layer.

[0216] In the present invention, such coating layers are aligned so as to be in contact with each other, and while performing heat treatment, reduced pressure treatment, or both, a load in the thickness direction of the semiconductor substrate and the support substrate is applied to adhere the two layers, and then a post-heat treatment is performed, whereby the laminate of the present invention can be obtained. The choice of whether to adopt heat treatment, reduced pressure treatment, or a combination of both is appropriately determined in consideration of various factors such as the type of the adhesive composition, the specific composition of the release agent composition, the compatibility of the films obtained from both compositions, the film thickness, and the required adhesive strength.

[0217] The heat treatment is usually appropriately determined from the range of 20 to 150 °C from the viewpoints of softening the adhesive coating layer to achieve favorable bonding with the release agent coating layer and favorably curing an organic resin or the like of a type that is not sufficiently cured by the heating during the formation of the release agent coating layer. In particular, from the viewpoint of suppressing or avoiding excessive curing or unnecessary alteration of the adhesive component (S), it is preferably 130 °C or lower, more preferably 90 °C or lower, and the heating time is usually 30 seconds or more, preferably 1 minute or more, from the viewpoint of surely expressing favorable adhesion, but is usually 10 minutes or less, preferably 5 minutes or less, from the viewpoint of suppressing alteration of the adhesive layer and other members.

[0218] For the reduced pressure treatment, the adhesive coating layer and the release agent coating layer in contact with each other may be exposed to an atmospheric pressure of 10 Pa to 10,000 Pa. The time for the reduced pressure treatment is usually 1 to 30 minutes.

[0219] From the viewpoint of reproducibly obtaining a laminate in which the substrate can be easily separated, the adhesive coating layer and the release agent coating layer that are in contact with each other are preferably bonded by a reduced-pressure treatment, more preferably by a combined use of a heat treatment and a reduced-pressure treatment.

[0220] The load in the thickness direction of the semiconductor substrate and the support substrate is not particularly limited as long as it does not adversely affect the semiconductor substrate, the support substrate, and the two layers therebetween, and can firmly adhere them, but is usually in the range of 10 to 1000 N.

[0221] From the viewpoint of realizing a sufficient curing rate and the like, the post-heating temperature is preferably 120°C or higher, and from the viewpoint of preventing deterioration of the substrate and each layer and the like, it is preferably 260°C or lower. From the viewpoint of realizing suitable bonding of the substrate and the layers constituting the laminate, the post-heating time is usually 1 minute or longer, preferably 5 minutes or longer, and from the viewpoint of suppressing or avoiding adverse effects on each layer due to excessive heating and the like, it is usually 180 minutes or shorter, preferably 120 minutes or shorter. Heating can be performed using a hot plate, an oven, or the like. When performing post-heating using a hot plate, either the semiconductor substrate or the support substrate of the laminate may be placed below for heating, but from the viewpoint of reproducibly realizing suitable peeling, it is preferable to perform post-heating with the semiconductor substrate placed below. Note that one of the purposes of the post-heating treatment is to realize a more suitable self-supporting film, that is, an adhesive layer and a release layer, and particularly to preferably realize curing by a hydrosilylation reaction.

[0222] The method for manufacturing a processed semiconductor substrate of the present invention includes a first step of processing the semiconductor substrate of the laminate of the present invention, a second step of separating the semiconductor substrate and the support substrate, and a third step of washing the separated semiconductor substrate with a cleaning agent composition.

[0223] The processing performed on the semiconductor substrate in the first step is, for example, processing on the side opposite to the polished surface of the wafer, and examples thereof include thinning of the wafer by polishing the back surface of the wafer. Thereafter, formation of through-silicon vias (TSVs) or the like is performed, and then the thinned wafer is peeled off from the support substrate to form a laminate of wafers, which is three-dimensionally mounted. Before and after that, formation of an electrode on the back surface of the wafer or the like is also performed. In the thinning of the wafer and the TSV process, heat of about 250 to 350 °C is applied while being adhered to the support substrate. The laminate of the present invention includes an adhesive layer and a release layer and has heat resistance against such an applied load. Note that the processing is not limited to the above-described examples, and includes, for example, implementation of a semiconductor component mounting process when temporarily adhering to a support substrate to support a base material for mounting the semiconductor component.

[0224] In the second step, methods for separating (peeling) the semiconductor substrate and the support substrate include, but are not limited to, laser peeling, mechanical peeling using a device having a sharp portion, peeling by pulling between the support and the wafer. When the support substrate has light transmissivity, by irradiating light from the support substrate side to the release layer, separation or decomposition of the release layer occurs as described above, and then, for example, by pulling up either one of the substrates, the semiconductor substrate and the support substrate can be easily separated.

[0225] Irradiation of light on the release layer does not necessarily need to be performed on the entire area of the release layer. Even if there are areas irradiated with light and areas not irradiated with light mixed together, as long as the releasability of the entire release layer is sufficiently improved, for example, the semiconductor substrate and the support substrate can be separated by a slight external force such as pulling up the support substrate. The ratio and positional relationship between the area irradiated with light and the area not irradiated with light vary depending on the type of adhesive used, its specific composition, the thickness of the adhesive layer, the thickness of the release layer, the intensity of the light irradiated, etc. However, those skilled in the art can appropriately set the conditions without requiring excessive testing. For such reasons, according to the method for manufacturing a processed semiconductor substrate of the present invention, when the support substrate of the laminate used has light transmissivity, it is possible to shorten the light irradiation time when peeling by light irradiation. As a result, not only can an improvement in throughput be expected, but physical stress for peeling, etc. can be avoided, and the semiconductor substrate and the support substrate can be easily and efficiently separated only by light irradiation. Generally, the irradiation amount of light for peeling is 50 to 3,000 mJ / cm 2 is. The irradiation time is appropriately determined according to the wavelength and irradiation amount. The irradiation of light may be performed using laser light or may be performed using non-laser light from a light source such as an ultraviolet lamp.

[0226] In the third step, after cleaning by spraying a cleaning agent composition on the surface of the separated semiconductor substrate or immersing the separated semiconductor substrate in the cleaning agent composition, usually, rinsing and drying using a solvent are performed. Examples of the cleaning agent composition include those described above.

[0227] In the method for manufacturing a processed semiconductor substrate of the present invention, the processed semiconductor substrate manufactured through the third step is well cleaned by the cleaning agent composition. However, it is not prevented that the surface of the processed semiconductor substrate is further cleaned using a removal tape or the like. If necessary, the surface may be further cleaned using a removal tape or the like.

[0228] Regarding the components and method elements related to the above-described steps of the method for manufacturing a processed semiconductor substrate of the present invention, various modifications may be made without departing from the gist of the present invention. The method for manufacturing a processed semiconductor substrate of the present invention may include steps other than the above-described steps.

[0229] The peeling method of the present invention separates the semiconductor substrate and the support substrate of the laminate by irradiating light from the support substrate side to the peeling layer when the support substrate of the laminate of the present invention has light transmissivity. In the laminate of the present invention, since the semiconductor substrate and the support substrate are preferably temporarily adhered so as to be peelable by the adhesive layer and the peeling layer, when the support substrate has light transmissivity, the semiconductor substrate and the support substrate can be easily separated by irradiating light from the support substrate side of the laminate to the peeling layer. Usually, peeling is performed after processing the semiconductor substrate of the laminate.

Example

[0230] [Equipment] (1) Stirrer: Autorevolution Revolution Mixer ARE-500 manufactured by Shinky Co., Ltd. (2) Rheometer: Viscoelasticity measuring device MCR302 manufactured by Anton Paar Japan Co., Ltd. (3) Vacuum laminating device: Manual Bonder manufactured by Zeus Microtech Co., Ltd. (4) High-rigidity grinding machine: HRG300 manufactured by Tokyo Seimitsu Co., Ltd. (5) Measuring device for 5% weight loss temperature: 2010SR manufactured by NETZSCH (heating from room temperature to 400 °C at 10 °C / min under air) (6) Optical film thickness meter (film thickness measurement): F-50 manufactured by Filmmetrics Co., Ltd. (7) Laser irradiation device (Lambda SX manufactured by Coherent Co., Ltd.)

[0231] [Measurement conditions for molecular weight of polysilane] The weight-average molecular weight of the polysilane was measured using a GPC apparatus (EcoSEC, HLC-8220GPC manufactured by Tosoh Corporation) and GPC columns (Shodex KF-803L, KF-802, and KF-801 manufactured by Showa Denko K.K. in this order), with the column temperature set at 40 °C, tetrahydrofuran used as the eluent (elution solvent), the flow rate (flow velocity) set at 1.00 mL / min, and polystyrene (manufactured by Sigma-Aldrich) used as the standard sample.

[0232] [1] Preparation of the Adhesive Composition [Preparation Example 1] Into a 600 mL container dedicated for a stirrer, 80 g of an MQ resin (manufactured by Wacker Chemie) containing a polysiloxane skeleton and vinyl groups, 2.52 g of an SiH group-containing linear polydimethylsiloxane with a viscosity of 100 mPa·s (manufactured by Wacker Chemie), 5.89 g of an SiH group-containing linear polydimethylsiloxane with a viscosity of 70 mPa·s (manufactured by Wacker Chemie), and 0.22 g of 1-ethynyl-1-cyclohexanol (manufactured by Wacker Chemie) were placed and stirred with a stirrer for 5 minutes. To the obtained mixture, 0.147 g of a platinum catalyst (manufactured by Wacker Chemie) and 5.81 g of a vinyl group-containing linear polydimethylsiloxane with a viscosity of 1,000 mPa·s (manufactured by Wacker Chemie) were stirred with a stirrer for 5 minutes, and 3.96 g of a separately obtained mixture was added and stirred with a stirrer for 5 minutes. Finally, the obtained mixture was filtered through a 300-mesh nylon filter to obtain the adhesive composition.

[0233] [2] Preparation of the Detergent Composition [Preparation Example 2] 5 g of tetrabutylammonium fluoride trihydrate (manufactured by Kanto Chemical Co., Inc.) was mixed with 95 g of N-methyl-2-pyrrolidone and stirred well to obtain the detergent composition.

[0234] [3] Synthesis of the Novolak Resin [Synthesis Example 1] Into a flask, 56.02 g of N-phenyl-1-naphthylamine, 50.00 g of 1-pyrenecarboxaldehyde, 6.67 g of 4-(trifluoromethyl)benzaldehyde and 2.46 g of methanesulfonic acid were placed, and 86.36 g of 1,4-dioxane and 86.36 g of toluene were added thereto, followed by reflux stirring for 18 hours under a nitrogen atmosphere. After allowing the reaction mixture to cool, 96 g of tetrahydrofuran was added for dilution, and the resulting diluted solution was dropped into methanol to obtain a precipitate. The obtained precipitate was collected by filtration, the filtrate was washed with methanol, and dried under reduced pressure at 60 °C to obtain 72.12 g of a novolak resin. (Hereinafter abbreviated as PPNAPCA-F). As a result of measurement by the above method, the weight average molecular weight of the novolak resin as a polymer was 1,100.

[0235] [4] Preparation of Release Agent Composition [Comparative Example 1-1] 3.6 g of the novolak resin obtained in Synthesis Example 1 and 0.72 g of 3,3’,5,5’-tetrakis(methoxymethyl)-[1,1’-biphenyl]-4,4’-diol (hereinafter referred to as TMOM-BP) as a crosslinking agent were dissolved in 95.68 g of propylene glycol monomethyl ether acetate, and the resulting solution was filtered using a polyethylene microfilter with a pore size of 0.2 μm to obtain a release agent composition.

[0236] [Comparative Example 1-2] 3.6 g of the novolak resin obtained in Synthesis Example 1, 0.72 g of TMOM-BP as a crosslinking agent and 0.1 g of pyridinium p-toluenesulfonate were dissolved in 95.58 g of propylene glycol monomethyl ether acetate, and the resulting solution was filtered using a polyethylene microfilter with a pore size of 0.2 μm to obtain a release agent composition.

[0237] [Example 1] 3.6 g of the novolak resin obtained in Synthesis Example 1, 0.72 g of TMOM-BP as a crosslinking agent, and 3.6 g of OGSOL SI-20-10 (manufactured by Osaka Gas Chemical Co., Ltd.), which is a branched polysilane, were dissolved in 92.08 g of propylene glycol monomethyl ether acetate. The resulting solution was filtered using a polyethylene microfilter with a pore size of 0.2 μm to obtain a release agent composition. Note that OGSOL SI-20-10 is a branched polysilane represented by the formula (B-1). As a result of measurement by the above-described method, the weight average molecular weight was 1.7×10 3 and the 5% weight loss temperature was a value exceeding 400°C.

[0238] [Chemical formula] (Ph represents a phenyl group, R E represents a terminal substituent, represents an atom or a group, and n b represents the number of repeating units.)

[0239] [Comparative Examples 1-3] 3.6 g of the novolak resin obtained in Synthesis Example 1, 0.72 g of TMOM-BP as a crosslinking agent, and 3.6 g of OGSOL SI-10-10 (manufactured by Osaka Gas Chemical Co., Ltd.), which is a linear polysilane, were dissolved in 92.08 g of propylene glycol monomethyl ether acetate. The resulting solution was filtered using a polyethylene microfilter with a pore size of 0.2 μm to obtain a release agent composition. Note that OGSOL SI-10-10 is a linear polysilane represented by the formula (S-1). As a result of measurement by the above-described method, the weight average molecular weight was 1.28×10 4 and the 5% weight loss temperature was 370°C.

[0240] [Chemical formula] (Ph represents a phenyl group, R E represents a terminal substituent, represents an atom or a group, and n c1 represents the number of repeating units.)

[0241] [Comparative Examples 1-4] 3.6 g of the novolak resin obtained in Synthesis Example 1, 0.72 g of TMOM-BP as a crosslinking agent, and 3.6 g of Ogsool SI-10-20 (manufactured by Osaka Gas Chemical Co., Ltd.), which is a linear polysilane, were dissolved in 92.08 g of propylene glycol monomethyl ether acetate. The resulting solution was filtered using a polyethylene microfilter with a pore size of 0.2 μm to obtain a release agent composition. Note that OGSOL SI-10-20 is a linear polysilane represented by the formula (S-2). As a result of measurement by the above method, the weight average molecular weight was 2.4×10 3 and the 5% weight loss temperature was 390°C.

[0242] [Chemical formula] (Ph represents a phenyl group, R E represents a terminal substituent, represents an atom or a group, and n c2 represents the number of repeating units.)

[0243] [Comparative Examples 1-5] 3.6 g of the novolak resin obtained in Synthesis Example 1, 0.72 g of TMOM-BP as a crosslinking agent, and 3.6 g of diphenylsilanediol were dissolved in 92.08 g of propylene glycol monomethyl ether acetate. The resulting solution was filtered using a polyethylene microfilter with a pore size of 0.2 μm to obtain a release agent composition.

[0244] [5] Confirmation of removability of the film (film reduction rate) [Example 2] The release agent composition obtained in Example 1 was spin-coated on a silicon wafer cut into a 4 cm square with a final film thickness of 200 nm and heated at 250°C for 15 minutes to form a film on the substrate. The required number of substrates with the film formed was prepared (the same applies hereinafter).

[0245] [Comparative Examples 2-1 to 2-5] A film was formed on the substrate in the same manner as in Example 2, except that the release agent compositions obtained in Comparative Examples 1-1 to 1-5 were used instead of the release agent composition obtained in Example 1.

[0246] The film thicknesses of the films obtained in Example 2 and Comparative Examples 2-1 to 2-5 were measured (film thickness before immersion). Then, each film was immersed in 7 mL of the cleaning agent composition obtained in Preparation Example 2 for 10 minutes, dried with an air gun, and the film thickness of each film was measured again (film thickness after immersion). Also, the same operations were performed except that OK73 thinner (components: 70% propylene glycol monomethyl ether, 30% propylene glycol monomethyl ether acetate) (manufactured by Tokyo Ohka Kogyo Co., Ltd.) and N-methyl-2-pyrrolidone (NMP) were used instead of the cleaning agent composition, and the film thickness was measured. Furthermore, for the film obtained in Example 2, the same operations were performed except that a 5 mass% potassium hydroxide (KOH) aqueous solution, a 10 mass% hydrochloric acid aqueous solution, a 10 mass% p-toluenesulfonic acid aqueous solution, mesitylene, acetone, a 2.38 mass% tetramethylammonium hydroxide aqueous solution (TMAH aqueous solution), and 35 mass% hydrogen peroxide water were used instead of the cleaning agent composition, and the film thickness was measured. The film reduction rate (%) due to immersion was calculated by the formula: film thickness after immersion (nm) / film thickness before immersion (nm) × 100. The results are shown in Table 1. In the table, N / D means that there is no corresponding data.

[0247]

Table 1

[0248] As shown in Table 1, the film obtained in Comparative Example 2-1 had a film reduction rate of 100% when immersed in the cleaning agent composition, OK73 thinner, and NMP. This means that the film obtained in Comparative Example 2-1 dissolved in all of the cleaning agent composition, OK73 thinner, and NMP. On the other hand, the film obtained in Comparative Example 2-2 had a film reduction rate of 0% when immersed in the cleaning agent composition, OK73 thinner, and NMP. This means that the film obtained in Comparative Example 2-2 did not dissolve in any of the cleaning agent composition, OK73 thinner, and NMP. In Comparative Example 2-1 where no acid catalyst was added, the cross-linking reaction did not proceed, whereas in Comparative Example 2-2 where an acid catalyst was added, it is presumed that the cross-linking reaction proceeded. In Example 2 where a branched polysilane was added without adding an acid catalyst, the film reduction rate was 0% when immersed in various solvents, acidic aqueous solutions, basic aqueous solutions, and solutions commonly used in the manufacture of semiconductor elements (TMAH aqueous solution, hydrogen peroxide solution), but a film with a film reduction rate of 100% was obtained when immersed in the cleaning agent composition. That is, the film of Example 2 could not be suitably removed by various solvents, acidic aqueous solutions, basic aqueous solutions, and solutions commonly used in the manufacture of semiconductor elements, but could be suitably removed by the cleaning agent composition. On the other hand, in Comparative Examples 2-3 and 2-4 where a linear polysilane was added instead of the branched polysilane, in Comparative Example 2-4, although a slight improvement in resistance to OK73 thinner was observed, the property of being suitably removable by OK73 thinner or NMP as in the case of using the branched polysilane could not be realized, and it could not be suitably removed by the cleaning agent composition. Also, when diphenylsilanediol was used instead of the branched polysilane, the resistance of the obtained film to the cleaning agent composition and solvents could not be confirmed.

[0249] [6] Confirmation of peelability by manufacturing the laminate and irradiating light and cleanability by the cleaning agent composition [Example 3] The release agent composition obtained in Example 1 was spin-coated onto a 301 mm glass wafer (EAGLE-XG, manufactured by Corning, thickness 700 μm) as the substrate on the carrier side so that the film thickness in the finally obtained laminate would be 200 nm, and a release agent coating layer was formed on the glass wafer which is the support substrate. On the other hand, the adhesive composition obtained in Preparation Example 1 was spin-coated onto a 300 mm silicon wafer (thickness 775 μm) as the substrate on the device side so that the film thickness in the finally obtained laminate would be 60 μm, and an adhesive coating layer was formed on the silicon wafer which is the semiconductor substrate. Then, using a laminating apparatus, the glass wafer and the silicon wafer were laminated with the release agent coating layer and the adhesive coating layer sandwiched therebetween, and then a post-heat treatment was performed at 200 °C for 10 minutes to produce a laminate. The lamination was performed at a temperature of 23 °C and a reduced pressure of 1,500 Pa. The laminates were manufactured in a necessary number. After thinning the silicon wafer of the obtained laminate to 50 μm using a high-rigidity grinding machine, the laminate was placed in an oven and subjected to a high-temperature treatment at 250 °C for 1 hour. Then, the cooled laminate was attached and fixed to a dicing tape (manufactured by Nitto Denko Corporation, DU-300) with the thinned silicon wafer side facing down. Using a laser irradiation apparatus, a laser with a wavelength of 308 nm was irradiated onto the release layer from the glass wafer side of the fixed laminate, and the lowest irradiation amount at which peeling occurred was defined as the optimum irradiation amount. Then, the entire surface of the release layer was irradiated with a laser with a wavelength of 308 nm at the optimum irradiation amount from the glass wafer side of the fixed laminate, and the peelability was confirmed by manually lifting the support substrate. After peeling and removing the fixed semiconductor substrate, the separated semiconductor wafer and glass wafer were each cut into 4 cm × 4 cm, and the cut wafers were immersed in 7 mL of the cleaning agent composition obtained in Preparation Example 2 for 10 minutes, and the presence or absence of residues such as films remaining on the surface of the wafers was visually confirmed (cleanability test). Further, the cleaning agent composition after cleaning the wafers was recovered, and it was visually confirmed whether foreign substances remained in the composition (foreign substance confirmation).

[0250] [Comparative Example 3-1] A laminate was produced in the same manner as in Example 3, except that the release agent composition obtained in Comparative Example 2-2 was used instead of the release agent composition obtained in Example 1. The releasability was confirmed, and the cleaning test and foreign matter confirmation were performed.

[0251]

Table 2

[0252] As shown in Table 2, when the semiconductor substrate and the support substrate of the laminate provided with the film obtained using the release agent composition containing the branched polysilane as the release layer were separated by irradiating the release layer with light (Example 3), each separated substrate could be suitably cleaned without leaving residues on the substrate by cleaning with the cleaning agent composition. Also, no foreign matter was confirmed in each of the cleaning agent compositions used for cleaning each substrate. On the other hand, when the semiconductor substrate and the support substrate of the laminate provided with the film obtained using the release agent composition containing no polysilane but containing an acid catalyst as the release layer were similarly separated (Comparative Example 3-1), after cleaning each separated substrate, no foreign matter was confirmed in the semiconductor substrate formed such that the adhesive layer was in contact with its surface, whereas residues were confirmed in the support substrate formed such that the release layer was in contact with its surface. Also, foreign matter was confirmed in each of the cleaning agent compositions used for cleaning each substrate. From the above, it was confirmed that by using the release agent composition containing the branched polysilane, a film suitable as a release layer showing good removability or solubility even after peeling, particularly after peeling by light irradiation, can be obtained.

Claims

1. A semiconductor substrate, a support substrate, an adhesive layer and a release layer provided between the semiconductor substrate and the support substrate, wherein the release layer is a film obtained from a release agent composition containing an organic resin, a branched polysilane, and a solvent. The laminate is characterized by this.

2. The laminate according to Claim 1, wherein the branched polysilane contains a structural unit represented by the formula (B). 【Chemical 1】 (wherein, R Ｂ represents a hydrogen atom, a hydroxyl group, a silyl group or an organic group.)

3. The above R Ｂ The laminate according to claim 2, wherein R is an aryl group.

4. The above R Ｂ The laminate according to claim 3, wherein R is a phenyl group.

5. The laminate according to any one of Claims 1 to 4, wherein the weight average molecular weight of the branched polysilane is 50 to 30,000.

6. The laminate according to any one of Claims 1 to 5, wherein the 5% weight loss temperature of the branched polysilane is 300°C or higher.

7. The laminate according to any one of Claims 1 to 6, wherein the organic resin is a novolak resin.

8. The laminate according to Claim 7, wherein the novolak resin is a polymer containing one or more selected from the group consisting of a unit represented by the formula (C1-1), a unit represented by the formula (C1-2), and a unit represented by the formula (C1-3). 【Chemical 2】 (In the formula, C １ represents a group derived from an aromatic compound containing a nitrogen atom, C ２ represents a group containing a tertiary carbon atom having at least one selected from the group consisting of a secondary carbon atom, a quaternary carbon atom, and an aromatic ring in a side chain, C ３ represents a group derived from an aliphatic polycyclic compound, C ４ represents a group derived from phenol, a group derived from bisphenol, a group derived from naphthol, a group derived from biphenyl, or a group derived from biphenol.)

9. The laminate according to any one of Claims 1 to 8, wherein the release agent composition contains a crosslinking agent.

10. The laminate according to any one of Claims 1 to 9, wherein the adhesive layer is a film obtained by using an adhesive composition containing an adhesive component (S) including at least one selected from a polysiloxane-based adhesive, an acrylic resin-based adhesive, an epoxy resin-based adhesive, a polyamide-based adhesive, a polystyrene-based adhesive, a polyimide adhesive, and a phenol resin-based adhesive.

11. The laminate according to Claim 10, wherein the adhesive component (S) contains a polysiloxane-based adhesive.

12. The laminate according to Claim 11, wherein the polysiloxane-based adhesive contains a polysiloxane component (A) that cures by a hydrosilylation reaction.

13. A release agent composition for forming the release layer of a laminate including a semiconductor substrate, a support substrate, an adhesive layer, and a release layer provided between the semiconductor substrate and the support substrate, which is a release agent composition containing an organic resin, a branched polysilane, and a solvent.

14. The release agent composition according to Claim 13, wherein the branched polysilane contains a structural unit represented by the formula (B). [Chemical Formula 3] (wherein, R Ｂ represents a hydrogen atom, a hydroxyl group, a silyl group or an organic group.)

15. The above R Ｂ The release agent composition according to claim 14, wherein R is an aryl group.

16. The above R Ｂ The release agent composition according to claim 15, wherein R is a phenyl group.

17. The release agent composition according to any one of Claims 13 to 16, wherein the weight average molecular weight of the branched polysilane is 50 to 30,000.

18. The release agent composition according to any one of claims 13 to 17, wherein the 5% weight loss temperature of the branched-chain polysilane is 300 °C or higher.

19. The release agent composition according to any one of claims 13 to 18, wherein the organic resin is a novolak resin.

20. The release agent composition according to claim 19, wherein the novolak resin is a polymer containing one or more selected from the group consisting of a unit represented by formula (C1-1), a unit represented by formula (C1-2), and a unit represented by formula (C1-3). 【Chemical Formula 4】 (In the formula, C １ represents a group derived from an aromatic compound containing a nitrogen atom, and C ２ represents a group containing a tertiary carbon atom having at least one selected from the group consisting of a secondary carbon atom, a quaternary carbon atom, and an aromatic ring in a side chain, and C ３ represents a group derived from an aliphatic polycyclic compound, and C ４ represents a group derived from phenol, a group derived from bisphenol, a group derived from naphthol, a group derived from biphenyl, or a group derived from biphenol.)

21. The release agent composition according to any one of claims 13 to 20, comprising a crosslinking agent.

22. The release agent composition according to any one of claims 13 to 21, wherein the adhesive layer is a film obtained by using an adhesive composition containing an adhesive component (S) containing at least one selected from the group consisting of a polysiloxane-based adhesive, an acrylic resin-based adhesive, an epoxy resin-based adhesive, a polyamide-based adhesive, a polystyrene-based adhesive, a polyimide adhesive, and a phenol resin-based adhesive.

23. The release agent composition according to claim 22, wherein the adhesive component (S) contains a polysiloxane-based adhesive.

24. The release agent composition according to claim 23, wherein the polysiloxane-based adhesive contains a polysiloxane component (A) that cures by a hydrosilylation reaction.

25. A method for manufacturing a processed semiconductor substrate, comprising: a first step of processing a semiconductor substrate of the laminate according to any one of claims 1 to 12; a second step of separating the semiconductor substrate and the support substrate; and a third step of washing the separated semiconductor substrate with a cleaning agent composition. A method for manufacturing a processed semiconductor substrate, including the above steps.

26. The method for manufacturing a processed semiconductor substrate according to claim 25, wherein the second step includes a step of irradiating light onto the release layer.

27. The method for manufacturing a processed semiconductor substrate according to claim 25 or 26, wherein the cleaning agent composition is a cleaning agent composition containing a quaternary ammonium salt and an organic solvent.

28. The method for manufacturing a processed semiconductor substrate according to claim 27, wherein the quaternary ammonium salt is a halogen-containing quaternary ammonium salt.

29. The method for manufacturing a processed semiconductor substrate according to claim 28, wherein the halogen-containing quaternary ammonium salt is a fluorine-containing quaternary ammonium salt.

Images