Method for manufacturing laminates, release agent compositions, and processed semiconductor substrates

Abstract

A laminate is characterized by comprising: a semiconductor substrate, a support substrate, and an adhesive layer and a release layer disposed between the semiconductor substrate and the support substrate, wherein the release layer is a film obtained from a release agent composition comprising an organic resin, a branched polysilane, and a solvent.

Description

Technical Field

[0001] This invention relates to a method for manufacturing laminates, release agent compositions, and processed semiconductor substrates. Background Technology

[0002] In contrast to traditional semiconductor wafers integrated in a two-dimensional planar direction, semiconductor integration technology aims for further integration in a three-dimensional direction (layering). This three-dimensional layering involves wiring via through-silicon vias (TSVs) and integration into multiple layers. During multi-layer integration, grinding is used to thin the side (back side) of each wafer to be integrated, opposite to the circuit surface, and the thinned semiconductor wafers are then layered.

[0003] Before thinning, the semiconductor wafer (hereinafter simply referred to as the wafer) is bonded to a support for polishing using a polishing apparatus. This bonding must be easily peeled off after polishing; therefore, it is called a temporary bond. This temporary bond must be easily detachable from the support to prevent the thinned semiconductor wafer from being cut or deformed when subjected to significant force during removal. However, it is undesirable for the wafer to detach or shift due to polishing stress during back-side polishing. Therefore, the desired performance for a temporary bond is: resistance to the stress during polishing and easy removal after polishing.

[0004] For example, the following properties are desired: high stress (strong adhesion) relative to the planar direction during grinding, and low stress (weak adhesion) relative to the longitudinal direction during disassembly.

[0005] For such bonding and separation processes, methods using laser irradiation have been disclosed (see, for example, Patent Documents 1 and 2), but with recent advancements in the semiconductor field, there is a growing demand for new technologies related to peeling using irradiation with light such as lasers.

[0006] Existing technical documents

[0007] Patent documents

[0008] Patent Document 1: Japanese Patent Application Publication No. 2004-64040

[0009] Patent Document 2: Japanese Patent Application Publication No. 2012-106486 Summary of the Invention

[0010] The problem that the invention aims to solve

[0011] The present invention was made in view of the above circumstances, and its object is to provide a laminate having a release layer, a release agent composition suitable as such a release layer, and a method for manufacturing a processed semiconductor substrate using such a laminate. The release layer has excellent heat resistance when bonding a support substrate and a semiconductor substrate, when processing the back side of the semiconductor substrate, when mounting components, etc., can be easily peeled off when peeling the support substrate and the semiconductor substrate, and cannot be properly removed by any of organic solvents, acids, or alkaline developing solutions, hydrogen peroxide solutions, etc. used in the manufacture of semiconductor devices, but can be properly removed by a cleaning agent composition.

[0012] Solution for solving the problem

[0013] In order to solve the above-mentioned problems, the inventors conducted in-depth research and found that the above-mentioned problems could be solved by means of the following method, thereby completing the present invention: as a release layer of a laminate comprising a semiconductor substrate, a support substrate, and an adhesive layer and a release layer disposed between the semiconductor substrate and the support substrate, a film obtained by means of a release agent composition comprising an organic resin, a branched polysilane, and a solvent is used.

[0014] That is, the present invention provides the following content.

[0015] 1. A laminate, characterized in that it comprises: a semiconductor substrate, a support substrate, and an adhesive layer and a release layer disposed between the semiconductor substrate and the support substrate, wherein the release layer is a film obtained from a release agent composition comprising an organic resin, a branched polysilane, and a solvent.

[0016] 2. The laminate according to 1, wherein the branched polysilane comprises the structural unit shown in formula (B).

[0017]

[0018] (where R is in the formula) B (This represents a hydrogen atom, hydroxyl group, silyl group, or organic group.)

[0019] 3. The laminate according to claim 2, wherein the above-mentioned R B It is an aryl group.

[0020] 4. The laminate according to claim 3, wherein the above-mentioned R B It is a phenyl group.

[0021] 5. The laminate according to any one of 1 to 4, wherein the weight-average molecular weight of the branched polysilane is 50 to 30,000.

[0022] 6. The laminate according to any one of 1 to 5, wherein the temperature at which the branched polysilane is reduced by 5% by weight is 300°C or higher.

[0023] 7. The laminate according to any one of 1 to 6, wherein the organic resin is a phenolic varnish resin.

[0024] 8. The laminate according to 7, wherein the phenolic varnish resin is one or more polymers comprising units selected from the group consisting of units shown in formula (C1-1), units shown in formula (C1-2), and units shown in formula (C1-3).

[0025]

[0026] (where C) 1 A group representing an aromatic compound containing a nitrogen atom, C 2 C represents a group containing a tertiary carbon atom whose side chain has at least one selected from the group consisting of secondary carbon atoms, quaternary carbon atoms, and aromatic rings. 3 The C group represents a group derived from aliphatic polycyclic compounds. 4 This indicates 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 biphenyl.

[0027] 9. The laminate according to any one of 1 to 8, wherein the release agent composition comprises a crosslinking agent.

[0028] 10. The laminate according to any one of 1 to 9, wherein the adhesive layer is a film obtained using an adhesive composition comprising an adhesive component (S), said adhesive component (S) comprising at least one selected from polysiloxane adhesives, acrylic resin adhesives, epoxy resin adhesives, polyamide adhesives, polystyrene adhesives, polyimide adhesives, and phenolic resin adhesives.

[0029] 11. The laminate according to 10, wherein the adhesive component (S) comprises a polysiloxane-based adhesive.

[0030] 12. The laminate according to 11, wherein the polysiloxane adhesive comprises a polysiloxane component (A) cured by a hydrosilylation reaction.

[0031] 13. A release agent composition for forming the release layer of a laminate comprising a semiconductor substrate, a support substrate, and an adhesive layer and a release layer disposed between the semiconductor substrate and the support substrate, the release agent composition comprising an organic resin, a branched polysilane, and a solvent.

[0032] 14. The stripping agent composition according to 13, wherein the branched polysilane comprises the structural unit shown in formula (B).

[0033]

[0034] (where R is in the formula) B (This represents a hydrogen atom, hydroxyl group, silyl group, or organic group.)

[0035] 15. The stripping agent composition according to 14, wherein the above-mentioned R B It is an aryl group.

[0036] 16. The stripping agent composition according to 15, wherein the above-mentioned R B It is a phenyl group.

[0037] 17. The stripping agent composition according to any one of 13 to 16, wherein the weight-average molecular weight of the branched polysilane is 50 to 30,000.

[0038] 18. The stripping agent composition according to any one of 13 to 17, wherein the temperature at which the branched polysilane is reduced by 5% by weight is 300°C or higher.

[0039] 19. The stripping agent composition according to any one of 13 to 18, wherein the organic resin is a phenolic varnish resin.

[0040] 20. The stripping agent composition according to 19, wherein the phenolic varnish resin is one or more polymers comprising units selected from the group consisting of units of formula (C1-1), units of formula (C1-2), and units of formula (C1-3).

[0041]

[0042] (where C) 1 A group representing an aromatic compound containing a nitrogen atom, C 2 C represents a group containing a tertiary carbon atom whose side chain has at least one selected from the group consisting of secondary carbon atoms, quaternary carbon atoms, and aromatic rings. 3 The C group represents a group derived from aliphatic polycyclic compounds. 4 This indicates 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 biphenyl.

[0043] 21. The stripping agent composition according to any one of 13 to 20, comprising a crosslinking agent.

[0044] 22. The release agent composition according to any one of 13 to 21, wherein the adhesive layer is a film obtained using an adhesive composition comprising an adhesive component (S), said adhesive component (S) comprising at least one selected from polysiloxane adhesives, acrylic resin adhesives, epoxy resin adhesives, polyamide adhesives, polystyrene adhesives, polyimide adhesives, and phenolic resin adhesives.

[0045] 23. The release agent composition according to 22, wherein the adhesive component (S) comprises a polysiloxane-based adhesive.

[0046] 24. The release agent composition according to 23, wherein the polysiloxane adhesive comprises a polysiloxane component (A) cured by a hydrogenation silanization reaction.

[0047] 25. A method for manufacturing a processed semiconductor substrate, comprising: a first step of processing a semiconductor substrate of a laminate as described in any one of 1 to 12; a second step of separating the semiconductor substrate and a support substrate; and a third step of cleaning the separated semiconductor substrate with a cleaning agent composition.

[0048] 26. The method for manufacturing the processed semiconductor substrate according to 25, wherein the second step includes a step of irradiating the release layer with light.

[0049] 27. The method for manufacturing the processed semiconductor substrate according to 25 or 26, wherein the cleaning agent composition is a cleaning agent composition comprising a quaternary ammonium salt and an organic solvent.

[0050] 28. The method for manufacturing the processed semiconductor substrate according to 27, wherein the quaternary ammonium salt is a halogen-containing quaternary ammonium salt.

[0051] 29. The method for manufacturing the processed semiconductor substrate according to 28, wherein the halogen-containing quaternary ammonium salt is a fluorine-containing quaternary ammonium salt.

[0052] Invention Effects

[0053] The laminate of the present invention comprises a semiconductor substrate, a support substrate, and an adhesive layer and a release layer disposed between the semiconductor substrate and the support substrate. The release layer is a film obtained by a release agent composition comprising an organic resin, a branched polysilane, and a solvent. Therefore, the semiconductor substrate and the support substrate can be separated without applying excessive load to the semiconductor substrate for release. Furthermore, by cleaning the separated semiconductor substrate with a cleaning agent composition, proper cleaning of the substrate can be achieved without leaving any residue of the release layer on its surface.

[0054] In particular, when the support substrate of the laminate of the present invention is light-transmitting, by irradiating the release layer with light from the support substrate side, the organic resin in the release layer absorbs the light and undergoes appropriate deterioration, thereby achieving good release ability. As a result, the semiconductor substrate and the support substrate can be separated without applying excessive physical load to the semiconductor substrate for release, and by cleaning the separated semiconductor substrate with a cleaning agent composition, proper cleaning of the substrate can be achieved without leaving residue of the release layer on its surface.

[0055] Furthermore, the release layer of the laminate of the present invention cannot be properly removed by any of the organic solvents, acids, or solutions used in the manufacture of semiconductor devices (alkaline developer, hydrogen peroxide, etc.).

[0056] By using the laminate of the present invention having such characteristics, for example, when separating the processed silicon wafer from the glass substrate serving as a support substrate after processing the back side of the silicon wafer, the processed silicon wafer can be easily separated without applying excessive load for peeling. Therefore, when the support substrate is light-transmitting, the processed silicon wafer can be further easily separated by irradiating light from the support substrate side without further applying excessive load for peeling. Thus, mechanical stress on the silicon wafer can be avoided, and as a result, damage such as warping and deformation of the silicon wafer can be avoided.

[0057] Furthermore, the release layer of the laminate of the present invention cannot be properly removed by organic solvents, acids, or solutions used in the manufacture of semiconductor devices (such as alkaline developer, hydrogen peroxide water, etc.). Therefore, even if the laminate is exposed to any of the organic solvents, acids, or solutions used in the manufacture of semiconductor devices before the final separation of the semiconductor substrate and the support substrate, and the release layer comes into contact with the solution, the possibility of accidental peeling can be sufficiently reduced. On the other hand, the release layer can be properly removed by a cleaning agent composition. Therefore, by cleaning the separated semiconductor substrate with a cleaning agent composition after the separation of the semiconductor substrate and the support substrate, good cleaning can be achieved without leaving any residue of the release layer on its surface.

[0058] The release agent composition of the present invention comprises an organic resin and a solvent, and contains a branched polysilane, thus providing a film with excellent uniformity easily and reproducibly by wet methods such as spin coating. Furthermore, when the organic resin contained in the release agent composition deteriorates due to light absorption, by irradiating the film obtained from the release agent composition with light, the organic resin in the film absorbs light and undergoes appropriate necessary deterioration, thereby exhibiting good release ability, resulting in improved release properties.

[0059] Furthermore, the stripping agent composition contains branched polysilane, so the film obtained from the stripping agent composition cannot be properly removed by any of the organic solvents, acids, and solutions used in the manufacture of semiconductor devices, but can be properly removed by the cleaning agent composition.

[0060] By using a film obtained from the release agent composition of the present invention having such characteristics as a release layer, and disposing it together with an adhesive layer between a semiconductor substrate and a support substrate, a laminate that can be separated without applying excessive load for peeling to the workpieces such as the support substrate and the semiconductor substrate can be obtained. In the case that the support substrate is light-transmitting, by irradiating light from the support substrate side, a laminate that can be separated without further applying excessive load for peeling to the workpieces such as the support substrate and the semiconductor substrate can be obtained. Furthermore, even if such a laminate is exposed to any of the organic solvents, acids, or chemical solutions used in the manufacturing process of semiconductor devices, the possibility of accidental peeling is sufficiently reduced. On the other hand, the release layer can be properly removed by a cleaning agent composition. Therefore, by cleaning the separated semiconductor substrate with a cleaning agent composition after separating the semiconductor substrate and the support substrate, good cleaning can be achieved without leaving any residue of the release layer on its surface.

[0061] By using the laminate and release agent composition of the present invention having the features described above, a method for manufacturing well-processed semiconductor substrates can be achieved, and the manufacture of semiconductor devices with higher reliability can be expected. Detailed Implementation

[0062] The laminate of the present invention comprises: a semiconductor substrate, a support substrate, and an adhesive layer and a release layer disposed between the semiconductor substrate and the support substrate, wherein the release layer is a film obtained by a release agent composition comprising an organic resin, a branched polysilane, and a solvent.

[0063] Semiconductor substrates are, for example, wafers. As a specific example, silicon wafers with a diameter of about 300 mm and a thickness of about 770 μm can be listed, but are not limited to this.

[0064] A support substrate is a support (carrier) used to support a semiconductor substrate.

[0065] There are no particular restrictions on the support substrate as long as it can support the semiconductor substrate through functional layers such as adhesive layers and release layers. However, when the support substrate and the semiconductor substrate are separated by irradiating the release layer with light from the support substrate side, the support substrate needs to be light-transmitting.

[0066] The light transmittance of the support substrate when it is stripped by light irradiation is typically 50% or more, preferably 60% or more, more preferably 70% or more, even more preferably 80% or more, and even more preferably 90% or more.

[0067] The wavelength of the light used for stripping is not particularly limited as long as it is absorbed by the organic resin, and is typically in the range of 100 nm to 600 nm. For example, preferred wavelengths are 308 nm, 343 nm, 355 nm, or 365 nm. The amount of light required for stripping is the amount that causes appropriate deterioration, such as decomposition, as described later.

[0068] The light used for stripping can be a laser or a non-laser light source such as a lamp.

[0069] As a specific example of a support substrate, a glass wafer with a diameter of about 300 mm and a thickness of about 700 μm can be cited, but it is not limited to this.

[0070] In one embodiment, the laminate of the present invention has a semiconductor substrate, a support substrate, and only two layers between the semiconductor substrate and the support substrate, one of which is an adhesive layer and the other is a release layer.

[0071] In a preferred embodiment, the laminate of the present invention comprises a semiconductor substrate, a support substrate, an adhesive layer disposed between the semiconductor substrate and the support substrate and disposed in contact with the semiconductor substrate, and a release layer disposed in contact with the support substrate and the adhesive layer. Furthermore, in one embodiment, the support substrate is light-transmitting, and the organic resin is a resin that deteriorates upon absorbing light irradiation, so that the release layer of the laminate of the present invention can be peeled off by irradiating it with light.

[0072] When the support substrate of the laminate of the present invention is transparent, the release layer can be peeled off without applying excessive load for peeling by irradiating light from the support substrate side. As a result, the semiconductor substrate and the support substrate can be easily separated.

[0073] That is, when the support substrate of the laminate of the present invention is light-transmitting, the release layer of the laminate of the present invention receives light irradiation from the support substrate side, and the release capability is improved compared with that before irradiation. In the laminate of the present invention, for example, during the thinning and other processing of the silicon wafer, which is a semiconductor substrate, it is properly supported by a glass wafer, which is a support substrate for transmitting light, through functional layers such as adhesive layers and release layers. After the processing is completed, when light is irradiated from the support substrate side, the light transmitted through the support substrate is absorbed by the release layer. As a result, the release layer separates or decomposes 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, proper release can be achieved without applying excessive load for release.

[0074] Moreover, as described later, by cleaning the separated semiconductor substrate with a cleaning agent composition, proper cleaning of the substrate can be achieved without leaving any residue of the stripping layer on the substrate.

[0075] As described above, the release layer of the laminate of the present invention is a film obtained from a release agent composition comprising an organic resin, a branched polysilane, and a solvent. In one embodiment, the film is a cured film obtained by curing the film components in the release agent composition.

[0076] The above-described release agent composition comprises an organic resin. Such an organic resin is preferably one that exhibits appropriate release ability, wherein, in the case of separating the semiconductor substrate from the support substrate by irradiating the release layer with light, the organic resin absorbs the light and appropriately undergoes the necessary deterioration, such as decomposition, to enhance the release ability.

[0077] Phenolic varnish resin is a preferred example of an organic resin.

[0078] When the release layer of the laminate of the present invention is peeled off by irradiating it with light, it is preferably a phenolic varnish resin that deteriorates by absorbing light with a wavelength of 190 nm to 600 nm, and more preferably a phenolic varnish resin that deteriorates by irradiating light such as lasers with wavelengths of 308 nm, 343 nm, 355 nm or 365 nm.

[0079] If a specific example is given, phenolic varnish resin is a polymer comprising one or more units selected from the group consisting of units shown in formula (C1-1), units shown in formula (C1-2), and units shown in formula (C1-3).

[0080]

[0081] C 1 A group representing an aromatic compound containing a nitrogen atom, C 2 C represents a group containing a tertiary carbon atom whose side chain has at least one selected from the group consisting of secondary carbon atoms, quaternary carbon atoms, and aromatic rings. 3 The C group represents a group derived from aliphatic polycyclic compounds. 4 This indicates 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 biphenyl.

[0082] That is, the polymer as a phenolic varnish resin contains one or more units selected from the group consisting of: a unit having a group derived from a nitrogen-containing aromatic compound and a group containing a tertiary carbon atom having at least one of the group consisting of a secondary carbon atom, a quaternary carbon atom, and an aromatic ring in the side chain (Formula (C1-1)); a unit having a group derived from a nitrogen-containing aromatic compound and a group derived from an aliphatic polycyclic compound (Formula (C1-2)); and a unit having 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 biphenyl and a group containing a tertiary carbon atom having at least one of the group consisting of a quaternary carbon atom and an aromatic ring in the side chain (Formula (C1-3)).

[0083] In a preferred embodiment, the polymer as a phenolic varnish resin comprises any or both of the following units: a unit having a group derived from a nitrogen-containing aromatic compound and a group containing a tertiary carbon atom in the side chain having at least one of the groups selected from secondary carbon atoms, quaternary carbon atoms and aromatic rings (Formula (C1-1)); and a unit having a group derived from a nitrogen-containing aromatic compound and a group derived from an aliphatic polycyclic compound (Formula (C1-2)).

[0084] C 1 That is, groups derived from nitrogen-containing aromatic compounds can be, for example, groups derived from carbazole, groups derived from N-phenyl-1-naphthylamine, N-phenyl-2-naphthylamine-1-naphthylamine, etc., but are not limited to these.

[0085] C 2 That is, the side chain has at least one group consisting of a secondary carbon atom, a quaternary carbon atom, and an aromatic ring, and includes a tertiary carbon atom. For example, it can be a group derived from 1-naphthaldehyde, a group derived from 1-pyrene formaldehyde, a group derived from 4-(trifluoromethyl)benzaldehyde, a group derived from acetaldehyde, etc., but is not limited to these.

[0086] C 3 That is, the groups derived from aliphatic polycyclic compounds can be derived from dicyclopentadiene, but are not limited to this.

[0087] C 4 It 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 biphenyl.

[0088] In a preferred embodiment, the polymer described above includes, for example, the unit represented by formula (C1-1-1) as the unit represented by formula (C1-1).

[0089]

[0090] In formula (C1-1-1), R 901 and R 902 The substituents representing substitutions on the ring, each independently representing a halogen atom, nitro, cyano, amino, hydroxyl, carboxyl, optionally substituted alkyl, optionally substituted alkenyl, or optionally substituted aryl, R 903 R represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group. 904 R represents a hydrogen atom, an optionally substituted aryl group, or an optionally substituted heteroaryl group. 905 R represents an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted heteroaryl group. 904 Group and R 905 The groups can be optionally bonded to each other to form divalent groups. As substituents for alkyl and alkenyl groups, examples include halogen atoms, nitro, cyano, amino, hydroxyl, carboxyl, aryl, and heteroaryl groups. As substituents for aryl and heteroaryl groups, examples include halogen atoms, nitro, cyano, amino, hydroxyl, carboxyl, alkyl, and alkenyl groups.

[0091] h 1 and h 2 Each can independently represent an integer from 0 to 3.

[0092] The number of carbon atoms in the optionally substituted alkyl and optionally substituted alkenyl groups is generally 40 or less, preferably 30 or less, and more preferably 20 or less, from the viewpoint of solubility.

[0093] The number of carbon atoms in the optionally substituted aryl and heteroaryl groups is generally 40 or less, preferably 30 or less, and more preferably 20 or less, from the viewpoint of solubility.

[0094] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine.

[0095] Specific examples of alkyl groups that may be optionally substituted include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 1-methyl n-butyl, 2-methyl n-butyl, 3-methyl n-butyl, 1,1-dimethyl n-propyl, 1,2-dimethyl n-propyl, 2,2-dimethyl n-propyl, 1-ethyl n-propyl, n-hexyl, 1-methyl n-pentyl, 2-methyl n-pentyl, 3-methyl n-pentyl, 4 -Methyl-n-pentyl, 1,1-dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1,3-dimethyl-n-butyl, 2,2-dimethyl-n-butyl, 2,3-dimethyl-n-butyl, 3,3-dimethyl-n-butyl, 1-ethyl-n-butyl, 2-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl, 1,2,2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl, 1-ethyl-2-methyl-n-propyl, etc., but not limited to these.

[0096] Specific examples of the optionally substituted alkenyl groups include: vinyl, 1-propenyl, 2-propenyl, 1-methyl-1-vinyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl, 1-ethylvinyl, 1-methyl-1-propenyl, 1-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-n-propylvinyl, 1-methyl-1-butenyl, 1-methyl-2-butenyl, 1-methyl-3-butenyl, 2-ethyl-2-propenyl, 2-methyl-1-butenyl, 2-methyl-2-butenyl, 2-methyl- 3-Butenyl, 3-methyl-1-butenyl, 3-methyl-2-butenyl, 3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl, 1-isopropylvinyl, 1,2-dimethyl-1-propenyl, 1,2-dimethyl-2-propenyl, 1-cyclopentenyl, 2-cyclopentenyl, 3-cyclopentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1-pentenyl, 1-methyl-2-pentenyl, 1-methyl-3-pentenyl, 1-methyl-4-pentenyl, 1-n-butylvinyl, 2-methyl-1-pentenyl, 2-methyl-2-pentenyl, 2-methyl-3-pentenyl alkenyl, 2-methyl-4-pentenyl, 2-n-propyl-2-propenyl, 3-methyl-1-pentenyl, 3-methyl-2-pentenyl, 3-methyl-3-pentenyl, 3-methyl-4-pentenyl, 3-ethyl-3-butenyl, 4-methyl-1-pentenyl, 4-methyl-2-pentenyl, 4-methyl-3-pentenyl, 4-methyl-4-pentenyl, 1,1-dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl, 1,2-dimethyl-1-butenyl, 1,2-dimethyl-2-butenyl, 1,2-dimethyl-3-butenyl, 1-methyl-2-ethyl-2-propenyl, 1-sec-butylvinyl, 1,3 -Dimethyl-1-butenyl, 1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl, 1-isobutylvinyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 2-isopropyl-2-propenyl, 3,3-dimethyl-1-butenyl, 1-ethyl-1-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 1-n-propyl-1-propenyl, 1-n-propyl-2-propenyl, 2-ethyl-1-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1,1,2-Trimethyl-2-propenyl, 1-tert-butylvinyl, 1-Methyl-1-ethyl-2-propenyl, 1-Ethyl-2-methyl-1-propenyl, 1-Ethyl-2-methyl-2-propenyl, 1-Isopropyl-1-propenyl, 1-Isopropyl-2-propenyl, 1-Methyl-2-cyclopentenyl, 1-Methyl-3-cyclopentenyl, 2-Methyl-1-cyclopentenyl, 2-Methyl-2-cyclopentenyl, 2 The range includes, but is not limited to, methyl-3-cyclopentenyl, 2-methyl-4-cyclopentenyl, 2-methyl-5-cyclopentenyl, 2-methylenecyclopentenyl, 3-methyl-1-cyclopentenyl, 3-methyl-2-cyclopentenyl, 3-methyl-3-cyclopentenyl, 3-methyl-4-cyclopentenyl, 3-methyl-5-cyclopentenyl, 3-methylenecyclopentenyl, 1-cyclohexenyl, 2-cyclohexenyl, and 3-cyclohexenyl.

[0097] Specific examples of aryl groups that may be optionally substituted include: phenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 4-methoxyphenyl, 4-ethoxyphenyl, 4-nitrophenyl, 4-cyanophenyl, 1-naphthyl, 2-naphthyl, biphenyl-4-yl, biphenyl-3-yl, biphenyl-2-yl, 1-anthrayl, 2-anthrayl, 9-anthrayl, 1-phenanthyl, 2-phenanthyl, 3-phenanthyl, 4-phenanthyl, 9-phenanthyl, etc., but are not limited to these.

[0098] Specific examples of heteroaryl groups that may be optionally substituted include: 2-thienyl, 3-thienyl, 2-furanyl, 3-furanyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 3-isooxazolyl, 4-isooxazolyl, 5-isooxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl, etc., but are not limited to these.

[0099] The following are specific examples of the unit shown in equation (C1-1-1), but are not limited to this.

[0100]

[0101] In a preferred embodiment, the polymer described above includes, for example, the unit represented by formula (C1-1-2) as the unit represented by formula (C1-1).

[0102]

[0103] In formula (C1-1-2), Ar 901 and Ar 902 Each independently represents an aromatic ring such as a benzene ring or a naphthalene ring, R 901 ~R 905 and h1 and h 2 It means the same as above.

[0104] The following are specific examples of the unit shown in equation (C1-1-2), but are not limited to this.

[0105]

[0106] In a preferred embodiment, the polymer may contain, for example, units represented by formula (C1-2-1) or (C1-2-2) as units represented by formula (C1-2).

[0107]

[0108] In the above formula, R 906 ~R 909 Substituents that are bonded to the ring are each independently represented by a halogen atom, nitro group, cyano group, amino group, hydroxyl group, carboxyl group, optionally substituted alkyl group, optionally substituted alkenyl group, or optionally substituted aryl group. Specific examples and preferred carbon numbers of halogen atoms, optionally substituted alkyl groups, optionally substituted alkenyl groups, and optionally substituted aryl groups can be listed as above. 3 ~h 6 Each element independently represents an integer from 0 to 3, R 901 ~R 903 and h 1 and h 2 It means the same as above.

[0109] The following are specific examples of the units shown in equations (C1-2-1) and (C1-2-2), but are not limited to these examples.

[0110]

[0111] The following are specific examples of the units shown in equation (C1-3), but are not limited to these.

[0112]

[0113] The phenolic varnish resin used as the polymer in this invention can be obtained by condensing a carbazole compound with an aldehyde compound or a ketone compound.

[0114] Specific examples of carbazole compounds include: carbazole, 1,3,6,8-tetranitrocarbazole, 3,6-diaminocarbazole, 3,6-dibromo-9-ethylcarbazole, 3,6-dibromo-9-phenylcarbazole, 3,6-dibromocarbazole, 3,6-dichlorocarbazole, 3-amino-9-ethylcarbazole, 3-bromo-9-ethylcarbazole, 4,4'-bis(9H-carbazole-9-yl)biphenyl, 4-glycidylcarbazole, 4-hydroxycarbazole, 9-(1H-phenylene) Examples of carbazoles include (1-(-triazolylmethyl)-9H-carbazole, 9-acetyl-3,6-diiodocarbazole, 9-benzoylcarbazole, 9-benzoylcarbazole-6-dicarbaldehyde, 9-benzylcarbazole-3-carbaldehyde, 9-methylcarbazole, 9-phenylcarbazole, 9-vinylcarbazole, carbazole potassium, carbazole-N-formyl chloride, N-ethylcarbazole-3-carbaldehyde, and N-((9-ethylcarbazole-3-yl)methylene)-2-methyl-1-dihydroindoleamine, but these are not limited to these examples.

[0115] Carbazole compounds can be used alone or in combination of two or more.

[0116] Specific examples of aldehyde compounds include: saturated aliphatic aldehydes such as formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, pentanal, hexanal, 2-methylbutyraldehyde, hexanal, undecanoal, 7-methoxy-3,7-dimethyloctaldehyde, cyclohexaneformaldehyde, 3-methyl-2-butanaldehyde, glyoxal, malondialdehyde, succinaldehyde, glutaraldehyde, and adipaldehyde; unsaturated aliphatic aldehydes such as acrolein and methacrolein; heterocyclic aldehydes such as furfural and pyridineformaldehyde; and aromatic aldehydes such as benzaldehyde, naphthaldehyde, anthracene formaldehyde, phenanthrene formaldehyde, salicylaldehyde, phenylacetaldehyde, 3-phenylpropanaldehyde, tolualdehyde, (N,N-dimethylamino)benzaldehyde, and acetoxybenzaldehyde, but are not limited to these. Aromatic aldehydes are preferred.

[0117] Aldehyde compounds can be used alone or in combination of two or more.

[0118] Specific examples of ketone compounds include diphenyl ketones, phenylnaphthyl ketones, dinaphthyl ketones, phenyltolyl ketones, xylyl ketones, and other diaryl ketone compounds, but are not limited to these.

[0119] Ketone compounds can be used alone or in combination of two or more.

[0120] In the condensation reaction used to obtain the above polymer, an aldehyde or ketone compound is typically used in a ratio of 0.1 to 10 equivalents relative to the benzene ring constituting the carbazole compound.

[0121] In the condensation reaction used to obtain the above polymer, an acid catalyst is usually used.

[0122] Examples of acid catalysts include: inorganic 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, but are not limited to these.

[0123] The amount of acid catalyst is appropriately determined according to the type of acid used, etc., and therefore cannot be specified in general terms. However, it is usually appropriately determined in the range of 0.001 to 10,000 parts by mass relative to 100 parts by mass of carbazole compound.

[0124] The condensation reaction used to obtain the above polymer can sometimes be carried out without a solvent if either the raw material compound or the acid catalyst used is liquid, but it is usually carried out with a solvent.

[0125] There are no particular limitations on such solvents as long as they do not hinder the reaction. Typical examples include ether compounds such as tetrahydrofuran and dioxane.

[0126] The reaction temperature is usually appropriately determined within the range of 40℃ to 200℃. The reaction time varies depending on the reaction temperature, so it cannot be specified in general terms, but it is usually appropriately determined within the range of 30 minutes to 50 hours.

[0127] After the reaction is complete, if necessary, the resin is purified and separated using conventional methods, and the resulting phenolic varnish resin is used in the preparation of the stripping agent composition.

[0128] If one is skilled in the art, one can determine the manufacturing conditions of phenolic varnish resin without excessive burden based on the above description and common technical knowledge, and therefore, phenolic varnish resin can be manufactured.

[0129] The weight-average molecular weight of organic resins such as phenolic varnish resins used as polymers is typically 500 to 200,000. From the viewpoint of ensuring solubility in solvents and obtaining a uniform film by good mixing with branched polysilanes during film formation, it is preferable to have a molecular weight of 100,000 or less, more preferably 50,000 or less, even more preferably 10,000 or less, even more preferably 5,000 or less, and even more preferably 3,000 or less. From the viewpoint of improving film strength, it is preferable to have a molecular weight of 600 or more, more preferably 700 or more, even more preferably 800 or more, even more preferably 900 or more, and even more preferably 1,000 or more.

[0130] It should be noted that, in this invention, the weight-average molecular weight, number-average molecular weight, and dispersity of organic resins such as phenolic varnish resins, which are polymers, can be determined, for example, using a gel permeation chromatography (GPC) apparatus (EcoSEC, HLC-8320GPC, Tosoh Corporation) and a GPC column (TSKgel SuperMultipore HZ-N, TSKgel SuperMultipore HZ-H, Tosoh Corporation). The column temperature is set to 40°C, tetrahydrofuran is used as the eluent (dissolution solvent), the flow rate is set to 0.35 mL / min, and polystyrene (Sigma Aldrich) is used as the standard sample.

[0131] The resin contained in the above-mentioned release agent composition is preferably a phenolic varnish resin. Therefore, the above-mentioned release agent composition preferably contains phenolic varnish resin alone as an organic resin, but for the purpose of adjusting film properties, it may also contain phenolic varnish resin and other polymers.

[0132] Other examples of such polymers include: polyacrylate compounds, polymethacrylate compounds, polyacrylamide compounds, polymethacrylamide compounds, polyvinyl compounds, polystyrene compounds, polymaleimide compounds, polymaleic anhydride, polyacrylonitrile compounds, etc.

[0133] The above-described stripping agent composition may contain a crosslinking agent. By including a crosslinking agent, crosslinking between resins can be appropriately carried out, and appropriate curing can be achieved. As a result, a film that cannot be properly removed by organic solvents, acids, and solutions used in the manufacture of semiconductor devices (alkaline developer, hydrogen peroxide, etc.) but can be properly removed by a cleaning agent composition can be obtained with good reproducibility.

[0134] As specific examples of such crosslinking agents, there are no particular limitations as long as they can crosslink with the aforementioned organic resins. Typical examples include phenolic crosslinking agents, melamine crosslinking agents, urea crosslinking agents, and thiourea crosslinking agents that have crosslinking-forming groups such as hydroxymethyl, methoxymethyl, butoxymethyl, etc., within the molecule. These can be low-molecular-weight compounds or high-molecular-weight compounds.

[0135] The crosslinking agent contained in the above-mentioned stripping agent composition usually has two or more crosslinking forming groups, but from the viewpoint of achieving more appropriate curing with good reproducibility, the number of crosslinking forming groups contained in the compound as a crosslinking agent is preferably 2 to 10, more preferably 2 to 6.

[0136] From the viewpoint of achieving higher heat resistance, the crosslinking agent contained in the above-mentioned stripping agent composition preferably has an aromatic ring (e.g., benzene ring, naphthalene ring) in the molecule. Phenolic crosslinking agents are typical examples of such crosslinking agents, but are not limited thereto.

[0137] A phenolic crosslinking agent having a crosslinking forming group refers to 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 alkoxy groups derived from the phenolic hydroxyl group include methoxy and butoxy, but it is not limited to these.

[0138] The aromatic rings bonded by the cross-linking groups and the aromatic rings bonded by the phenolic hydroxyl groups and / or the alkoxy groups derived from the phenolic hydroxyl groups are not limited to non-condensed aromatic rings such as benzene rings, but can also be condensed aromatic rings such as naphthalene rings and anthracene rings.

[0139] In the case of multiple aromatic rings within the molecule of a phenolic crosslinking agent, the crosslinking forming group, phenolic hydroxyl group, and alkoxy group derived from phenolic hydroxyl group can bond to the same aromatic ring within the molecule or to different aromatic rings.

[0140] The aromatic rings bonded by cross-linking groups, phenolic hydroxyl groups, and alkoxy groups derived from phenolic hydroxyl groups can be further replaced by alkyl groups such as methyl, ethyl, and butyl, hydrocarbon groups such as aryl groups such as phenyl, and halogen atoms such as fluorine atoms.

[0141] For example, as a specific example of a phenolic crosslinking agent having a crosslinking-forming group, compounds represented by any one of formulas (L1) to (L4) can be listed.

[0142]

[0143] In each formula, each R' independently represents a fluorine atom, aryl group, or alkyl group, and each R” independently represents a hydrogen atom or alkyl group. 1 and L 2 Each independently represents a single bond, methylene, or propane-2,2-diyl, L 3Determined by q1, representing a single bond, methylene, propane-2,2-diyl, methane-triyl, or ethane-1,1,1-triyl, 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≤t2 7≤4, 0≤t28≤4, 0≤t29≤4, and t24+t25+t26≤4 are integers; t31, t32, and t33 are integers satisfying 2≤t31≤4, 1≤t32≤3, 0≤t33≤2, and t31+t32+t33≤5 are integers; t41, t42, and t43 are integers satisfying 2≤t41≤3, 1≤t42≤2, 0≤t43≤1, and t41+t42+t43≤4 are integers; q1 is 2 or 3; q2 represents the number of repetitions and is an integer greater than or equal to 0. As specific examples of the above aryl and alkyl groups, the same groups as the specific examples below can be listed, but phenyl is preferred as aryl, and methyl or tert-butyl is preferred as alkyl.

[0144] The following are specific examples of compounds represented by formulas (L1) to (L22) and (L1M) to (L22M), but are not limited to these examples. It should be noted that these compounds can be synthesized by known methods, and can also be obtained as products of Asahi Organic Materials Co., Ltd. and Honshu Chemical Co., Ltd.

[0145]

[0146]

[0147] A melamine-based crosslinking agent with a crosslinking-forming group refers to a melamine derivative, a 2,4-diamino-1,3,5-triazine derivative, or a 2-amino-1,3,5-triazine derivative formed by replacing at least one hydrogen atom of the amino group bonded to its triazine ring with a crosslinking-forming group, wherein the triazine ring may further have substituents such as phenyl or aryl groups.

[0148] Specific examples of melamine-based crosslinking agents with crosslinking-forming groups include: mono-, bis-, tri-, tetra-, penta-, or hexaalkoxymethyl melamines such as N,N,N',N',N",N”-hexa(methoxymethyl)melamine and N,N,N',N',N”-hexa(butoxymethyl)melamine; mono-, bis-, tri-, or tetraalkoxymethyl benzoguanamines such as N,N,N',N'-tetra(methoxymethyl)benzoguanamine and N,N,N',N’-tetra(butoxymethyl)benzoguanamine, but are not limited to these.

[0149] Urea-based crosslinking agents with crosslinking-forming groups are derivatives of compounds containing urea bonds, which have a structure in which at least one of the hydrogen atoms of the NH group constituting the urea bond is replaced by a crosslinking-forming group.

[0150] Specific examples of urea-based crosslinking agents having crosslinking-forming groups include: mono-, di-, tri-, or tetraalkoxymethyl urea such as 1,3,4,6-tetra(methoxymethyl) urea and 1,3,4,6-tetra(butoxymethyl) urea; mono-, di-, tri-, or tetraalkoxymethyl urea such as 1,3-bis(methoxymethyl) urea and 1,1,3,3-tetramethoxymethyl urea; but are not limited to these.

[0151] Thiourea-based crosslinking agents with crosslinking-forming groups refer to derivatives of compounds containing thiourea bonds, which have a structure in which at least one of the hydrogen atoms of the NH group constituting the thiourea bond is replaced by a crosslinking-forming group.

[0152] Specific examples of thiourea-based crosslinking agents with crosslinking-forming groups include mono-, di-, tri-, or tetra-alkoxymethyl thioureas such as 1,3-bis(methoxymethyl)thiourea and 1,1,3,3-tetramethoxymethylthiourea, but are not limited to these.

[0153] The amount of crosslinking agent contained in the above-mentioned release agent composition varies depending on the coating method used, the desired film thickness, etc., and therefore cannot be specified in general terms. However, relative to the film composition, it is usually 0.001% to 80% by mass. From the viewpoint of achieving proper curing and obtaining a laminate in which the semiconductor substrate and the support substrate can be well separated, it is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, even more preferably 0.5% by mass or more, even more preferably 1.0% by mass or more, preferably 50% by mass or less, more preferably 40% by mass or less, even more preferably 20% by mass or less, and even more preferably 10% by mass or less.

[0154] For the purpose of promoting cross-linking reactions, the above-mentioned stripping agent composition may contain an acid-producing agent or an acid.

[0155] From the viewpoint of obtaining a film suitable as a release layer with good reproducibility, the release agent composition generally does not contain acid-generating agents or acids, and the release layer has the following characteristics: it cannot be properly removed by organic solvents, acids, or chemical solutions used in the manufacture of semiconductor devices (alkaline developer, hydrogen peroxide water, etc.), but can be properly removed by a cleaning agent composition.

[0156] Examples of acid-producing agents include thermal acid-producing agents and photoacid-producing agents.

[0157] There are no particular limitations on thermally generated acid-producing agents, as long as they produce acid through heat. Specific examples include: 2,4,4,6-tetrabromocyclohexadienone, benzoin tosylate, 2-nitrobenzyl tosylate, K-PURE (registered trademark) CXC-1612, K-PURE CXC-1614, K-PURE TAG-2172, K-PURE TAG-2179, K-PURE TAG-2678, K-PURE TAG-2689, K-PURE 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 organic alkyl sulfonic acid esters, but they are not limited to these.

[0158] Examples of photoacid-generating agents include: onium salt compounds, sulfonylimide compounds, and disulfonyldiazomethane compounds.

[0159] Specific examples of onionium salt compounds include: diphenyliodonium hexafluorophosphate, diphenyliodonium trifluoromethane sulfonate, diphenyliodonium nonafluoron-butane sulfonate, diphenyliodonium perfluoron-octane sulfonate, diphenyliodonium camphor sulfonate, bis(4-tert-butylphenyl)iodonium camphor sulfonate, bis(4-tert-butylphenyl)iodonium trifluoromethane sulfonate, etc.; sulfonium salt compounds such as triphenylsulfonium hexafluoroantimonate, triphenylsulfonium nonafluoron-butane sulfonate, triphenylsulfonium camphor sulfonate, triphenylsulfonium trifluoromethane sulfonate, etc., but are not limited to these.

[0160] Specific examples of sulfonylimide compounds include: N-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluoron-butanesulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, N-(trifluoromethanesulfonyloxy)naphthalenediformimide, etc., but are not limited to these.

[0161] Specific examples of disulfonyl diazonium methane compounds include: bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(2,4-dimethylsulfonyl)diazomethane, methylsulfonyl-p-toluenesulfonyl diazonium methane, etc., but are not limited to these.

[0162] Specific examples of acids include: p-toluenesulfonic acid, pyridonium p-toluenesulfonic acid (pyridonium p-toluenesulfonate), pyridonium phenolsulfonic acid, 5-sulfosalicylic acid, 4-phenolsulfonic acid, 4-chlorobenzenesulfonic acid, benzenedisulfonic acid, 1-naphthalenesulfonic acid, and other aryl sulfonic acids, pyridonium salts, and their salts; salicylic acid, benzoic acid, hydroxybenzoic acid, naphtholic acid, and other aryl carboxylic acids, and their salts; trifluoromethanesulfonic acid, camphorsulfonic acid, and other chain or cyclic alkyl sulfonic acids and their salts; citric acid and other chain or cyclic alkyl carboxylic acids and their salts, but are not limited to these.

[0163] The amount of acid-generating agent and acid contained in the above-mentioned stripping agent composition varies depending on the type of crosslinking agent used, the heating temperature during film formation, etc., and therefore cannot be specified in general terms. It is usually 0.01% to 5% by mass relative to the film composition.

[0164] The release agent composition may contain a surfactant for the purpose of adjusting the liquid properties of the composition itself, the membrane properties of the obtained membrane, and preparing a highly uniform release agent composition with good reproducibility.

[0165] Examples of surfactants include: polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oil-based ether; polyoxyethylene alkyl aryl 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; and nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate. EFTOP Fluorinated surfactants such as EF301, EF303, EF352 (manufactured by Tohkem Products Co., Ltd., trade name), MEGAFACE F171, F173, R-30, R-30N (manufactured by DIC Co., Ltd., trade name), Fluorad FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd., trade name), AsahiGuard AG710, SURFLON S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd., trade name), and organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), etc.

[0166] Surfactants can be used alone or in combination of two or more.

[0167] The amount of surfactant relative to the film composition of the above-mentioned stripper composition is typically less than 2% by mass.

[0168] The above-mentioned stripping agent composition contains branched polysilane.

[0169] Branched polysilanes have Si-Si bonds and a branched structure. Because the release agent composition contains branched polysilanes, the release layer formed by the resulting film cannot be adequately removed by any of organic solvents, acids, or chemicals used in the manufacture of semiconductor devices (alkaline developer, hydrogen peroxide, etc.), but can be adequately removed by a cleaning agent composition. As a result, by cleaning each substrate with a cleaning agent composition after separating the semiconductor substrate and the support substrate of the laminate of the present invention, residues of the release layer on the substrate can be adequately removed. The reason is not yet clear, but it is speculated as follows: depending on the type of terminal groups (terminal substituents (atoms)) of the polysilane, the polysilane can react with organic resins to crosslink. In addition, branched polysilanes have more terminal groups (terminal substituents (atoms)) than linear polysilanes. Therefore, it is believed that branched polysilanes have more crosslinking points than linear polysilanes. Through moderate and appropriate curing via these more crosslinking points in branched polysilanes, it is possible to achieve both the property that cannot be properly removed by organic solvents, acids and chemical solutions used in the manufacture of semiconductor devices (alkaline developer, hydrogen peroxide water, etc.) and the property that can be properly removed by cleaning agent compositions.

[0170] Branched polysilanes preferably contain the structural units shown in formula (B).

[0171]

[0172] R B The term represents a hydrogen atom, hydroxyl group, silyl group, or organic group. Specific examples of such organic groups include: hydrocarbon groups (optionally substituted alkyl, optionally substituted alkenyl, optionally substituted aryl, optionally substituted aralkyl), and corresponding ether groups (optionally substituted alkoxy, optionally substituted aryloxy, optionally substituted aralkoxy, etc.). These organic groups are typically hydrocarbon groups such as alkyl, alkenyl, aryl, and aralkyl. Furthermore, hydrogen atoms, hydroxyl groups, alkoxy groups, silyl groups, etc., are often terminally substituted.

[0173] The alkyl group that may be optionally substituted may be any of the following: straight-chain, branched, or cyclic.

[0174] Specific examples of the optionally substituted straight-chain or branched alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 1-methyl n-butyl, 2-methyl n-butyl, 3-methyl n-butyl, 1,1-dimethyl n-propyl, 1,2-dimethyl n-propyl, 2,2-dimethyl n-propyl, 1-ethyl n-propyl, n-hexyl, 1-methyl n-pentyl, 2-methyl n-pentyl, 3-methyl n-pentyl, 4-methyl n-pentyl, 1,1- Dimethyl n-butyl, 1,2-dimethyl n-butyl, 1,3-dimethyl n-butyl, 2,2-dimethyl n-butyl, 2,3-dimethyl n-butyl, 3,3-dimethyl n-butyl, 1-ethyl n-butyl, 2-ethyl n-butyl, 1,1,2-trimethyl n-propyl, 1,2,2-trimethyl n-propyl, 1-ethyl-1-methyl n-propyl, 1-ethyl-2-methyl n-propyl, etc., but not limited to these, and the number of carbon atoms is usually 1 to 14, preferably 1 to 10, and more preferably 1 to 6.

[0175] Specific examples of optionally substituted cyclic alkyl groups include: cyclopropyl, cyclobutyl, 1-methylcyclopropyl, 2-methylcyclopropyl, cyclopentyl, 1-methylcyclobutyl, 2-methylcyclobutyl, 3-methylcyclobutyl, 1,2-dimethylcyclopropyl, 2,3-dimethylcyclopropyl, 1-ethylcyclopropyl, 2-ethylcyclopropyl, cyclohexyl, 1-methylcyclopentyl, 2-methylcyclopentyl, 3-methylcyclopentyl, 1-ethylcyclobutyl, 2-ethylcyclobutyl, 3-ethylcyclobutyl, 1,2-dimethylcyclobutyl, 1,3-dimethylcyclobutyl, 2,2-dimethylcyclobutyl, 2,3-dimethylcyclobutyl, 2,4-dimethylcyclobutyl Cycloalkyl groups such as 3,3-dimethylcyclobutyl, 1-n-propylcyclopropyl, 2-n-propylcyclopropyl, 1-isopropylcyclopropyl, 2-isopropylcyclopropyl, 1,2,2-trimethylcyclopropyl, 1,2,3-trimethylcyclopropyl, 2,2,3-trimethylcyclopropyl, 1-ethyl-2-methylcyclopropyl, 2-ethyl-1-methylcyclopropyl, 2-ethyl-2-methylcyclopropyl, 2-ethyl-3-methylcyclopropyl; and dicycloalkyl groups such as dicyclobutyl, dicyclopentyl, dicyclohexyl, dicycloheptyl, dicyclooctyl, dicyclononyl, and dicyclodecyl, but not limited to these, and the number of carbon atoms is usually 3 to 14, preferably 4 to 10, and more preferably 5 to 6.

[0176] Alkenes can be linear, branched, or cyclic.

[0177] Specific examples of linear or branched alkenyl groups that may be optionally substituted include vinyl, allyl, butenyl, pentenyl, etc., but are not limited thereto. The number of carbon atoms is usually 2 to 14, preferably 2 to 10, and more preferably 1 to 6.

[0178] Specific examples of cyclic alkenyl groups that may be optionally substituted include cyclopentenyl, cyclohexenyl, etc., but are not limited thereto. The number of carbon atoms is usually 4 to 14, preferably 5 to 10, and more preferably 5 to 6.

[0179] Specific examples of aryl groups that may be optionally substituted include phenyl, 4-methylphenyl, 3-methylphenyl, 2-methylphenyl, 3,5-dimethylphenyl, 1-naphthyl, 2-naphthyl, etc., but are not limited thereto. The number of carbon atoms is usually 6 to 20, preferably 6 to 14, and more preferably 6 to 12.

[0180] Specific examples of optionally substituted aralkyl groups include benzyl, phenethyl, and phenylpropyl, but are not limited thereto. 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 replaced by an aryl group having 6 to 20 carbon atoms.

[0181] The alkyl portion of the optionally substituted alkoxy group can be any of the following: straight-chain, branched, or cyclic.

[0182] Specific examples of linear or branched alkoxy groups that may be optionally substituted include methoxy, ethoxy, propoxy, isopropoxy, butoxy, tert-butoxy, pentooxy, etc., but are not limited thereto. The number of carbon atoms is usually 1 to 14, preferably 1 to 10, and more preferably 1 to 6.

[0183] Specific examples of cyclic alkoxy groups that may be optionally substituted include cyclopentoxy, cyclohexyloxy, etc., but are not limited thereto. The number of carbon atoms is usually 3 to 14, preferably 4 to 10, and more preferably 5 to 6.

[0184] Specific examples of aryloxy groups that may be optionally substituted include phenoxy, 1-naphthoxy, 2-naphthoxy, etc., but are not limited thereto. The number of carbon atoms is usually 6 to 20, preferably 6 to 14, and more preferably 6 to 10.

[0185] Specific examples of optionally substituted arylalkoxy groups include benzyloxy, phenylethoxy, and phenylpropoxy, but are not limited to these. The optionally substituted arylalkoxy group is preferably a group formed by replacing one hydrogen atom of an alkoxy group having 1 to 4 carbon atoms with an aryl group having 6 to 20 carbon atoms.

[0186] Specific examples of silyl groups include silyl, disilyl, trisilyl, etc., but are not limited to these. The number of silicon atoms is usually 1 to 10, preferably 1 to 6.

[0187] In R BIn the case of the aforementioned organic group or silyl group, at least one of its hydrogen atoms is optionally substituted with a substituent. Specific examples of such substituents include hydroxyl, alkyl, aryl, alkoxy, etc.

[0188] From the viewpoint of suppressing accidental peeling when the laminate of the present invention comes into contact with any of the organic solvents, acids, or chemical solutions (alkaline developing solutions, hydrogen peroxide water, etc.) used in the manufacture of semiconductor devices, and from the viewpoint of properly removing residues of the peeling layer on the substrate after separating the semiconductor substrate and the support substrate of the laminate of the present invention and cleaning each substrate with a cleaning agent composition, R B Preferably alkyl or aryl, more preferably aryl, even more preferably phenyl, 1-naphthyl or 2-naphthyl, and even more preferably phenyl.

[0189] The branched polysilane used in this invention may include the structural units shown in formula (S) and formula (N) together with the structural unit shown in formula (B). However, from the viewpoint of suppressing accidental peeling when the laminate of this invention comes into contact with any of the organic solvents, acids, or chemical solutions (alkaline developer, hydrogen peroxide water, etc.) used in the manufacture of semiconductor devices, and from the viewpoint of properly removing residues of the peeling layer on the substrate after cleaning each substrate with a cleaning agent composition after separating the semiconductor substrate and the support substrate of the laminate of this invention, the content of the structural unit shown in formula (B) in the branched polysilane is generally 50 mol% or more, preferably 60 mol% or more, more preferably 70 mol% or more, even more preferably 80 mol% or more, even more preferably 90% or more, and even more preferably 95 mol% or more.

[0190]

[0191] (R S1 and R S2 Indicates with R B Same meaning.

[0192] The terminal groups (terminal substituents (atoms)) of branched polysilanes can typically be hydrogen atoms, hydroxyl groups, halogen atoms (chlorine atoms, etc.), alkyl groups, aryl groups, alkoxy groups, silyl groups, etc. Among these, hydroxyl, methyl, and phenyl groups are most common, with methyl being the preferred choice. The terminal group can be trimethylsilyl.

[0193] In one embodiment, the average degree of polymerization of the branched polysilane, expressed in terms of silicon atoms (i.e., the average number of silicon atoms per molecule), is typically 2 to 100, preferably 3 to 80, more preferably 5 to 50, and even more preferably 10 to 30.

[0194] In one embodiment, the upper limit of the weight-average molecular weight of the branched polysilane is typically 30,000, preferably 20,000, more preferably 10,000, even more preferably 5,000, further preferably 2,000, and even more preferably 1,500. The lower limit is typically 50, preferably 100, more preferably 150, even more preferably 200, even more preferably 300, and even more preferably 500.

[0195] Regarding the average degree of polymerization and weight-average molecular weight of the polysilanes used in this invention, for example, a GPC apparatus (EcoSEC, HLC-8220GPC manufactured by Tosoh Corporation) and a GPC column (Showa Denko Corporation, using Shodex KF-803L, KF-802 and KF-801 in sequence) can be used, with the column temperature set to 40°C, tetrahydrofuran used as the eluent (dissolution solvent), the flow rate set to 1.00 mL / min, and polystyrene (manufactured by Sigma Aldrich) used as the standard sample, the determination can be performed.

[0196] If the degree of polymerization and weight-average molecular weight of the branched polysilane used are too small, the polysilane may vaporize due to heating during the formation of the film as a release layer or during the processing of the laminate containing the obtained release layer, or adverse conditions may occur due to poor film strength. If the degree of polymerization and weight-average molecular weight of the branched polysilane used are too large, precipitation may occur in the composition due to insufficient solubility of the solvent used in the preparation of the release agent composition, or the mixing with the resin may become insufficient, making it impossible to obtain a highly uniform film with good reproducibility.

[0197] Therefore, from the viewpoint of obtaining a laminate with a release layer that is conducive to the proper manufacture of semiconductor devices with good reproducibility, it is ideal for the degree of polymerization and weight-average molecular weight of the branched polysilane to meet the above-mentioned range.

[0198] From the viewpoint of obtaining a release layer with good reproducibility and excellent heat resistance, the branched polysilane used in this invention is typically reduced by 5% at a temperature of 300°C or higher, preferably 350°C or higher, more preferably 365°C or higher, even more preferably 380°C or higher, even more preferably 395°C or higher, and still more preferably 400°C or higher.

[0199] Regarding the temperature at which the polysilane used in this invention is reduced by 5% by weight, for example, it can be measured by heating from room temperature (25°C) to 400°C in air at a rate of 10°C / min using NETZSCH 2010SR.

[0200] From the viewpoints of properly removing residues of the release layer on the substrate after cleaning each substrate with a cleaning agent composition following separation of the semiconductor substrate and support substrate of the laminate of the present invention, and from the viewpoints of preparing a release agent composition with excellent reproducibility and uniformity, the branched polysilane used in the present invention is preferably soluble in any one of the following: ether compounds such as tetrahydrofuran; aromatic compounds such as toluene; glycol ether ester compounds such as propylene glycol monomethyl ether acetate; ketone compounds such as cyclohexanone and methyl ethyl ketone; and glycol ether compounds such as propylene glycol monomethyl ether. It should be noted that, in this case, dissolution refers to the situation where, when attempting to dissolve the solution at room temperature (25°C) using a shaker to obtain a 10% by mass solution, it can be visually confirmed that the solution dissolves within 1 hour.

[0201] Branched polysilanes can be in either solid or liquid form at room temperature.

[0202] The branched polysilanes used in this invention can be manufactured using methods known in Japanese Patent Application Publication No. 2011-208054, Japanese Patent Application Publication No. 2007-106894, Japanese Patent Application Publication No. 2007-145879, and WO2005 / 113648, and can also be obtained as commercially available products. Specific examples of commercially available products include polysilanes OGSOLSI-20-10 and SI-20-14 for silicon materials manufactured by Osaka Gas Chemical Co., Ltd., but are not limited to these.

[0203] As a preferred example of branched polysilanes, the following substances can be listed, but are not limited to.

[0204]

[0205] (Ph represents phenyl, R) E Indicates terminal substituents, representing atoms or groups, n b This indicates the number of repeating units.

[0206] The content of branched polysilane in the above-mentioned stripping agent composition is generally 10 to 90% by mass relative to the film composition. However, from the viewpoint of achieving good reproducibility of a film that cannot be properly removed by organic solvents, acids or chemical solutions used in the manufacture of semiconductor devices (alkaline developer, hydrogen peroxide, etc.) but can be properly removed by the 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 even more preferably 30% to 50% by mass.

[0207] The above-mentioned stripping agent composition contains a solvent.

[0208] As such solvents, for example, highly polar solvents that can effectively dissolve film-forming components such as organic resins and branched polysilanes can be used. Low-polarity solvents can be used as needed, for purposes such as adjusting viscosity and surface tension. It should be noted that, in this invention, a low-polarity solvent is defined as a solvent with a relative permittivity of less than 7 at a frequency of 100 kHz, and a highly polar solvent is defined as a solvent with a relative permittivity of 7 or higher at a frequency of 100 kHz. One solvent can be used alone, or two or more solvents can be used in combination.

[0209] In addition, examples of highly polar solvents include: amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylisobutyramide, N-methylpyrrolidone, and 1,3-dimethyl-2-imidazolinone; ketone solvents such as ethyl methyl ketone, isophorone, and cyclohexanone; cyano solvents such as acetonitrile and 3-methoxypropionitrile; polyol solvents such as ethylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, 1,3-butanediol, and 2,3-butanediol; monohydric alcohol solvents other than aliphatic alcohols such as propylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monophenyl ether, triethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, benzyl alcohol, 2-phenoxyethanol, 2-benzyloxyethanol, 3-phenoxybenzyl alcohol, and tetrahydrofurfuryl alcohol; and sulfoxide solvents such as dimethyl sulfoxide.

[0210] Examples of low-polarity solvents include: chloroform, chlorobenzene, and other chlorine-based solvents; alkylbenzene-based solvents such as toluene, xylene, tetrahydronaphthalene, cyclohexylbenzene, and decylbenzene; aliphatic alcohol-based solvents such as 1-octanol, 1-nonanol, and 1-decanol; ether-based solvents such as tetrahydrofuran, dioxane, anisole, 4-methoxytoluene, 3-phenoxytoluene, dibenzyl ether, diethylene glycol dimethyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, and triethylene glycol butyl methyl ether; and ester-based solvents such as methyl benzoate, ethyl benzoate, butyl benzoate, isoamyl benzoate, bis(2-ethylhexyl) phthalate, dibutyl maleate, dibutyl oxalate, hexyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, and diethylene glycol monobutyl ether acetate.

[0211] The solvent content can be appropriately set considering factors such as the desired viscosity of the composition, the coating method used, and the thickness of the film produced, and is preferably 99% or less of the total composition, and more preferably 70% to 99% of the total composition. That is, in this case, the amount of the film-forming component is 1% to 30% of the total composition. It should be noted that, in this invention, the film-forming component refers to components other than the solvent contained in the composition.

[0212] The viscosity and surface tension of the above-mentioned stripping agent composition can be appropriately adjusted by taking into account various factors such as the coating method used and the desired film thickness, and by changing the type of solvent used, their ratio, and the concentration of film components.

[0213] In one aspect of the present invention, from the viewpoints of obtaining a composition with good reproducibility and high homogeneity, obtaining a composition with good reproducibility and high storage stability, and obtaining a composition with good reproducibility that provides a film with high homogeneity, the above-mentioned stripping agent composition comprises a glycol-based solvent. It should be noted that the term "glycol-based solvent" as used herein refers to a general term for glycols, glycol monoethers, glycol diethers, glycol monoesters, glycol diesters, and glycol ester ethers.

[0214] An example of a preferred diol solvent is represented by formula (G).

[0215]

[0216] In formula (G), R G1 Each independently represents a straight-chain or branched alkylene group having 2 to 4 carbon atoms, R G2 and R G3 Each independently represents a hydrogen atom, a straight-chain or branched alkyl group having 1 to 8 carbon atoms, or an alkyl group whose alkyl portion is a straight-chain or branched alkyl group having 1 to 8 carbon atoms, n g It is an integer from 1 to 6.

[0217] Specific examples of straight-chain or branched alkylene groups with 2 to 4 carbon atoms include: ethylene, trimethylene, 1-methylethylene, tetramethylene, 2-methylpropane-1,3-diyl, pentamethylene, hexamethylene, etc., but are not limited to these.

[0218] From the viewpoints of obtaining a composition with good reproducibility and high uniformity, obtaining a composition with good reproducibility and high storage stability, and obtaining a composition with good reproducibility that provides a film with high uniformity, it is preferable to use a straight-chain or branched alkylene group having 2 to 3 carbon atoms, and more preferably a straight-chain or branched alkylene group having 3 carbon atoms.

[0219] Specific examples of linear or branched alkyl groups having 1 to 8 carbon atoms include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl, 1,2-dimethyl-n-propyl, 2,2-dimethyl-n-propyl, 1-ethyl-n-propyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n-propyl. n-Amyl, 4-methyln-amyl, 1,1-dimethyln-butyl, 1,2-dimethyln-butyl, 1,3-dimethyln-butyl, 2,2-dimethyln-butyl, 2,3-dimethyln-butyl, 3,3-dimethyln-butyl, 1-ethyln-butyl, 2-ethyln-butyl, 1,1,2-trimethyln-propyl, 1,2,2-trimethyln-propyl, 1-ethyl-1-methyln-propyl, 1-ethyl-2-methyln-propyl, etc., but not limited to these.

[0220] From the viewpoints of obtaining a composition with good reproducibility and high uniformity, obtaining a composition with good reproducibility and high storage stability, and obtaining a composition with good reproducibility that provides a film with high uniformity, methyl or ethyl is preferred, and methyl is more preferred.

[0221] Specific examples of alkyl acyl groups having 1 to 8 carbon atoms in a straight-chain or branched alkyl group having 1 to 8 carbon atoms can be listed as the same groups as the specific examples described above.

[0222] From the viewpoints of obtaining a composition with good reproducibility and high uniformity, obtaining a composition with good reproducibility and high storage stability, and obtaining a composition with good reproducibility that provides a film with high uniformity, methyl carbonyl or ethyl carbonyl is preferred, and methyl carbonyl is more preferred.

[0223] From the perspectives of obtaining compositions with good reproducibility and high homogeneity, obtaining compositions with good reproducibility and high storage stability, and obtaining compositions with good reproducibility that provide highly uniform films, n g Preferably 4 or less, more preferably 3 or less, even more preferably 2 or less, and most preferably 1.

[0224] From the viewpoints of obtaining a composition with good reproducibility and high homogeneity, obtaining a composition with good reproducibility and high storage stability, and obtaining a composition with good reproducibility that provides a film with high homogeneity, R is preferred in formula (G). G2 and R G3 At least one of them is a linear or branched alkyl group having 1 to 8 carbon atoms, more preferably R. G2 and R G3One side is a straight-chain or branched alkyl group with 1 to 8 carbon atoms, and the other side is an alkyl acyl group with hydrogen atoms or an alkyl part consisting of a straight-chain or branched alkyl group with 1 to 8 carbon atoms.

[0225] From the viewpoints of obtaining a composition with good reproducibility and high uniformity, obtaining a composition with good reproducibility and high storage stability, and obtaining a composition with good reproducibility that provides a film with high uniformity, the content of the glycol solvent relative to the solvent contained in the above-mentioned stripping agent composition is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, even more preferably 90% by mass or more, and even more preferably 95% by mass or more.

[0226] From the viewpoints of obtaining a composition with good reproducibility and high uniformity, obtaining a composition with good reproducibility and high storage stability, and obtaining a composition with good reproducibility and providing a film with high uniformity, the film components in the above-mentioned stripping agent composition are uniformly dispersed or dissolved in the solvent, preferably dissolved.

[0227] The above-mentioned stripping agent composition can be manufactured by mixing an organic resin, a branched polysilane, and a solvent.

[0228] The mixing order is not particularly limited. As an example of a method for easily and reproducibly manufacturing a release agent composition, methods include: dissolving the organic resin and branched polysilane in a solvent in one step; dissolving a portion of the organic resin and branched polysilane in a solvent, dissolving the remainder separately in a solvent, and mixing the resulting solutions. However, this method is not limited to these methods. It should be noted that, in this case, the organic resin solution can also be used directly, or by concentrating or diluting the reaction solution obtained during the synthesis of the organic resin. Furthermore, when preparing the release agent composition, appropriate heating can be applied within a range that does not cause decomposition or deterioration of the components.

[0229] In this invention, for the purpose of removing foreign matter, the solvent, solution, etc. used may be filtered using a submicron-sized filter or the like during the manufacturing of the stripping agent composition or after mixing all the components.

[0230] The thickness of the release layer in the laminate of the present invention is typically 5 nm to 100 μm, 10 nm to 1 μm in one embodiment, and 50 nm to 500 nm in other embodiments.

[0231] The release agent composition described above is also the subject of this invention, and the relevant conditions (preferred conditions, manufacturing conditions, etc.) are as described above. By using the release agent composition of this invention, for example, it is possible to reproducibly manufacture films suitable as release layers for use in the manufacture of semiconductor devices.

[0232] In particular, the release agent composition of the present invention can be adapted to form the release layer of the above-mentioned laminate, which includes a semiconductor substrate, a support substrate, an adhesive layer disposed between the semiconductor substrate and the support substrate and attached to the semiconductor substrate, and a release layer disposed attached to the support substrate and the adhesive layer. When the support substrate of such a laminate is light-transmitting, the separation or decomposition of the release layer is properly performed as described above by irradiating the release layer from the support substrate side. As a result, the semiconductor substrate can be separated from the support substrate without further applying excessive load for peeling, and by cleaning the separated semiconductor substrate with a cleaning agent composition, proper cleaning of the substrate can be achieved without leaving any residue of the release layer on the substrate.

[0233] One characteristic of the release layer obtained from the release agent composition of the present invention is that it cannot be adequately removed by organic solvents, acids, or solutions used in the manufacture of semiconductor devices (alkaline developers, hydrogen peroxide, etc.), but can be adequately removed by a cleaning agent composition. This specific and selective removeability is achieved by the branched polysilane contained in the release agent composition of the present invention, which functions as a solubility enhancer or removeability enhancer of the release layer in the cleaning agent composition, and further functions as a solubility reducer or removeability reducer of the release layer in organic solvents, acids, or solutions used in the manufacture of semiconductor devices (alkaline developers, hydrogen peroxide, etc.).

[0234] As described above, the release layer obtained from the release agent composition of the present invention cannot be properly removed by organic solvents, acids, or solutions used in the manufacture of semiconductor devices (alkali developing solutions, hydrogen peroxide water, etc.).

[0235] Specific examples of such organic solvents typically include: straight-chain or branched aliphatic saturated hydrocarbons such as hexane, heptane, octane, nonane, decane, undecane, dodecane, and isododecane; cyclic aliphatic saturated hydrocarbons such as cyclohexane, cycloheptane, cyclooctane, isopropylcyclohexane, and p-menthane; cyclic aliphatic unsaturated hydrocarbons such as limonene; aromatic hydrocarbons such as benzene, toluene, o-xylene, m-xylene, p-xylene, mesitylene, 1,2,4-trimethylbenzene, cumene, 1,4-diisopropylbenzene, and p-isopropyltoluene; dialkyl ketones such as MIBK (methyl isobutyl ketone), methyl ethyl ketone, acetone, diisobutyl ketone, 2-octanone, 2-nonanone, and 5-nonanone; and cyclohexane... Ketones such as cycloalkyl ketones and aliphatic saturated hydrocarbon ketones; ketones such as isophorones and alkenyl ketones and aliphatic unsaturated hydrocarbon ketones; dialkyl ethers such as diethyl ether, di(n-propyl) ether, di(n-butyl) ether, and di(n-pentyl) ether; ethers such as tetrahydrofuran and dioxane cyclic alkyl ethers; sulfides such as diethyl sulfide, di(n-propyl) sulfide, and di(n-butyl) sulfide; amides such as N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylisobutyramide, N-methylpyrrolidone, and 1,3-dimethyl-2-imidazolinone; nitriles such as acetonitrile and 3-methoxypropionitrile; polyols such as ethylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, 1,3-butanediol, and 2,3-butanediol; and propylene glycol monomethyl ether and diethylene glycol. Monomethyl ethers, triethylene glycol monomethyl ethers, dipropylene glycol monomethyl ethers, and other diethanol monoalkyl ethers; diethylene glycol monophenyl ethers, diethanol monoaryl ethers, and other diethanol monohydrocarbon ethers; straight-chain or branched alkyl monools such as methanol, ethanol, and propanol; cyclohexanols and other cyclic alkyl alcohols; monoalcohols other than alkyl alcohols such as diacetone alcohol, benzyl alcohol, 2-phenoxyethanol, 2-benzyloxyethanol, 3-phenoxybenzyl alcohol, and tetrahydrofurfuryl alcohol; diols such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, tripropylene glycol, hexanediol, triethylene glycol, 1,2-butanediol, 2,3-butanediol, 1,3-butanediol, 1,4-butanediol, and 1,5-pentanediol; ethylene glycol monohexyl ether, propylene glycol monobutyl ether, diethylene glycol monoethyl ether, dipropylene glycol monobutyl ether, and ethylene glycol monobutyl ether. Monobutyl ethers of alcohols, 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, tripropylene glycol monobutyl ether, etc., dialkyl ethers of glycols; 2-phenoxyethanol and other diaryl ethers of glycols; dibutyl ether of ethylene glycol, dimethyl ether of diethylene glycol, diethyl ether of diethylene glycol, diethyl ether of diethylene glycol, dibutyl ether of propylene glycol, dimethyl n-propyl ether of dipropylene glycol, dimethyl ether of dipropylene glycol, diethyl ether of dipropylene glycol, dibutyl ether of dipropylene glycol, dimethyl ether of diethylene glycol, triethylene glycol dimethyl ether, triethylene glycol butyl methyl ether, tetraethylene glycol dimethyl ether, etc., dialkyl ethers of glycols, etc.Dipropylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, and other diol monoalkyl ether acetates; cyclic carbonates such as ethylene carbonate, propylene carbonate, and vinylene carbonate; esters such as butyl acetate and amyl acetate, etc.

[0236] Examples of such acids include: inorganic acids such as phosphoric acid, hydrochloric acid, perchloric acid, nitric acid, and sulfuric acid, and their salts; aryl sulfonic acids such as p-toluenesulfonic acid, pyridonium p-toluenesulfonic acid (pyridonium p-toluenesulfonate), pyridonium phenolsulfonic acid, 5-sulfosalicylic acid, 4-phenolsulfonic acid, 4-chlorobenzenesulfonic acid, benzenedisulfonic acid, and 1-naphthalenesulfonic acid, and their salts; aryl carboxylic acids such as salicylic acid, benzoic acid, hydroxybenzoic acid, and naphthoic acid, and their salts; chain or cyclic alkyl sulfonic acids such as trifluoromethanesulfonic acid and camphorsulfonic acid, and their salts; chain or cyclic alkyl carboxylic acids such as citric acid, and their salts, but are not limited to these.

[0237] Examples of such alkaline developing solutions include: aqueous solutions of alkali metal hydroxides such as potassium hydroxide and sodium hydroxide; aqueous solutions of quaternary ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline; and alkaline aqueous solutions of amines such as ethanolamine, propylamine, and ethylenediamine, but these are not limited to these examples.

[0238] The characteristic that the release layer obtained from the release agent composition of the present invention cannot be properly removed by organic solvents, acids or solutions used in the manufacture of semiconductor devices (alkaline developer, hydrogen peroxide water, etc.) can be evaluated by the following methods.

[0239] That is, a 200 nm thick film formed on a 4 cm square silicon wafer can be immersed together with the silicon wafer in 7 mL of evaluation liquid, and the film thickness before and after immersion can be compared, and the evaluation is based on the film thickness reduction rate (%) of the film thickness after immersion relative to the film thickness before immersion.

[0240] The release layer obtained from the release agent composition of the present invention exhibits a low film reduction rate even after being immersed in organic solvents, acids, or solutions used in the manufacture of semiconductor devices (alkaline developer, hydrogen peroxide, etc.) in such a manner, typically less than 6%, less than 5% in a preferred embodiment, less than 4% in a more preferred embodiment, less than 3% in a further preferred embodiment, less than 2% in a further preferred embodiment, less than 1% in an even more preferred embodiment, and 0% in the most preferred embodiment. It should be noted that the film reduction rate can be calculated using the formula: film thickness after immersion (nm) / film thickness before immersion (nm) × 100.

[0241] As described above, the stripping layer obtained from the stripping agent composition of the present invention can be appropriately removed by a cleaning agent composition, which typically contains salt and solvent.

[0242] As a preferred example of a cleaning agent composition, a cleaning agent composition comprising a quaternary ammonium salt and a solvent can be cited.

[0243] Quaternary ammonium salts consist of quaternary ammonium cations and anions, and there are no particular limitations as long as they are used for this purpose.

[0244] Typical examples of such quaternary ammonium cations include tetra(hydrocarbon)ammonium cations. On the other hand, examples of their paired anions include hydroxide ions (OH-). － ); Fluoride ions (F － ), chloride ions (Cl) － ), bromide ions (Br) － ), iodide ions (I) － Halogen ions such as tetrafluoroborate ions (BF4) － ); hexafluorophosphate ion (PF6) － (etc.), but not limited to this.

[0245] In this invention, the quaternary ammonium salt is preferably a halogenated quaternary ammonium salt, and more preferably a fluorine-containing quaternary ammonium salt.

[0246] In quaternary ammonium salts, halogen atoms can be contained in cations or anions, preferably in anions.

[0247] In a preferred embodiment, the fluorinated quaternary ammonium salt is tetra(hydrocarbon)ammonium fluoride.

[0248] Specific examples of hydrocarbon groups in tetraammonium fluoride include: alkyl groups with 1 to 20 carbon atoms, alkenyl groups with 2 to 20 carbon atoms, alkynyl groups with 2 to 20 carbon atoms, and aryl groups with 6 to 20 carbon atoms.

[0249] In a more preferred embodiment, tetra(hydrocarbon)ammonium fluoride comprises tetraalkylammonium fluoride.

[0250] Specific examples of tetraalkylammonium fluoride include tetramethylammonium fluoride, tetraethylammonium fluoride, tetrapropylammonium fluoride, and tetrabutylammonium fluoride (also known as tetrabutylammonium fluoride), but are not limited to these. Among them, tetrabutylammonium fluoride is preferred.

[0251] Quaternary ammonium salts such as tetra(hydrocarbon)ammonium fluoride can be used in hydrate form. Furthermore, quaternary ammonium salts such as tetra(hydrocarbon)ammonium fluoride can be used alone or in combination of two or more.

[0252] There is no particular limitation on the amount of quaternary ammonium salt as long as it is dissolved in the solvent contained in the cleaning agent composition, which is usually 0.1% to 30% by mass relative to the cleaning agent composition.

[0253] The solvent contained in the cleaning agent composition used in this invention is not particularly limited as long as it is used for this purpose and can dissolve the aforementioned quaternary ammonium salts and other salts. From the viewpoints of obtaining a cleaning agent composition with good reproducibility and excellent cleaning properties, and of obtaining a cleaning agent composition with good dissolution of quaternary ammonium salts and other salts and excellent uniformity, it is preferable that the cleaning agent composition used in this invention contains one or more amide solvents.

[0254] As a preferred example of an amide solvent, an amide derivative represented by formula (Z) can be cited.

[0255]

[0256] In the formula, R 0 The symbol represents ethyl, propyl, or isopropyl, preferably ethyl or isopropyl, and more preferably ethyl. R A and R B Each alkyl group independently represents an alkyl group having 1 to 4 carbon atoms. Alkyl groups having 1 to 4 carbon atoms can be straight-chain, branched, or cyclic, and specific examples include methyl, ethyl, propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, and cyclobutyl. Among these, R... A and R B Preferably, it is methyl or ethyl.

[0257] Examples of amide derivatives 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, and N-ethyl-N-methylisobutyramide. Among these, N,N-dimethylpropionamide is particularly preferred.

[0258] The amide derivatives shown in formula (Z) can be synthesized by substitution reaction of the corresponding carboxylic acid ester with an amine, or by using commercially available products.

[0259] Another example of a preferred amide solvent is the lactam compound represented by formula (Y).

[0260]

[0261] In the above formula (Y), specific examples of alkyl groups having 1 to 6 carbon atoms include methyl, ethyl, n-propyl, n-butyl, etc., and specific examples of alkylene groups having 1 to 6 carbon atoms include methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, etc., but are not limited to these.

[0262] As specific examples of the lactam compounds shown in the above formula (Y), α-lactam compounds, β-lactam compounds, γ-lactam compounds, δ-lactam compounds, etc. can be listed, and they can be used alone or in combination of two or more.

[0263] In a preferred embodiment of the invention, the lactam compound represented by formula (Y) above comprises 1-alkyl-2-pyrrolidone (N-alkyl-γ-butyrolactam), in a more preferred embodiment it comprises N-methylpyrrolidone (NMP) or N-ethylpyrrolidone (NEP), and in a further preferred embodiment it comprises N-methylpyrrolidone (NMP).

[0264] The cleaning agent composition used in this invention may contain one or more other organic solvents that are different from the amide compounds described above.

[0265] There are no particular limitations on other organic solvents, as long as they are used for this purpose and are compatible with the aforementioned amide compounds.

[0266] Other preferred solvents include alkylene glycol dialkyl ethers, aromatic hydrocarbon compounds, and ether compounds containing cyclic structures, but are not limited to these.

[0267] Regarding the amount of other organic solvents different from the aforementioned amide compounds, as long as the quaternary ammonium salt contained in the cleaning agent composition does not precipitate or separate and is uniformly mixed with the aforementioned amide compounds, it is generally appropriately determined to be less than 95% by mass in the solvent contained in the cleaning agent composition.

[0268] It should be noted that the cleaning agent composition used in this invention may contain water as a solvent, but from the viewpoint of avoiding substrate corrosion, organic solvents are generally only intentionally used as solvents. It should be noted that this does not mean that the hydrated water containing salt in the cleaning agent composition or the trace amounts of water contained in the organic solvent are excluded. The water content of the cleaning agent composition used in this invention is generally 5% by mass or less.

[0269] The property that the release layer obtained from the release agent composition of the present invention can be properly removed by the cleaning agent composition can be evaluated in the same way as described above, in terms of film reduction rate (%).

[0270] The release layer obtained from the release agent composition of the present invention, after being impregnated with the cleaning agent composition by the method described above, exhibits the following high film reduction rate, typically 94% or more, preferably 95% or more, more preferably 96% or more, even more preferably 97% or more, even more preferably 98% or more, even more preferably 99% or more, and most preferably 100%.

[0271] The adhesive layer of the laminate of the present invention may, for example, be a film obtained from an adhesive composition containing adhesive component (S).

[0272] Such adhesive component (S) is not particularly limited as long as it is an adhesive component used for this purpose. Examples include: polysiloxane adhesives, acrylic resin adhesives, epoxy resin adhesives, polyamide adhesives, polystyrene adhesives, polyimide adhesives, phenolic resin adhesives, etc., but it is not limited to these.

[0273] Among them, the adhesive exhibits appropriate bonding ability during the processing of wafers, etc., can be properly peeled off after processing, has excellent heat resistance, and can be properly removed by the cleaning agent composition described above. Therefore, as the adhesive component (S), a polysiloxane-based adhesive is preferred.

[0274] In a preferred embodiment, the adhesive composition used in this invention comprises a polyorganosiloxane component (A) cured by a hydrosilylation reaction as an adhesive component. In a more preferred example, the polyorganosiloxane component (A) cured by a hydrosilylation reaction comprises a polysiloxane (A1) and a platinum group metal catalyst (A2), wherein the polysiloxane (A1) comprises siloxane units (Q units) selected from SiO2 and R... 1 R 2 R 3 SiO 1 / 2 The siloxane unit (M unit) and R shown are shown. 4 R 5 SiO 2 / 2 The siloxane unit (D unit) and R shown are shown. 6 SiO 3 / 2 The polysiloxane (A1) comprises one or more units from the group consisting of the shown siloxane units (T units), wherein the polysiloxane (A1) includes polyorganosiloxane (a1) and polyorganosiloxane (a2), and the polyorganosiloxane (a1) includes siloxane units (Q' units) selected from SiO2 and R... 1 'R 2 'R 3 'SiO 1 / 2 The siloxane unit (M' unit) and R shown are shown. 4 'R5 'SiO 2 / 2 The siloxane unit (D' unit) and R shown are shown. 6 'SiO 3 / 2 The polyorganosiloxane (a2) comprises one or more units selected from the group consisting of the siloxane units (T' units) shown, and includes at least one unit selected from the group consisting of the M' units, D' units, and T' units described above. 1 R 2 R 3 "SiO" 1 / 2 The siloxane unit (M” unit) and R shown 4 R 5 "SiO" 2 / 2 The siloxane unit (D” unit) and R shown are shown. 6 "SiO" 3 / 2 The siloxane unit (T” unit) shown is one or more units from the group consisting of the siloxane unit (T” unit) shown, and includes at least one unit selected from the group consisting of the M” unit, D” unit and T” unit.

[0275] R 1 ~R 6 Each group or atom bonded to a silicon atom is independently represented as an alkyl, alkenyl, or hydrogen atom.

[0276] R 1 '~R 6 'A group bonded to a silicon atom, each independently representing an alkyl or alkenyl group, but R 1 '~R 6 At least one of them is an alkenyl group.

[0277] R 1 "~R 6 "R represents a group or atom bonded to a silicon atom, each independently representing an alkyl group or a hydrogen atom." 1 "~R 6 At least one of the atoms in the symbol is a hydrogen atom.

[0278] The alkyl group can be any of straight-chain, branched, or cyclic, preferably straight-chain or branched alkyl groups. The number of carbon atoms is not particularly limited, usually 1 to 40, preferably 30 or less, more preferably 20 or less, and even more preferably 10 or less.

[0279] Specific examples of straight-chain or branched alkyl groups can be listed in relation to R. 901 and R 902 The same groups as the aforementioned optionally substituted linear or branched alkyl groups. Among them, methyl is preferred.

[0280] Specific examples of cyclic alkyl groups can be listed in relation to R. 901 and R 902 The above-mentioned optional substituted cyclic alkyl groups are the same as the specific examples of the groups.

[0281] The alkenyl group can be either linear or branched, and its number of carbon atoms is not particularly limited, usually ranging from 2 to 40, preferably 30 or less, more preferably 20 or less, and even more preferably 10 or less.

[0282] As specific examples of alkenes, those related to R can be listed. 901 and R 902 The same group as the aforementioned optionally substituted alkenyl groups. Among them, vinyl and 2-propenyl groups are preferred.

[0283] As described above, the polysiloxane (A1) comprises polyorganosiloxane (a1) and polyorganosiloxane (a2). The alkenyl group contained in polyorganosiloxane (a1) and the hydrogen atoms (Si-H groups) contained in polyorganosiloxane (a2) form a cross-linked structure and are cured through a hydrosilylation reaction based on a platinum group metal catalyst (A2). As a result, a cured film is formed.

[0284] The polyorganosiloxane (a1) comprises one or more units selected from the group consisting of Q' units, M' units, D' units, and T' units, and comprises at least one unit selected from the group consisting of the aforementioned M' units, D' units, and T' units. Two or more polyorganosiloxanes satisfying this condition may also be used in combination as the polyorganosiloxane (a1).

[0285] As for two or more preferred combinations selected from the group consisting of Q' unit, M' unit, D' unit and T' unit, examples 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 to these.

[0286] Furthermore, when the polyorganosiloxane contained in two or more polyorganosiloxanes (a1) is included, combinations of (Q' units and M' units) and (D' units and M' units), combinations of (T' units and M' units) and (D' units and M' units), and combinations of (Q' units, T' units and M' units) and (T' units and M' units) are preferred, but not limited thereto.

[0287] The polyorganosiloxane (a2) comprises one or more units selected from the group consisting of Q” units, M” units, D” units and T” units, and comprises at least one unit selected from the group consisting of the aforementioned M” units, D” units and T” units. As the polyorganosiloxane (a2), two or more polyorganosiloxanes satisfying such conditions may also be used in combination.

[0288] As for two or more preferred combinations selected from the group consisting of Q” units, M” units, D” units and T” units, examples include: (M” units and D” units), (Q” units and M” units), (Q” units, T” units and M” units), but are not limited to these.

[0289] Polyorganosiloxanes (a1) are composed of siloxane units formed by the bonding of alkyl and / or alkenyl groups to their silicon atoms, R 1 '~R 6 The proportion of alkenyl groups in all the substituents shown is preferably 0.1 mol% to 50.0 mol%, more preferably 0.5 mol% to 30.0 mol%, with the remainder being R. 1 '~R 6 'It can be set as an alkyl group.'

[0290] Polyorganosiloxanes (a2) are composed of siloxane units formed by the bonding of alkyl and / or hydrogen atoms with their silicon atoms, R 1 "~R 6 The proportion of hydrogen atoms in all substituents and substituted atoms shown is preferably 0.1 mol% to 50.0 mol%, more preferably 10.0 mol% to 40.0 mol%, with the remainder being R. 1 "~R 6 "It can be set as an alkyl group."

[0291] Polysiloxane (A1) comprises polyorganosiloxane (a1) and polyorganosiloxane (a2). In a preferred embodiment of the present invention, the molar ratio of the alkenyl group contained in polyorganosiloxane (a1) to the hydrogen atoms constituting Si-H bonds contained in polyorganosiloxane (a2) is in the range of 1.0:0.5 to 1.0:0.66.

[0292] The weight-average molecular weights of polysiloxanes such as polyorganosiloxane (a1) and polyorganosiloxane (a2) are typically 500 to 1,000,000, but from the viewpoint of achieving the effects of the present invention with good reproducibility, 5,000 to 50,000 are preferred.

[0293] It should be noted that, in this invention, the weight-average molecular weight, number-average molecular weight, and dispersity of the polyorganosiloxane can be determined, for example, using a GPC apparatus (Tosoh EcoSEC, HLC-8320GPC) and a GPC column (Tosoh TSKgel SuperMultipore HZ-N, TSKgel SuperMultipore HZ-H), with the column temperature set to 40°C, tetrahydrofuran used as the eluent (dissolution solvent), the flow rate set to 0.35 mL / min, and polystyrene (Sigma Aldrich) used as the standard sample.

[0294] The viscosities of polyorganosiloxane (a1) and polyorganosiloxane (a2) are typically 10 to 1,000,000 mPa·s, and preferably 50 to 10,000 mPa·s from the viewpoint of achieving the effects of the present invention with good reproducibility. It should be noted that the viscosities of polyorganosiloxane (a1) and polyorganosiloxane (a2) are values ​​measured at 25°C using an E-type rotational viscometer.

[0295] Polyorganosiloxane (a1) and polyorganosiloxane (a2) react with each other to form a film via a hydrosilylation reaction. Therefore, their curing mechanism is different from that via silanol groups, and thus, no siloxane needs to contain silanol groups, such as alkoxy groups, which are functional groups that form silanol groups through hydrolysis.

[0296] In a preferred embodiment of the present invention, the adhesive component (S) also includes the polysiloxane (A1) and platinum group metal catalyst (A2) described above.

[0297] Such platinum-based metal catalysts are used to promote the hydrosilylation reaction of the alkenyl group of polyorganosiloxane (a1) with the Si-H group of polyorganosiloxane (a2).

[0298] Specific examples of platinum-based metal catalysts include: platinum black, platinum tetrachloride, chloroplatinic acid, the reaction product of chloroplatinic acid and a monohydric alcohol, the complex of chloroplatinic acid and an olefin, and platinum diacetate, but are not limited to these.

[0299] Examples of platinum complexes with alkenes include, but are not limited to, complexes of divinyltetramethyldisiloxane with platinum.

[0300] The amount of platinum group metal catalyst (A2) relative to the total amount of polyorganosiloxane (a1) and polyorganosiloxane (a2) is typically in the range of 1.0 ppm to 50.0 ppm.

[0301] For the purpose of inhibiting the hydrosilylation reaction, the polyorganosiloxane component (A) may also contain a polymerization inhibitor (A3).

[0302] There are no particular limitations on polymerization inhibitors as long as they can inhibit the hydrosilylation reaction. Specific examples include 1-ethynyl-1-cyclohexanol, 1,1-diphenyl-2-propynyl-1-ol, and other alkynyl alcohols.

[0303] The amount of polymerization inhibitor relative to the total amount of polyorganosiloxane (a1) and polyorganosiloxane (a2) is generally considered to be above 1000.0 ppm from the viewpoint of achieving its effect, and below 10000.0 ppm from the viewpoint of preventing excessive inhibition of the hydrosilanization reaction.

[0304] The adhesive composition used in this invention may also contain a release agent component (B). By including such a release agent component (B) in the adhesive composition, the resulting adhesive layer can be reproducibly and properly released.

[0305] As such a stripping agent component (B), typically, polyorganosiloxanes can be listed, and specific examples include: epoxy-containing polyorganosiloxanes, methyl-containing polyorganosiloxanes, phenyl-containing polyorganosiloxanes, etc., but are not limited to these.

[0306] Preferred examples of polyorganosiloxanes as stripping agent component (B) include, but are not limited to, epoxy-containing polyorganosiloxanes, methyl-containing polyorganosiloxanes, and phenyl-containing polyorganosiloxanes.

[0307] The weight-average molecular weight of the polyorganosiloxane used as the stripping agent component (B) is typically 100,000 to 2,000,000, and preferably 200,000 to 1,200,000, more preferably 300,000 to 900,000, from the viewpoint of achieving the effects of the present invention with good reproducibility. Its dispersibility is typically 1.0 to 10.0, and preferably 1.5 to 5.0, more preferably 2.0 to 3.0, from the viewpoint of achieving appropriate stripping with good reproducibility. It should be noted that the weight-average molecular weight and dispersibility can be determined by the methods described above related to the polysiloxane.

[0308] The viscosity of the polyorganosiloxane used as the stripping agent component (B) is typically 1000 mm. 2 / s~2000000mm 2 / s. It should be noted that the viscosity of the polyorganosiloxane, which is the stripping agent component (B), is expressed as kinematic viscosity, cSt = mm. 2 / s. Alternatively, viscosity (mPa·s) can be divided by density (g / cm³). 3The value can be determined from the viscosity and density measured at 25°C using a type E rotational viscometer, and can be derived from the kinematic viscosity (mm). 2 / s) = viscosity (mPa·s) / density (g / cm³) 3 ) can be calculated using such a formula.

[0309] As epoxy-containing polyorganosiloxanes, examples include those containing R 11 R 12 SiO 2 / 2 The siloxane unit shown (D) 10 Polyorganosiloxane (unit).

[0310] R 11 The group that bonds to silicon atoms represents an alkyl group, R. 12 The group that bonds to silicon atoms represents an epoxy group or an organic group containing an epoxy group. Specific examples of alkyl groups can be listed above.

[0311] The epoxy group in an organic group containing an epoxy group can be an independent epoxy group that does not condense with other rings, or it can be an epoxy group that forms a condensation ring with other rings, such as 1,2-epoxycyclohexyl.

[0312] Specific examples of organic groups containing epoxy groups include 3-epoxypropoxypropyl and 2-(3,4-epoxycyclohexyl)ethyl, but are not limited to these.

[0313] In this invention, as a preferred example of an epoxy-containing polyorganosiloxane, an epoxy-containing polydimethylsiloxane can be listed, but it is not limited thereto.

[0314] Epoxy-containing polyorganosiloxanes comprise the aforementioned siloxane units (D 10 (unit), but except for D 10 In addition to the unit, it may also include the above-mentioned Q unit, M unit and / or T unit.

[0315] In a preferred embodiment of the present invention, specific examples of epoxy-containing polyorganosiloxanes include: those consisting only of D 10 Polyorganosiloxanes composed of units; containing D 10 Polyorganosiloxanes containing D and Q units; 10 Polyorganosiloxanes containing D and M units; 10 Polyorganosiloxanes containing D and T units; 10 Polyorganosiloxanes containing D, Q, and M units; 10 Polyorganosiloxanes containing D, M, and T units; 10Polyorganosiloxanes with units such as Q-unit, M-unit, and T-unit.

[0316] The epoxy-containing polyorganosiloxane is preferably a polydimethylsiloxane with an epoxy value of 0.1 to 5, and its weight-average molecular weight is usually 1,500 to 500,000, preferably 100,000 or less from the viewpoint of inhibiting precipitation in the adhesive.

[0317] Specific examples of epoxy-containing polyorganosiloxanes include those shown in formulas (E1) to (E3), but are not limited to these examples.

[0318]

[0319] (m1 and n1 represent the number of each repeating unit, which are positive integers.)

[0320]

[0321] (m2 and n2 represent the number of each repeating unit, which are positive integers, and R is an alkylene group with 1 to 10 carbon atoms.)

[0322]

[0323] (m3, n3, and o3 represent the number of each repeating unit, which are positive integers, and R is an alkylene group with 1 to 10 carbon atoms.)

[0324] As methyl-containing polyorganosiloxanes, examples include those containing R 210 R 220 SiO 2 / 2 The siloxane unit shown (D) 200 Polyorganosiloxanes (units), preferably containing R 21 R 21 SiO 2 / 2 The siloxane unit shown (D) 20 Polyorganosiloxane (unit).

[0325] R 210 and R 220 The groups bonded to silicon atoms are each independently represented as alkyl groups, but at least one of them is methyl. The examples above can be listed as specific examples of alkyl groups.

[0326] R 21 The group that bonds to a silicon atom is represented by an alkyl group. Specific examples of alkyl groups can be listed above. Wherein, as R... 21 Methyl group is preferred.

[0327] In this invention, polydimethylsiloxane is a preferred example of a methyl-containing polyorganosiloxane, but it is not limited thereto.

[0328] Methyl-containing polyorganosiloxanes contain the aforementioned siloxane units (D... 200 Unit or D 20 (unit), but except for D 200 Unit and D 20 In addition to the unit, it may also include the above-mentioned Q unit, M unit and / or T unit.

[0329] In one aspect of the present invention, as a specific example of a methyl-containing polyorganosiloxane, the following can be listed: consisting only of D 200 Polyorganosiloxanes composed of units; containing D 200 Polyorganosiloxanes containing D and Q units; 200 Polyorganosiloxanes containing D and M units; 200 Polyorganosiloxanes containing D and T units; 200 Polyorganosiloxanes containing D, Q, and M units; 200 Polyorganosiloxanes containing D, M, and T units; 200 Polyorganosiloxanes with units of Q, M, and T.

[0330] In a preferred embodiment of the present invention, specific examples of methyl-containing polyorganosiloxanes include: those consisting only of D 20 Polyorganosiloxanes composed of units; containing D 20 Polyorganosiloxanes containing D and Q units; 20 Polyorganosiloxanes containing D and M units; 20 Polyorganosiloxanes containing D and T units; 20 Polyorganosiloxanes containing D, Q, and M units; 20 Polyorganosiloxanes containing D, M, and T units; 20 Polyorganosiloxanes with units of Q, M, and T.

[0331] As specific examples of methyl-containing polyorganosiloxanes, methyl-containing polyorganosiloxanes of formula (M1) can be listed, but are not limited thereto.

[0332]

[0333] (n4 represents the number of repeating units, which is a positive integer.)

[0334] As phenyl-containing polyorganosiloxanes, examples include those containing R 31 R 32 SiO 2 / 2 The siloxane unit shown (D) 30(unit) phenyl-containing polyorganosiloxanes.

[0335] R 31 The group that bonds to silicon atoms represents a phenyl or alkyl group, R. 32 The group that bonds to silicon atoms is represented by phenyl. Specific examples of alkyl groups can be listed above, with methyl being preferred.

[0336] Phenyl-containing polyorganosiloxanes comprise the aforementioned siloxane units (D 30 (unit), but except for D 30 In addition to the unit, it may also include the above-mentioned Q unit, M unit and / or T unit.

[0337] In a preferred embodiment of the present invention, specific examples of phenyl-containing polyorganosiloxanes include those composed solely of D... 30 Polyorganosiloxanes composed of units; containing D 30 Polyorganosiloxanes containing D and Q units; 30 Polyorganosiloxanes containing D and M units; 30 Polyorganosiloxanes containing D and T units; 30 Polyorganosiloxanes containing D, Q, and M units; 30 Polyorganosiloxanes containing D, M, and T units; 30 Polyorganosiloxanes with units of Q, M, and T.

[0338] Specific examples of methyl-containing polyorganosiloxanes include, but are not limited to, those represented by formula (P1) or (P2).

[0339]

[0340] (m5 and n5 represent the number of each repeating unit, which are positive integers.)

[0341]

[0342] (m6 and n6 represent the number of each repeating unit, which are positive integers.)

[0343] In a preferred embodiment, the adhesive composition used in this invention comprises a polyorganosiloxane component (A) cured by a hydrosilanization reaction and a release agent component (B). In a preferred embodiment, the polyorganosiloxane is included as the release agent component (B).

[0344] The adhesive composition used in this invention may contain adhesive component (S) and release agent component (B) in any ratio. Considering the balance between adhesion and release properties, the ratio of component (S) to component (B) by mass is preferably 99.995:0.005 to 30:70, more preferably 99.9:0.1 to 75:25.

[0345] That is, when the polyorganosiloxane component (A) is included and cured by the hydrosilanization reaction, the ratio of component (A) to component (B) by mass is preferably 99.995:0.005 to 30:70, more preferably 99.9:0.1 to 75:25.

[0346] For purposes such as viscosity adjustment, the adhesive composition used in this invention may also contain a solvent, and specific examples include aliphatic hydrocarbons, aromatic hydrocarbons, ketones, etc., but are not limited thereto.

[0347] More specifically, examples include: hexane, heptane, octane, nonane, decane, undecane, dodecane, isododecane, menthol, limonene, toluene, xylene, mesitylene, cumene, MIBK (methyl isobutyl ketone), butyl acetate, diisobutyl ketone, 2-octanone, 2-nonanone, 5-nonanone, etc., but are not limited to these. Such solvents can be used alone or in combination of two or more.

[0348] When the adhesive composition used in this invention contains a solvent, its content is appropriately set taking into account the desired viscosity of the composition, the coating method used, the thickness of the film produced, etc., and is in the range of about 10% to 90% by mass relative to the total composition.

[0349] The viscosity of the adhesive composition used in this invention is typically 500 mPa·s to 20000 mPa·s at 25°C, preferably 1000 mPa·s to 5000 mPa·s. The viscosity of the adhesive composition used in this invention can be adjusted by changing the type of solvent used, their ratio, and the concentration of film components, taking into account various factors such as the coating method used and the desired film thickness.

[0350] The adhesive composition used in this invention can be manufactured by mixing the adhesive component (S) with the release agent component (B) and solvent as used in the case of application.

[0351] The mixing order is not particularly limited. As an example of a method for easily and reproducibly producing an adhesive composition, examples include: dissolving the adhesive component (S) and the release agent component (B) in a solvent; dissolving a portion of the adhesive component (S) and the release agent component (B) in a solvent, dissolving the remaining portion in the solvent, and mixing the resulting solutions. However, this method is not limited to these approaches. It should be noted that during the preparation of the adhesive composition, appropriate heating can be performed within a range that does not cause the components to decompose or deteriorate.

[0352] In this invention, for the purpose of removing foreign matter, the solvent, solution, etc. used may be filtered using a submicron-sized filter or the like during the manufacturing of the adhesive composition or after all the components have been mixed.

[0353] The thickness of the adhesive layer in the laminate of the present invention is typically 5 μm to 500 μm, but from the viewpoint of maintaining film strength, the film thickness is preferably 10 μm or more, more preferably 20 μm or more, and even more preferably 30 μm or more. From the viewpoint of avoiding non-uniformity caused by thick film, the film thickness is preferably 200 μm or less, more preferably 150 μm or less, even more preferably 120 μm or less, and even more preferably 70 μm or less.

[0354] The laminate of the present invention can be manufactured, for example, by a method comprising the following steps: a first step, 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, 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, while subjecting at least one of a heat treatment or a decompression treatment to the adhesive coating layer of the semiconductor substrate and the release agent coating layer of the support substrate, applying a load in the thickness direction of the semiconductor substrate and the support substrate to make them adhere, and then performing a post-heat treatment, thereby forming the laminate.

[0355] Furthermore, the laminate of the present invention can be manufactured, for example, by a method comprising the following steps: a first step, applying a release agent composition to the surface of a semiconductor substrate, and heating it if necessary to form a release agent coating layer; a second step, applying an adhesive composition to the surface of a support substrate, and heating it if necessary to form an adhesive coating layer; and a third step, applying a load in the thickness direction of the semiconductor substrate and the support substrate to make them adhere while subjecting at least one of a heat treatment and a decompression treatment to the release agent coating layer of the semiconductor substrate and the adhesive coating layer of the support substrate, and then performing a post-heat treatment to thereby form the laminate.

[0356] It should be noted that, as long as the effect of the present invention is not compromised, the substrates of either party can be coated and heated sequentially with each composition.

[0357] There are no particular limitations on the coating method; spin coating is the most common. It should be noted that alternative methods, such as spin coating, can be used to form a coating film, which can then be adhered as an adhesive or release agent layer.

[0358] The heating temperature of the adhesive composition after coating varies depending on the type and amount of adhesive components contained in the adhesive composition, whether it contains solvent, the boiling point of the solvent used, the desired thickness of the adhesive layer, etc., so it cannot be specified in general terms, but it is usually 80℃ to 150℃, and the heating time is usually 30 seconds to 5 minutes.

[0359] When the adhesive composition contains a solvent, the coated adhesive composition is typically heated.

[0360] The heating temperature of the coated release agent composition varies depending on the type and amount of the acid-producing agent, the boiling point of the solvent used, and the desired thickness of the release layer, so it cannot be specified in general terms. However, from the viewpoint of achieving a suitable release layer with good reproducibility, it should be above 80°C, and from the viewpoint of inhibiting the decomposition of the acid-producing agent, it should be below 300°C. The heating time is usually appropriately determined in the range of 10 seconds to 10 minutes depending on the heating temperature.

[0361] When the release agent composition contains a solvent, the coated release agent composition is typically heated.

[0362] Heating can be done using heating plates, ovens, etc.

[0363] The thickness of the adhesive coating layer obtained by coating the adhesive composition and heating it is typically around 5 μm to 500 μm, and is appropriately determined in a way that ultimately becomes the thickness range of the aforementioned adhesive layer.

[0364] The thickness of the release agent coating layer obtained by coating the release agent composition and heating it is typically about 10 nm to 10 μm, and is appropriately determined in a way that ultimately becomes the thickness range of the release layer described above.

[0365] In this invention, the coated layers can be joined together in an adjoint manner, and while performing heat treatment or depressurization treatment, or both, a load in the thickness direction of the semiconductor substrate and the support substrate is applied to bring the two layers into close contact. Afterwards, a post-heat treatment is performed, thereby obtaining the laminate of this invention. It should be noted that the choice between heat treatment, depressurization treatment, or a combination of both is appropriately determined based on considerations such as the type of adhesive composition, the specific composition of the release agent composition, the phase properties of the films obtained from the two compositions, the film thickness, and the calculated adhesive strength.

[0366] From the viewpoint of softening the adhesive coating layer to achieve proper adhesion with the release agent coating layer, and from the viewpoint of properly curing organic resins that have not been fully cured during the heating process when forming the release agent coating layer, the heat treatment is generally appropriately determined within the range of 20°C to 150°C. In particular, from the viewpoint of suppressing or avoiding excessive curing and unwanted deterioration of the adhesive component (S), the heat treatment is preferably 130°C or lower, more preferably 90°C or lower. From the viewpoint of reliably achieving proper adhesion, the heating time is generally 30 seconds or more, preferably 1 minute or more. From the viewpoint of suppressing deterioration of the adhesive layer and other components, the heating time is generally 10 minutes or less, preferably 5 minutes or less.

[0367] The decompression treatment simply involves exposing the adhesive coating layers and release agent coating layers that are in contact with each other to a pressure of 10 Pa to 10,000 Pa. The decompression treatment time is usually 1 minute to 30 minutes.

[0368] From the viewpoint of obtaining a laminate with good reproducibility and good separation of the substrate, the adhesive coating layer and the release agent coating layer that are in contact with each other are preferably bonded by depressurization treatment, and more preferably by a combination of heat treatment and depressurization treatment.

[0369] The load in the thickness direction of the semiconductor substrate and the support substrate is not particularly limited as long as it does not adversely affect the semiconductor substrate and the support substrate and the two layers between them, and firmly seals them together, but it is usually in the range of 10N to 1000N.

[0370] From the viewpoint of achieving sufficient curing speed, the post-heating temperature is preferably 120°C or higher, and from the viewpoint of preventing deterioration of the substrate and each layer, the post-heating temperature is preferably 260°C or lower.

[0371] From the viewpoint of achieving proper bonding between the substrate and the layers constituting the laminate, the post-heating time is usually 1 minute or more, preferably 5 minutes or more. From the viewpoint of suppressing or avoiding adverse effects on each layer caused by excessive heating, the post-heating time is usually 180 minutes or less, preferably 120 minutes or less.

[0372] Heating can be performed using a heating plate, oven, or similar equipment. When using a heating plate for post-heating, either the semiconductor substrate or the support substrate of the laminate can be heated with the semiconductor substrate facing downwards. However, from the viewpoint of achieving proper peeling with good reproducibility, it is preferable to heat the laminate with the semiconductor substrate facing downwards.

[0373] It should be noted that one of the purposes of the post-heat treatment is to achieve a more suitable adhesive and release layer as a self-supporting membrane, and in particular, to achieve proper curing based on the hydrosilanization reaction.

[0374] The method for manufacturing the 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 cleaning the separated semiconductor substrate with a cleaning agent composition.

[0375] In the first process, the processing performed on the semiconductor substrate refers to processing on the opposite side of the circuit surface of the wafer, such as wafer thinning achieved by grinding the back side of the wafer. Afterwards, through-silicon vias (TSVs) are formed, and then the thinned wafer is peeled off from the support substrate to form a wafer stack for three-dimensional mounting. Furthermore, back-side electrodes are formed before and after three-dimensional mounting. During the wafer thinning and TSV processes, heat of approximately 250°C to 350°C is applied while the wafer is bonded to the support substrate. The laminate of the present invention includes an adhesive layer and a release layer, and possesses heat resistance to such loads.

[0376] It should be noted that the processing is not limited to the processing described above. For example, it also includes the implementation of the semiconductor component mounting process in cases where the substrate used to mount the semiconductor component is temporarily bonded to a support substrate.

[0377] In the second process, methods for separating (peeling) the semiconductor substrate and the support substrate can include: laser peeling, mechanical peeling using a device with a sharp point, peeling by tearing between the support and the wafer, etc., but are not limited to these.

[0378] When the support substrate is transparent, the release layer is separated or decomposed as described above by irradiating the release layer with light from the support substrate side. Afterwards, the semiconductor substrate and the support substrate can be easily separated by pulling up either substrate.

[0379] Irradiating the release layer with light does not necessarily require irradiating the entire area of ​​the release layer. Even if the irradiated and unirradiated areas are mixed, as long as the overall release layer's peeling ability is sufficiently improved, 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 irradiated and unirradiated areas vary depending on the type and specific composition of the adhesive used, the thickness of the adhesive layer, the thickness of the release layer, the intensity of the irradiated light, etc., but those skilled in the art can set appropriate conditions without excessive experimentation. Because of this, in the method for manufacturing the processed semiconductor substrate according to the present invention, when the support substrate of the laminate used is light-transmitting, the light irradiation time can be shortened during peeling by light irradiation. As a result, not only can an improvement in production volume be expected, but physical stress for peeling can also be avoided, and the semiconductor substrate and the support substrate can be easily and efficiently separated by light irradiation alone.

[0380] Typically, the light dose used for stripping is 50 mJ / cm². 2 ~3000mJ / cm 2 The irradiation time should be determined appropriately based on the wavelength and the amount of irradiation.

[0381] Light can be applied using lasers or non-laser sources such as ultraviolet lamps.

[0382] In the third step, a cleaning agent composition is sprayed onto the surface of the separated semiconductor substrate, or the separated semiconductor substrate is immersed in a cleaning agent composition or cleaned, and then typically rinsed and dried using a solvent. It should be noted that the cleaning agent composition may include the cleaning agent compositions described above.

[0383] In the manufacturing method of the processed semiconductor substrate of the present invention, the processed semiconductor substrate manufactured in the third step is well cleaned by the cleaning agent composition, but this does not prevent the surface of the processed semiconductor substrate from being further cleaned by removing adhesive tape or the like. If necessary, the surface can also be further cleaned by removing adhesive tape or the like.

[0384] Regarding the constituent elements and method elements related to the above-described steps of the method for manufacturing the processed semiconductor substrate of the present invention, various modifications may be made as long as they do not depart from the spirit of the present invention.

[0385] The manufacturing method of the processed semiconductor substrate of the present invention may also include steps other than those described above.

[0386] The peeling method of the present invention, when the support substrate of the laminate of the present invention is light-transmitting, separates the semiconductor substrate and the support substrate of the laminate by irradiating light from the support substrate side toward the peeling layer.

[0387] In the laminate of the present invention, the semiconductor substrate and the support substrate are appropriately and peelably temporarily bonded together by an adhesive layer and a release layer. Therefore, when the support substrate is light-transmitting, the semiconductor substrate and the support substrate can be easily separated by irradiating the release layer from the support substrate side of the laminate. Typically, the release is performed after the semiconductor substrate of the laminate has been processed.

[0388] Example

[0389] [Device]

[0390] (1) Mixer: ARE-500 self-rotating and revolution-rotating mixer manufactured by THINKY Corporation.

[0391] (2) Rheometer: MCR302 viscoelasticity measuring device manufactured by Anton Paar Japan Co., Ltd.

[0392] (3) Vacuum bonding device: SUSS MicroTec Co., Ltd., manual bonding machine.

[0393] (4) High-rigidity grinding machine: HRG300 manufactured by Tokyo Precision Co., Ltd.

[0394] (5) Temperature measuring device with a 5% weight reduction: NETZSCH 2010SR (in air, heating from room temperature to 400°C at 10°C / min).

[0395] (6) Optical film thickness gauge (film thickness measurement): Filmetrics F-50.

[0396] (7) Laser irradiation device (Lambda SX manufactured by Coherent Co., Ltd.).

[0397] [Conditions for determining the molecular weight of polysilanes]

[0398] The weight-average molecular weight of polysilanes was determined using a GPC apparatus (EcoSEC, HLC-8220GPC, Tosoh Corporation) and GPC columns (Shodex KF-803L, KF-802, and KF-801, successively, manufactured by Showa Denko Corporation). The column temperature was set to 40°C, tetrahydrofuran was used as the eluent (dissolution solvent), the flow rate was set to 1.00 mL / min, and polystyrene (manufactured by Sigma Aldrich) was used as the standard sample.

[0399] [1] Preparation of adhesive composition

[0400] [Preparation Example 1]

[0401] Add 80g of MQ resin (manufactured by Wacker Chemie) containing a polysiloxane backbone and vinyl groups, 2.52g of linear polydimethylsiloxane (manufactured by Wacker Chemie) containing SiH groups with a viscosity of 100mPa·s, 5.89g of linear polydimethylsiloxane (manufactured by Wacker Chemie) containing SiH groups with a viscosity of 70mPa·s, and 0.22g of 1-ethynyl-1-cyclohexanol (manufactured by Wacker Chemie) to a 600mL container for a mixer, and mix for 5 minutes.

[0402] Add 0.147 g of platinum catalyst (manufactured by Wacker Chemie) and 5.81 g of vinyl-containing linear polydimethylsiloxane (manufactured by Wacker Chemie) with a viscosity of 1000 mPa·s to the mixture obtained by stirring for 5 minutes, and add 3.96 g of the mixture obtained separately by stirring for 5 minutes.

[0403] Finally, the mixture was filtered through a 300-mesh nylon filter to obtain the adhesive composition.

[0404] [2] Preparation of cleaning agent composition

[0405] [Preparation Example 2]

[0406] A cleaning agent composition was obtained by mixing 5g of tetrabutylammonium fluoride trihydrate (manufactured by Kanto Chemical Co., Ltd.) with 95g of N-methyl-2-pyrrolidone and stirring thoroughly.

[0407] [3] Synthesis of phenolic varnish resin

[0408] [Synthesis example 1]

[0409] Add 56.02 g of N-phenyl-1-naphthylamine, 50.00 g of 1-pyrene formaldehyde, 6.67 g of 4-(trifluoromethyl)benzaldehyde, and 2.46 g of methanesulfonic acid to a flask. Then add 86.36 g of 1,4-dioxane and 86.36 g of toluene. Reflux and stir for 18 hours under a nitrogen atmosphere.

[0410] After cooling the reaction mixture, 96 g of tetrahydrofuran was added and diluted. The resulting diluted solution was added dropwise to methanol, thereby obtaining a precipitate. The precipitate was recovered by filtration, the filter was washed with methanol, and dried under reduced pressure at 60°C to obtain 72.12 g of phenolic varnish resin (hereinafter referred to as PPNAPCA-F). The weight-average molecular weight of the phenolic varnish resin as a polymer, as determined by the above method, is 1100.

[0411] [4] Preparation of the stripping agent composition

[0412] [Comparative Example 1-1]

[0413] 3.6 g of the phenolic varnish resin obtained in Synthesis Example 1 and 0.72 g of 3,3',5,5'-tetra(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. The resulting solution was filtered through a polyethylene microfilter with a pore size of 0.2 μm to obtain a stripping agent composition.

[0414] [Comparative Examples 1-2]

[0415] 3.6 g of the phenolic varnish 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. The resulting solution was filtered through a polyethylene microfilter with a pore size of 0.2 μm to obtain a stripping agent composition.

[0416] [Example 1]

[0417] 3.6 g of the phenolic varnish resin obtained in Synthesis Example 1, 0.72 g of TMOM-BP as a crosslinking agent, and 3.6 g of OGSOLSI-20-10 (manufactured by Osaka Gas Chemical Co., Ltd.) as a branched polysilane were dissolved in 92.08 g of propylene glycol monomethyl ether acetate. The solution was filtered through a polyethylene microfilter with a pore size of 0.2 μm to obtain a stripping agent composition. It should be noted that OGSOLSI-20-10 is a branched polysilane of formula (B-1), and the weight-average molecular weight determined by the above method is 1.7 × 10⁻⁶. 3 The temperature at which the weight is reduced by 5% is above 400°C.

[0418]

[0419] (Ph represents phenyl, R) E Indicates terminal substituents, representing atoms or groups, n b This indicates the number of repeating units.

[0420] [Comparative Examples 1-3]

[0421] 3.6 g of the phenolic varnish resin obtained in Synthesis Example 1, 0.72 g of TMOM-BP as a crosslinking agent, and 3.6 g of OGSOLSI-10-10 (manufactured by Osaka Gas Chemical Co., Ltd.) as a linear polysilane were dissolved in 92.08 g of propylene glycol monomethyl ether acetate. The solution was filtered through a polyethylene microfilter with a pore size of 0.2 μm to obtain a stripping agent composition. It should be noted that OGSOLSI-10-10 is a linear polysilane of formula (S-1), and the weight-average molecular weight determined by the above method is 1.28 × 10⁻⁶. 4 The temperature at which the weight is reduced by 5% is 370℃.

[0422]

[0423] (Ph represents phenyl, R) E Indicates terminal substituents, representing atoms or groups, n c1 This indicates the number of repeating units.

[0424] [Comparative Examples 1-4]

[0425] 3.6 g of the phenolic varnish resin obtained in Synthesis Example 1, 0.72 g of TMOM-BP as a crosslinking agent, and 3.6 g of OGSOL SI-10-20 (manufactured by Osaka Gas Chemical Co., Ltd.) as a linear polysilane were dissolved in 92.08 g of propylene glycol monomethyl ether acetate. The solution was filtered through a polyethylene microfilter with a pore size of 0.2 μm to obtain a stripping agent composition. It should be noted that OGSOL SI-10-20 is a linear polysilane as shown in formula (S-2), and the weight-average molecular weight determined by the above method is 2.4 × 10⁻⁶. 3 The temperature at which the weight is reduced by 5% is 390℃.

[0426]

[0427] (Ph represents phenyl, R) E Indicates terminal substituents, representing atoms or groups, n c2 This indicates the number of repeating units.

[0428] [Comparative Examples 1-5]

[0429] 3.6 g of the phenolic varnish 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 stripping agent composition.

[0430] [5] Confirmation of membrane removal performance (membrane reduction rate)

[0431] [Example 2]

[0432] The stripper composition obtained in Example 1 was spin-coated onto a silicon wafer cut to 4 cm square with a final film thickness of 200 nm. The wafer was heated at 250°C for 15 minutes to form a film on the substrate. Substrates with the film formed were produced in the required quantity (the same applies below).

[0433] [Comparative Examples 2-1 to 2-5]

[0434] The stripper compositions obtained in Comparative Examples 1-1 to 1-5 were used instead of the stripper composition obtained in Example 1, and otherwise, films were formed on the substrate by the same method as in Example 2.

[0435] The film thickness (film thickness before immersion) of each film obtained in Example 2 and Comparative Examples 2-1 to 2-5 was measured. Then, each film, together with the substrate, 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 (film thickness after immersion) of each film was measured again.

[0436] In addition, the same operation was performed and the film thickness was measured by using OK73 diluent (composed of 70% propylene glycol monomethyl ether and 30% propylene glycol monomethyl ether acetate) (manufactured by Tokyo Ohka Kogyo Co., Ltd.) and N-methyl-2-pyrrolidone (NMP) instead of the cleaning agent composition.

[0437] Furthermore, for the membrane obtained in Example 2, the same operation was performed to measure the membrane thickness, using 5% by mass potassium hydroxide (KOH) aqueous solution, 10% by mass hydrochloric acid aqueous solution, 10% by mass p-toluenesulfonic acid aqueous solution, mesitylene, acetone, 2.38% by mass tetramethylammonium hydroxide aqueous solution (TMAH aqueous solution), and 35% by mass hydrogen peroxide water instead of the cleaning agent composition.

[0438] The film reduction rate (%) caused by impregnation was calculated using the formula: film thickness after impregnation (nm) / film thickness before impregnation (nm) × 100. The results are shown in Table 1. It should be noted that in the table, N / D indicates that there is no corresponding data.

[0439] [Table 1]

[0440]

[0441] As shown in Table 1, the membrane loss rate of the membrane obtained in Comparative Example 2-1 was 100% when immersed in the cleaning agent composition, OK73 diluent, and NMP. This means that the membrane obtained in Comparative Example 2-1 dissolved in the cleaning agent composition, OK73 diluent, and NMP. On the other hand, the membrane loss rate of the membrane obtained in Comparative Example 2-2 was 0% when immersed in the cleaning agent composition, OK73 diluent, and NMP. This means that the membrane obtained in Comparative Example 2-2 did not dissolve in the cleaning agent composition, OK73 diluent, and NMP. It can be inferred that in Comparative Example 2-1 without the addition of an acid catalyst, the crosslinking reaction did not occur, while in Comparative Example 2-2 with the addition of an acid catalyst, the crosslinking reaction occurred.

[0442] In Example 2, where branched polysilane was added without an acid catalyst, a film reduction rate of 0% was obtained when immersed in various solvents, acidic aqueous solutions, alkaline aqueous solutions, and solutions commonly used in the manufacture of semiconductor devices (TMAH aqueous solution, hydrogen peroxide solution), while a film reduction rate of 100% was obtained when immersed in a cleaning agent composition. That is, the film of Example 2 cannot be adequately removed by various solvents, acidic aqueous solutions, alkaline aqueous solutions, and solutions commonly used in the manufacture of semiconductor devices, but can be adequately removed by a cleaning agent composition.

[0443] On the other hand, in Comparative Examples 2-3 and 2-4, which did not contain branched polysilane but contained linear polysilane, although it was confirmed that the resistance to OK73 diluent was slightly improved in Comparative Example 2-4, the following characteristics could not be achieved as in the case where branched polysilane was used: it could not be properly removed by OK73 diluent or NMP, but it could be properly removed by the cleaning agent composition.

[0444] Furthermore, when diphenylsilanediol was used instead of branched polysilane, the resistance of the resulting film to cleaning agent compositions and solvents could not be confirmed.

[0445] [6] Fabrication of laminates and confirmation of light-based stripping properties and cleaning properties based on cleaning agent compositions

[0446] [Example 3]

[0447] The release agent composition obtained in Example 1 was spin-coated onto a 301 mm glass wafer (EAGLE-XG, manufactured by Corning, 700 μm thick) serving as the substrate, with a film thickness of 200 nm in the final laminate, thus forming a release agent coating layer on the glass wafer serving as the support substrate.

[0448] On the other hand, the adhesive composition obtained in Preparation Example 1 was spin-coated onto a 300 mm thick silicon wafer (775 μm thick) serving as a substrate on the device side, with a film thickness of 60 μm in the final laminate, thus forming an adhesive coating layer on the silicon wafer serving as a semiconductor substrate.

[0449] Then, using a bonding apparatus, the glass wafer and silicon wafer are bonded together, sandwiching the release agent coating layer and the adhesive coating layer, and a laminate is fabricated by post-heat treatment at 200°C for 10 minutes. It should be noted that the bonding is performed at a temperature of 23°C and a pressure reduction of 1500 Pa. It should be noted that the laminates are manufactured in the required quantity.

[0450] After thinning the silicon wafer of the resulting laminate to 50 μm using a high-rigidity grinding machine, the laminate was placed in an oven and subjected to high-temperature treatment at 250°C for 1 hour. Then, the cooled laminate was attached to a dicing tape (made by Nitto Denko Corporation, DU-300) with the thinned silicon wafer side facing down and fixed in place.

[0451] Using a laser irradiation device, a 308nm wavelength laser was irradiated onto the release layer from the glass wafer side of the fixed laminate, and the minimum irradiation amount required to produce peeling was set as the optimal irradiation amount. Then, with the optimal irradiation amount, the entire surface of the release layer was irradiated with a 308nm wavelength laser from the glass wafer side of the fixed laminate, and the support substrate was manually lifted to confirm whether peeling was possible.

[0452] After peeling and removing the fixed semiconductor substrate, the separated semiconductor wafer and glass wafer were cut into 4cm × 4cm pieces. The cut wafers were immersed in 7mL of the cleaning agent composition obtained in Preparation Example 2 for 10 minutes, and the presence of any residue such as film remaining on the surface of the wafer was visually checked (cleanability test). In addition, the cleaning agent composition after cleaning the wafer was recovered, and the presence of any foreign matter remaining in the composition was visually checked (foreign matter confirmation).

[0453] [Comparative Example 3-1]

[0454] The stripper composition obtained in Comparative Examples 2-2 was used instead of the stripper composition obtained in Example 1. Otherwise, the laminate was manufactured by the same method as in Example 3, the peelability was confirmed, and the cleanability test and foreign matter confirmation were performed.

[0455] [Table 2]

[0456] Example 3 Comparative Example 3-1 Can laser ablation be performed (optimal irradiation level)? Energy (170mJ) Energy (180mJ) The state of the equipment side substrate after cleaning No residue No residue The state of the cleaning agent after cleaning the equipment side substrate No foreign objects There is a black foreign object State of the carrier-side substrate after cleaning No residue There are residues The state of the cleaning agent after cleaning the carrier-side substrate No foreign objects There is a black foreign object

[0457] As shown in Table 2, in the case of separating a semiconductor substrate and a support substrate having a film as a release layer obtained using a release agent composition containing branched polysilane as a release layer by irradiating the release layer with light (Example 3), each substrate after separation can be properly cleaned without leaving any residue on the substrate by cleaning each substrate with a cleaning agent composition. Furthermore, no foreign matter was detected in each cleaning agent composition used for cleaning each substrate.

[0458] On the other hand, when a semiconductor substrate and a support substrate, which are in the same manner separated as a laminate having a film obtained using a release agent composition containing an acid catalyst but without polysilane as a release layer (Comparative Example 3-1), after cleaning each separated substrate, no foreign matter was found in the semiconductor substrate to which an adhesive layer is formed and in contact with its surface, while residue was found in the support substrate to which a release layer is formed and in contact with its surface. Furthermore, foreign matter was found in each cleaning agent composition used for cleaning each substrate.

[0459] Based on the above, it can be confirmed that by using a stripper composition containing branched polysilane, even after stripping, especially after stripping by light irradiation, a film with good removability or solubility suitable as a stripping layer can be obtained.

Claims

1. A release agent composition for forming the release layer of a laminate comprising a semiconductor substrate, a support substrate, and an adhesive layer and a release layer disposed between the semiconductor substrate and the support substrate. The stripping agent composition comprises an organic resin, a branched polysilane, and a solvent, wherein the organic resin is a phenolic varnish resin, and the branched polysilane comprises the structural unit shown in formula (B). In the formula, R B Indicates a hydrogen atom, hydroxyl group, silyl group, or organic group. in, The content of the structural unit represented by formula (B) in the branched polysilane is more than 50 mol% in all structural units.

2. The stripping agent composition according to claim 1, wherein, The R B It is an aryl group.

3. The stripping agent composition according to claim 2, wherein, The R B It is a phenyl group.

4. The stripping agent composition according to any one of claims 1 to 3, wherein, The branched polysilane has a weight-average molecular weight of 50 to 30,000.

5. The stripping agent composition according to any one of claims 1 to 3, wherein, The branched polysilane is reduced by 5% at a temperature above 300°C.

6. The stripping agent composition according to any one of claims 1 to 3, wherein, The phenolic varnish resin is a polymer comprising one or more units selected from the group consisting of units shown in formula (C1-1), units shown in formula (C1-2), and units shown in formula (C1-3). In the formula, C 1 A group representing an aromatic compound containing a nitrogen atom, C 2 C represents a group containing a tertiary carbon atom whose side chain has at least one selected from the group consisting of secondary carbon atoms, quaternary carbon atoms, and aromatic rings. 3 The C group represents a group derived from aliphatic polycyclic compounds. 4 This indicates 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 biphenyl.

7. The stripping agent composition according to any one of claims 1 to 3, comprising a crosslinking agent.

8. The stripping agent composition according to any one of claims 1 to 3, wherein, The adhesive layer is a film obtained using an adhesive composition containing an adhesive component (S), wherein the adhesive component (S) comprises at least one selected from polysiloxane adhesives, acrylic resin adhesives, epoxy resin adhesives, polyamide adhesives, polystyrene adhesives, polyimide adhesives, and phenolic resin adhesives.

9. The stripping agent composition according to claim 8, wherein, The adhesive component (S) comprises a polysiloxane-based adhesive.

10. The stripping agent composition according to claim 9, wherein, The polysiloxane-based adhesive contains a polysiloxane component (A) that is cured by a hydrogenation silanization reaction.

11. A laminated body, characterized in that, have: Semiconductor substrate, Support substrate, and An adhesive layer and a release layer are disposed between the semiconductor substrate and the support substrate. The release layer is a film obtained from the release agent composition according to any one of claims 1 to 7.

12. The laminate according to claim 11, wherein, The adhesive layer is a film obtained using an adhesive composition containing an adhesive component (S), wherein the adhesive component (S) comprises at least one selected from polysiloxane adhesives, acrylic resin adhesives, epoxy resin adhesives, polyamide adhesives, polystyrene adhesives, polyimide adhesives, and phenolic resin adhesives.

13. The laminate according to claim 12, wherein, The adhesive component (S) comprises a polysiloxane-based adhesive.

14. The laminate according to claim 13, wherein, The polysiloxane-based adhesive contains a polysiloxane component (A) that is cured by a hydrogenation silanization reaction.

15. A method for manufacturing a processed semiconductor substrate, comprising: The first step involves processing the semiconductor substrate of the laminate as described in any one of claims 11 to 14; The second step involves separating the semiconductor substrate and the support substrate. as well as The third step involves cleaning the separated semiconductor substrate with a cleaning agent composition.

16. The method for manufacturing the processed semiconductor substrate according to claim 15, wherein, The second step includes irradiating the release layer with light.

17. The method for manufacturing the processed semiconductor substrate according to claim 15 or 16, wherein, The cleaning agent composition is a cleaning agent composition containing quaternary ammonium salt and organic solvent.

18. The method for manufacturing the processed semiconductor substrate according to claim 17, wherein, The quaternary ammonium salt is a halogen-containing quaternary ammonium salt.

19. The method for manufacturing the processed semiconductor substrate according to claim 18, wherein, The halogen-containing quaternary ammonium salt is a fluorine-containing quaternary ammonium salt.

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