Light-curable resin composition containing self-crosslinking polymers

Abstract

This invention provides a material capable of forming a protective film, which, in the manufacture of semiconductor devices, possesses sufficient etch resistance required for protecting the ends of a semiconductor manufacturing substrate. The solution is a photocurable composition comprising a self-crosslinking polymer and a solvent. The self-crosslinking polymer comprises: a first monomer unit containing aryl ketone residues in its side chain, and a second monomer unit containing aliphatic hydrocarbon residues and / or aromatic ring residues containing carbon atoms readily subjected to hydrogen abstraction reactions in its side chain; and a method for manufacturing a semiconductor device comprising the steps of forming a resist film on a semiconductor substrate, forming a resist pattern by irradiating the resist film with light or electron beams and subsequent imaging, and etching the semiconductor substrate, including the step of forming a protective film from the aforementioned photocurable composition on the surface ends and arbitrarily selected beveled and / or back ends of a semiconductor manufacturing wafer.

Description

Technical Field

[0001] This invention relates to a photocurable resin composition containing a crosslinked polymer; furthermore, it relates to a protective film on the end face of a semiconductor manufacturing substrate (wafer) in the semiconductor device manufacturing process, a protective film forming composition for forming the protective film, a semiconductor manufacturing wafer manufactured using the protective film, the semiconductor manufacturing wafer, and a method for manufacturing a semiconductor device. Prior Technology

[0002] In semiconductor device manufacturing, with the increasing complexity of processes, methods for coating metal-containing solutions onto wafers are being explored, such as to improve etch selectivity. Furthermore, considering the increased resolution and high etch resistance of resist patterns obtained using extreme ultraviolet (EUV) exposure, the use of resists containing inorganic metals to form resist films is being explored. However, metal adhesion to non-determined areas of the wafer during semiconductor device manufacturing significantly affects the electrical characteristics of the semiconductor device. As mentioned above, when forming a metal-containing coating film, the solution supplied to the wafer surface extends to the peripheral edges of the wafer's back surface, forming the coating film up to these non-determined peripheral edges, raising concerns about metal contamination in these areas. Furthermore, since the contaminated parts of the wafer come into contact with wafer processing equipment such as exposure devices or etching devices, or wafer transport mechanisms, wafers transported and processed after that wafer will also be contaminated with metal, which means there is a risk of cross-contamination.

[0003] To address this problem, a technique has been disclosed in which, when forming a coating film on the surface of a substrate, a protective film is formed at the periphery of the substrate, at least on the peripheral end face and the peripheral side of the back side of the substrate, so that the coating film is formed in a manner where the peripheral end face and the peripheral side of the back side of the substrate do not contact the coating film (Patent Document 1). Furthermore, a method for manufacturing a semiconductor device has been disclosed in which a simple additional step (forming a second mask by covering the first mask on the beveled surface to prevent it from collapsing) is used to suppress the film from peeling off from the beveled surface of the substrate (Patent Document 2).

[0004] However, as a film material that functions as a protective film at the end of a substrate, it requires high etching resistance, and further improvements are desired. [Previous Technical Documents] [Patent Literature]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 2017-098333 [Patent Document 2] Japanese Patent Application Publication No. 2011-228340 Summary of the Invention

[0006] [The problem that the invention aims to solve]

[0007] Therefore, the problem to be solved by this invention is to provide a resin material capable of forming a protective film, which has sufficient etch resistance required for protecting the ends of a semiconductor substrate (wafer) in the manufacture of semiconductor devices. Furthermore, the problem to be solved by the invention also includes providing: a protective film that can completely cover the end of a semiconductor manufacturing substrate (wafer) by a simple coating method in the manufacture of a semiconductor device; a protective film forming composition for forming the protective film; a semiconductor manufacturing wafer manufactured using the protective film; and a method for manufacturing the semiconductor manufacturing wafer and the semiconductor device. [Methods for solving the problem]

[0008] This invention includes the following. [1] A photocurable resin composition comprising a self-crosslinking polymer (A) and a solvent (B), wherein the self-crosslinking polymer (A) comprises: (a) A first monomeric unit containing aryl ketone residues in its side chain; and (b) Included in the side chain (b-1) contains aliphatic hydrocarbon residues containing carbon atoms that readily undergo hydrogen abstraction reactions. and / or (b-2) The second monomer unit of the aromatic ring residue. [1-1] The photocurable resin composition as described in [1], wherein the aforementioned self-crosslinking polymer (A) comprises a second monomer unit, the second monomer unit comprising (b-1) Contains aliphatic hydrocarbon residues containing carbon atoms that readily undergo hydrogen abstraction reactions. and (b-2) Aromatic ring residues. [2] The photocurable resin composition described in [1] further includes a crosslinking polymer or a crosslinking compound (C) other than the self-crosslinking polymer (A). [3] As described in [2], the crosslinking group in the aforementioned crosslinking polymer or crosslinking compound (C) is selected from the group consisting of epoxy, (meth)acrylate, vinyl, carboxylic acid, thiol, silicone, cinnamic acid and hydroxyl groups. [4] The photocurable resin composition described in any of [1] to [3] has a viscosity of less than 100 cps at 25°C. [5] A wafer end protective film forming composition for semiconductor manufacturing, which is composed of a photocurable resin composition as described in any one of [1] to [4]. [6] A protective film, which is a hardened coating film formed from a composition of a wafer end protective film for semiconductor manufacturing as described in [5]. [7] The protective film described in [6] has a thickness of 1 to 500 nm. [8] The protective film described in [6] or [7] is used to prevent metal contamination at the wafer tip. [9] The protective film described in any of [6] to [8] is hardened by light with a wavelength of 170 to 800 nm.

[10] A semiconductor manufacturing wafer is formed by coating a semiconductor manufacturing wafer end protection film as described in [5] at the end of a wafer precursor.

[11] A method for manufacturing a semiconductor device, comprising: (A) The step of forming a resist film on a semiconductor substrate. (B) The steps of forming a resist pattern by irradiating the resist film with light or electron beams and subsequent imaging, and (C) Steps for processing semiconductor substrates by etching; It includes: Step (X) involves forming a protective film from the semiconductor manufacturing wafer end protective film formation composition as described in [5] at the surface end and any selected bevel and / or back end of the semiconductor manufacturing wafer.

[12] A method for manufacturing a semiconductor device as described in

[11] includes step (X) before step (A).

[13] The method for manufacturing a semiconductor device as described in

[11] includes step (X) between step (A) and step (B).

[14] A method for manufacturing a semiconductor device as described in

[11] , wherein step (X) is included after step (B) or step (C).

[15] A method for manufacturing a semiconductor device as described in any of

[11] to

[14] , wherein after step (X), a step (Y) is included to remove a portion of the resist film on the aforementioned protective film.

[16] A method for manufacturing a semiconductor device as described in any of

[11] to

[14] , wherein after step (X), a step (Z) is included to remove the aforementioned protective film.

[17] The method for manufacturing a semiconductor device as described in

[15] includes a step (Z) after step (Y) of removing the aforementioned protective film.

[18] A method for manufacturing a semiconductor device as described in any of

[11] to

[17] , wherein the aforementioned resist film comprises a metal.

[19] A method for manufacturing a semiconductor device as described in any of

[11] to

[18] , wherein in the aforementioned step (X), a wafer end protective film for semiconductor manufacturing as described in [5] is coated to form a composition, and a specific area is exposed and developed.

[20] The method for manufacturing a semiconductor device as described in

[16] or

[17] includes step (Z) by ashing or treatment with hydrofluoric acid, organic solvent, alkaline developer or semiconductor cleaning solution.

[21] A method for manufacturing a wafer for semiconductor manufacturing includes the step of coating a wafer end protection film forming composition as described in [5] at the end of a wafer precursor, and manufacturing the aforementioned end-protected wafer.

[22] The photocurable resin composition described in any of [1] to [4], wherein the aforementioned aryl ketone residue is selected from acetophenone, benzophenone, anthraquinone, anthrone, or the following structural formula: The group of aryl ketone residues consisting of heteroatom-substituted anthrone analogs and their substituted derivatives. X is O, S, or NR, and R is a hydrogen atom, a hydrocarbon group, or a acetyl group.

[23] In any of the photocurable resin compositions described in [1] to [4], the carbon atoms in which the hydrogen abstraction reaction of the aforementioned hydrocarbon chain (b-1) is readily occurring are selected from the group consisting of tertiary carbon atoms, secondary carbon atoms and methyl, methylene or methine atoms directly attached to the aromatic ring.

[24] The photocurable resin composition described in any of [1] to [4], wherein the aromatic ring (b-2) is an aromatic ring with 6 to 40 carbon atoms that can be substituted.

[25] In any of the photocurable resin compositions described in [1] to [4], the ratio of the number of repetitions of the first monomer unit to the number of repetitions of monomer units other than the first monomer unit containing the second monomer unit is selected such that the transmittance of the film at a wavelength of 300 nm when forming a film with a thickness of 300 nm is 0.01% or more, preferably 0.1% or more, and more preferably 1% or more.

[26] A self-crosslinking polymer (A) comprising: (a) A first monomeric unit containing aryl ketone residues in its side chain; and (b) Included in the side chain (b-1) contains aliphatic hydrocarbon residues containing carbon atoms that readily undergo hydrogen abstraction reactions. and / or (b-2) The second monomer unit of the aromatic ring residue. [The effects of the invention]

[0009] By means of a photocurable resin composition of the present invention, a protective film with sufficient etch resistance can be formed even without a polymerization initiator, especially a wafer end protective film for semiconductor manufacturing. Furthermore, in the manufacturing of a semiconductor device according to one embodiment of the present invention, a protective film on the end of the semiconductor manufacturing substrate (wafer) can be completely covered by a simple coating method, and cross-contamination caused by metal contamination can be prevented in subsequent semiconductor device manufacturing processes, thereby improving the yield of semiconductor manufacturing devices. Implementation

[0010] [Forms of Invention]

[0011] <1. Photocurable resin composition[1] / Wafer end protective film forming composition for semiconductor manufacturing[5]> (1-1) One embodiment of the photocurable resin composition of the present invention comprises a self-crosslinking polymer (A) and a solvent (B). The photocurable resin composition may further include a crosslinked polymer or a crosslinked compound (C) other than the self-crosslinking polymer (A). Furthermore, this photocurable resin composition can be preferably used as a protective film forming composition for protecting the edge of a wafer used in semiconductor manufacturing (a protective film forming composition for the edge of a wafer used in semiconductor manufacturing, hereinafter also referred to as "protective film forming composition").

[0012] [1-2; Self-crosslinking polymer (A)] (1-2-1) The self-crosslinking polymer (A) comprises: (a) A first monomeric unit containing aryl ketone residues in its side chain; and (b) Included in the side chain (b-1) contains aliphatic hydrocarbon residues containing carbon atoms that readily undergo hydrogen abstraction reactions. and / or (b-2) The second monomeric unit of the aromatic ring residue; Polymers. In self-crosslinking polymers, monomer units other than the first and second monomer units described above may be selectively included without impairing the effects of the present invention.

[0013] (1-2-2) First single unit (1-2-2-1) The aryl ketone residue mentioned in the first monomer unit is a residue of a compound (monoaryl ketone or diaryl ketone) formed by one or two aryl groups directly bonded to a carbonyl group [-C(=O)-]. This aryl ketone residue acts as a photoreactive group and can be activated by light of a specific wavelength, such as ultraviolet light, to undergo a cross-linking reaction. Furthermore, in this specification, the term "residue" of a compound refers to an organic group in which a hydrogen atom bonded to a carbon atom or heteroatom (nitrogen, oxygen, sulfur, etc.) constituting the compound is replaced by a bond used for covalent bonding. Aryl ketone residues are formed in the side chains of the self-crosslinking polymer of the present invention via appropriate linking groups, such as ester bonds or amide bonds, to constitute the side chains of the self-crosslinking polymer. Furthermore, the term "side chain" used in this specification broadly includes chemical groups covalently bonded to the main chain and suspended to the side, and is used synonymously with the term "pendant group". Specific examples of aryl ketone residues include those selected from acetophenone, benzophenone, anthraquinone, and anthrone, with the following structural formulas: The group consisting of heteroatom-substituted anthrone analogs and their substituted derivatives, wherein X is O, S or NR, and R is a hydrogen atom, a hydrocarbon group (preferably 1 to 4 carbons) or a acetyl group (preferably 1 to 4 carbons). On the aromatic ring of these aryl ketone residues, there are substituents such as hydroxyl, amino, and carboxyl groups, or covalent bonds such as ester bonds (-O-CO- or -CO-O-), amide bonds (-NH-CO- or -CO-NH-), carbamate bonds (-NH-CO-O- or -O-CO-NH-), carbonate bonds (-O-CO-O-), and urea bonds (-NH-CO-NH-) are formed between X of nitrogen-substituted anthrone analogs (X=NH) and the functional groups such as carboxyl, hydroxyl, and amino groups of the polymer constituting the main chain, thus forming the side chain of the self-crosslinking polymer. It can also break ester bonds (-O-CO- or -CO-O-), amide bonds (-NH-CO- or... Covalent bonds can be two-way combinations, such as -CO-NH-, carbamate bonds (-NH-CO-O- or -O-CO-NH-), carbonate bonds (-O-CO-O-), and urea bonds (-NH-CO-NH-). These two covalent bonds can be linked together by a divalent linker, such as a heteroatom (oxygen atom, etc.), which connects the interrupted hydrocarbon chain. Examples include -CO-OLO-CO- and -CO-NH-L-NH-CO-.

[0014] (1-2-2-2) Among these aryl ketone residues, the residues of benzophenone or its substituted derivatives (hereinafter referred to as "benzophenone compounds") are preferred from the viewpoint that the least excited triplet state has a longer lifetime and is more likely to undergo photochemical reactions. Examples of benzophenone compounds include, for example, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxydisulfobenzophenone disodium, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2',3,4-tetrahydroxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2,2',3,4,4'-pentahydroxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,3,3 '4,4',5'-Hexahydroxybenzophenone, 2,3,4,4'-Tetrahydroxybenzophenone, 2,3,4-Trihydroxybenzophenone, 2,4,4'-Trihydroxybenzophenone, 2,4,5-Trihydroxybenzophenone, 2,4,6-Trihydroxybenzophenone, 2,4-Dihydroxy-4'-Diethylaminobenzophenone, 2,4-Dihydroxy-4'-Dimethylaminobenzophenone, 2,4-Dihydroxybenzophenone, 4,4'-Dihydroxybenzophenone, 2-Hydroxy-4- (2-Hydroxy-3-methylpropenoxy)propoxybenzophenone, 2-hydroxy-4'-dimethylaminobenzophenone, 2-hydroxy-4-i-octyloxybenzophenone, 2-hydroxy-4-n-octyloxybenzophenone, 2-hydroxy-4-octyloxybenzophenone, 2-hydroxy-4-acetyloxyethoxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone 2-Hydroxy-4-methoxy-5-sulfobenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxybenzophenone, 4,4'-dihydroxybenzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4',6-dihydroxy-2-naphthobenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 4-hydroxybenzophenone, N,N,N',N'-tetramethyl-4,4'-diaminobenzophenone, etc. Substituted vinylbenzophenones can also be cited. Furthermore, examples of structures capable of abstracting hydrogen radicals by ultraviolet irradiation include benzyl, o-benzoylbenzoate, thioxanthone, 3-ketocoumarinyl, 2-ethylanthraquinoneyl, and camphorquinoneyl. Compounds having these structures can be used as compounds derived from the aforementioned first monomer unit.

[0015] (1-2-2-3) As a monomer constituting the main chain portion of the first monomer unit, it is only necessary to have the ability to form ester bonds (-O-CO- or -CO-O-) or amide bonds with aryl ketone residues. Polymerizable monomers with functional groups (carboxyl, hydroxyl, amino, etc.) of covalent bonds such as -NH-CO- or -CO-NH-, carbamate bonds (-NH-CO-O- or -O-CO-NH-), carbonate bonds (-O-CO-O-), and urea bonds (-NH-CO-NH-) are all acceptable.

[0016] (1-2-2-4) As a specific example of the applicable first monomer unit, if we take an aryl ketone residue as an example of a benzophenone compound, the following can be listed: benzophenone, 4-propenyloxyethoxy-4'-bromobenzophenone, 4-methylpropenyloxybenzophenone, 4-methylpropenyloxyethoxybenzophenone, 4-methylpropenyloxy-4'-methoxybenzophenone, 4-methylpropenyloxyethoxy-4'-methoxybenzophenone, 4-methylpropenyloxy-4'-bromobenzophenone, 4-methylpropenyloxyethoxy-4'-bromobenzophenone, etc.

[0017] (1-2-3) Second Monomer Unit (1-2-3-1) The aliphatic hydrocarbon residue containing a carbon atom that readily undergoes hydrogen abstraction, as mentioned in the second monomer unit, refers to an aliphatic hydrocarbon residue (preferably a monovalent hydrocarbon residue) containing a carbon atom that facilitates cross-linking reactions, through photochemical reactions occurring on aryl ketone residues in the side chain. For example, it may be an aliphatic hydrocarbon chain containing carbon atoms selected from groups consisting of tertiary carbon atoms; secondary carbon atoms, preferably secondary carbon atoms with hydroxyl groups; and methyl, methylene, or methine groups directly attached to unsaturated organic groups (aromatic rings, ethyl groups, etc.); or methylene or methine groups directly attached to the hydroxyl oxygen atom. It may be arbitrarily substituted with substituents such as hydroxyl, alkoxy, or aryl groups. The aliphatic hydrocarbon residues mentioned here are interpreted as being easily replaced by aromatic rings because the hydrogen atom bonded to the carbon atom in the residue is prone to abstraction reactions. Alternatively, the chain of aliphatic hydrocarbon residues may be interrupted by the insertion of an aromatic ring along the way (e.g., -R-Ar-R, where R is an aliphatic hydrocarbon chain and Ar is an aromatic ring). Aliphatic hydrocarbon residues in the side chain can be directly covalently bonded to the main chain, but they can also be bonded to the functional groups such as carboxyl, hydroxyl, and amino groups of the polymer constituting the main chain via ester bonds (-O-CO- or -CO-O-), amide bonds (-NH-CO- or -NH-CO-), etc. Covalent bonds such as -CO-NH-, carbamate bonds (-NH-CO-O- or -O-CO-NH-), carbonate bonds (-O-CO-O-), and urea bonds (-NH-CO-NH-) form side chains. Covalent bonds such as ester bonds (-O-CO- or -CO-O-), amide bonds (-NH-CO- or -CO-NH-), carbamate bonds (-NH-CO-O- or -O-CO-NH-), carbonate bonds (-O-CO-O-), and urea bonds (-NH-CO-NH-) can combine two of these bonds, and these two covalent bonds can be connected by a divalent linker, such as a heteroatom (oxygen atom, etc.), to the hydrocarbon chain that has been interrupted. Examples include -CO-OLO-CO- and -CO-NH-L-NH-CO-. The preferred number of carbon atoms for this aliphatic hydrocarbon residue is 1 to 18. Furthermore, from the viewpoint of improving the adhesion between the self-crosslinking polymer and the coating surface, it is preferable to bond hydrophilic substituents such as hydroxyl groups to carbon atoms where hydrogen abstraction reactions are likely to occur. For example, -CH(OH)- and other aliphatic hydrocarbon residues containing such carbon atoms, such as CH3CH(OH)CH2-, are preferred.

[0018] (1-2-3-2) Specific examples of a second monomer containing this aliphatic hydrocarbon residue in its side chain can be given below. That is, As alkyl (meth)acrylates, there are acrylate monomers having branched or cyclic alkyl chains with 1 to 22 carbon atoms, such as 2-ethylhexyl (meth)acrylate, isobutyl (meth)acrylate, cyclohexyl (meth)acrylate, isocamphene (meth)acrylate, and dicyclopentyl (meth)acrylate monomers; 2-Hydroxyethyl methacrylate, 2-Hydroxypropyl methacrylate, 3-Hydroxypropyl methacrylate, 2-Hydroxybutyl methacrylate, 4-Hydroxybutyl methacrylate, 1,4-cyclohexanediethanol mono(meth)acrylate, 1-glycerol(meth)acrylate, 2-hydroxyethyl(meth)acrylamide, N-hydroxypropyl(meth)acrylamide, allyl alcohol, and other hydroxyl-containing monomers.

[0019] (1-2-3-3) The aromatic ring residues mentioned in the second monomer unit can be those that undergo photochemical reactions through the aryl ketone residues in the side chain, causing hydrogen abstraction reactions and facilitating cross-linking reactions, but they are different from the side chains of the first monomer unit containing aryl ketone residues. More specifically, examples include residues with an aromatic ring structure having 6 to 40 substituted carbon atoms, such as benzene, naphthalene, anthracene, acenaphthene, fumonisin, phenaene, indene, indane, benzo[a]indene, pyrene, β-phenanthrene, perylene, condensed tetraphenylene, condensed pentaphenylene, keratin, condensed heptaphenylene, benzo[a]anthracene, dibenzo[a,j]phenanthrene, and dibenzo[a,j]anthracene. The aforementioned aromatic ring residue system may have any chosen substituents. For example, some or all of the hydrogen atoms in the above-mentioned aromatic ring structure with 6 to 40 carbon atoms may be hydroxyl, halogen, carboxyl, nitro, cyano, methylenedioxy, acetoxy, methylthio, amino, or alkoxy with 1 to 9 carbon atoms. Examples of alkoxy groups with 1 to 9 carbon atoms include methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy, n-pentoxy, 1-methyl-n-butoxy, 2-methyl-n-butoxy, 3-methyl-n-butoxy, 1,1-dimethyl-n-propoxy, 1,2-dimethyl-n-propoxy, 2,2-dimethyl-n-propoxy, 1-ethyl-n-propoxy, n-hexyloxy, 1-methyl-n-pentoxy, 2-methyl-n-pentoxy, 3-methyl-n-pentoxy, 4-methyl-n-pentoxy, etc. The compounds include 1,1-dimethyl-n-butoxy, 1,2-dimethyl-n-butoxy, 1,3-dimethyl-n-butoxy, 2,2-dimethyl-n-butoxy, 2,3-dimethyl-n-butoxy, 3,3-dimethyl-n-butoxy, 1-ethyl-n-butoxy, 2-ethyl-n-butoxy, 1,1,2-trimethyl-n-propoxy, 1,2,2'-trimethyl-n-propoxy, 1-ethyl-1-methyl-n-propoxy, 1-ethyl-2-methyl-n-propoxy, n-heptoxy, n-octoxy, and n-nonoxy, etc.

[0020] (1-2-3-4) As the main chain portion constituting the second monomer unit, any polymerizable monomer can be any monomer that has a functional group (carboxyl, hydroxyl, amino, etc.) that can form covalent bonds with aliphatic hydrocarbon residues or aromatic ring residues containing carbon atoms that readily undergo hydrogen abstraction reactions. These functional groups can form ester bonds (-O-CO- or -CO-O-), amide bonds (-NH-CO- or -CO-NH-), carbamate bonds (-NH-CO-O- or -O-CO-NH-), carbonate bonds (-O-CO-O-), urea bonds (-NH-CO-NH-), etc. Here, the aliphatic hydrocarbon residues are the aliphatic hydrocarbon parts that constitute functional groups such as alkoxy or alkylamine groups, and can form covalent bonds with the functional groups (carboxyl, hydroxyl, amino, etc.) of the monomers that constitute the main chain. Furthermore, aromatic ring residues are also present on its aromatic ring, such as substituents such as hydroxyl, amino, and carboxyl groups, which can form covalent bonds with the functional groups such as carboxyl, hydroxyl, and amino groups that constitute the main chain of the polymer. These covalent bonds include ester bonds (-O-CO- or -CO-O-), amide bonds (-NH-CO- or -CO-NH-), carbamate bonds (-NH-CO-O- or -O-CO-NH-), carbonate bonds (-O-CO-O-), urea bonds (-NH-CO-NH-), etc. Furthermore, two covalent bonds, such as ester bonds (-O-CO- or -CO-O-), amide bonds (-NH-CO- or -CO-NH-), carbamate bonds (-NH-CO-O- or -O-CO-NH-), carbonate bonds (-O-CO-O-), and urea bonds (-NH-CO-NH-), can be combined. These two covalent bonds can be connected by a divalent linker, such as a heteroatom (oxygen atom, etc.), which links the interrupted hydrocarbon chain. Examples include -CO-OLO-CO- and -CO-NH-L-NH-CO-.

[0021] (1-2-3-5) The second monomer unit undergoes cross-linking via a photochemical reaction induced by the aryl ketone residues present in the first monomer unit, resulting in hardening. Here, "self-cross-linking" refers to hardening that occurs without the need for an addition of a polymerization initiator. The ratio of the number of repetitions of the first monomer unit to the number of repetitions of the second monomer unit is determined by taking into account the film thickness to be formed by photocuring of the self-crosslinking polymer and the light absorption of the aryl ketone residues. In order to ensure that the light used for curing reaches the bottom of the film to be formed sufficiently, it is necessary to explore the proportion of the first monomer unit, which serves as a measure of the degree of light absorption, and the film thickness corresponding to the distance that the light can reach. When forming a film with a thickness of 300 nm, the ratio of the number of repetitions of the first monomer unit to the number of repetitions of monomer units other than the first monomer unit (including the second monomer unit) can be adjusted so that the number of repetitions of the first monomer unit is 0.01% or more, preferably 0.1% or more, and more preferably 1% or more.

[0022] (1-2-3-6) When the self-crosslinking polymer further contains monomer units different from the first and second monomers, it is referred to as the ratio of the number of repetitions of the first monomer unit to the number of repetitions of monomer units other than the first monomer unit containing the second monomer unit, as described above (1-2-3-5).

[0023] (1-2-3-7) The self-crosslinking polymer of the present invention contains a first monomer unit with aryl ketone residues in the side chain as a monomer unit, so it can self-crosslink without adding a polymerization initiator, and at the same time, it can reduce the oxygen atom content, thereby improving the etching resistance.

[0024] (1-3: Solvent (B)) The solvent contained in the photocurable resin composition as one embodiment of the present invention may include, for example, water, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl ceroxythionate acetate, ethyl ceroxythionate acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, cycloheptanone, 4-methyl-2- Pentanol, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, ethyl ethoxylate, 2-hydroxyethyl acetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, 2-heptanone, methoxycyclopentane, anisole, γ-butyrolactone, N-methylpyrrolidone, N,N-dimethylformamide, and N,N-dimethylacetamide. These solvents can be used alone or in combination of two or more. The solvent can be added in such a way that it has a suitable viscosity for the photocurable resin composition as described in this invention. Generally, the amount is about 100 to 3,000 parts by mass relative to 100 parts by mass of the self-crosslinking polymer (A) and the crosslinking polymer or compound (C) that is optionally contained therein.

[0025] (1-4: Cross-linked polymers or cross-linked compounds (C)) (1-4-1) The photocurable resin composition of one embodiment of the present invention may further include a crosslinked polymer or a crosslinked compound (C). Crosslinked polymers or crosslinked compounds (C) are polymers or compounds with crosslinking groups, referring to those other than crosslinked polymers (A). Here, the term "crosslinking group" refers to a group that can form a crosslinked structure through the action of light, electron beams, other electromagnetic waves, free radicals, acids, heat, water, oxygen, etc. Examples include epoxy groups, acrylic groups, vinyl groups, carboxylic acid groups, thiol groups, silicone groups, cinnamic acid groups, and hydroxyl groups (including phenolic hydroxyl groups), but are not limited to these. Examples of cross-linked polymers or cross-linked compounds (C) are shown below, but are not limited thereto. ·Epoxy (meth)acrylates, Cinnamic acid-grafted epoxy phenolic varnish Phenolic plastics are thermosetting materials obtained through polycondensation and the formation of a three-dimensional mesh, accompanied by the removal of phenols and aldehydes by water. For example, melamine resins such as trimethylol melamine and hexamethylol melamine; urea resins such as dimethylolpropene urea, dimethylolvinyl urea, and dimethylolhydroxyurea; and amino plastic resins such as dimethylol uronic acid resin. • (Terminated) isocyanates, · Ethylene ether, • Polysiloxane resins containing (meth)acrylic acid groups, · Epoxy resin.

[0026] (1-4-2) The crosslinked polymer or crosslinked compound (C) may be a crosslinked compound disclosed in International Publication No. 2018 / 190380 that comprises at least one of the partial structures (I) shown in Formulas (1-1) to (1-7) below, preferably at least two partial structures. (in the formula, R1, R1a, R3, R5a, and R6a each independently represent an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms (the alkyl group and aryl group can be arbitrarily substituted by one or more amino or amine groups), an oxygen atom, a carbonyl group, a sulfur atom, -C(O)-NR a-, -NR b-, or a divalent group formed by combinations thereof. R 5 independently represents a nitrogen atom, or a trivalent group formed by a nitrogen atom and at least one group selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms (the alkyl group and the aryl group may be substituted by one or more amino groups), an oxygen atom, a carbonyl group, a sulfur atom, -C(O)-NR a- and -NR b-. R2, R2a, R4, and R6 each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a monovalent group consisting of a hydrogen atom and at least one group selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an oxygen atom, a carbonyl group, -C(O)-NR a-, and -NR b-. Ra represents an alkyl group with 1 to 10 carbon atoms. Rb represents a hydrogen atom, an alkyl group with 1 to 10 carbon atoms, or an alkyl carbonyl group with 1 to 10 carbon atoms. n represents the number of repeating units from 1 to 10, and The dashed line represents the chemical bond with the adjacent atom. The entire disclosure of International Publication No. 2018 / 190380 is incorporated herein by reference.

[0027] (1-4-3) The cross-linked polymer or cross-linked compound (C) may also be a combination of a polyfunctional epoxy (meth)acrylate compound and a polyfunctional thiol compound as disclosed in Japanese Patent Application Publication No. 2016-003160. This composite system can be appropriately crosslinked using a free radical polymerization initiator. The molecular weight of the above-mentioned multifunctional epoxy (meth)acrylate compounds can be 300 to 20,000. The aforementioned polyfunctional epoxy (meth)acrylate compounds may be bisphenol type polyfunctional epoxy (meth)acrylate compounds. The above-mentioned polyfunctional thiols can be in liquid form at 25°C. In addition to the combinations mentioned above, it may also contain polymerization inhibitors. The entire disclosure of Japanese Patent Application Publication No. 2016-003160 is used for reference in this case.

[0028] (1-4-4) Crosslinked polymers or crosslinked compounds (C) may also be photopolymerizable substances as described in International Publication No. 2009 / 104643. The aforementioned photopolymerizable substance may be a compound having at least one reactive group capable of cationic polymerization, or a compound having at least one reactive group capable of free radical polymerization. The aforementioned photopolymerizable compounds may be sugar compounds. The aforementioned sugar compounds can be monosaccharides or disaccharides. The aforementioned sugar compound can be represented by formula (10): (However, G1 represents the sugar backbone, T represents the divalent linker, R1 represents vinyl or glycidyl, R2 represents hydrogen or hydroxyl; n and L each represent an integer of 0 or 1, p is an integer and is the total number of hydroxyl groups in the sugar; m is an integer that satisfies 1≦m≦(pm), preferably 2≦m≦(pm).) The aforementioned photopolymerizable compounds may be alicyclic epoxy compounds or alicyclic oxobutane compounds. The aforementioned alicyclic epoxy compounds can be derivatives of cycloalkylene oxides. The aforementioned alicyclic epoxy compounds can be of formula (2) or formula (3): (However, G2 represents a 1- to 5-valent linkage group of alkyl, carbonyl, heterocyclic, aromatic ring or such combination, and G3 is an alkyl, alkylcarbonyl, heterocyclic, aromatic ring or such combination of organogroups, and n and m each represent 1 to 5, with m preferably representing an integer of 2 to 5). The entire disclosure of International Publication No. 2009 / 104643 is incorporated herein by reference.

[0029] (1-5: Resin Composition) There are no particular limitations on the preparation method of the photocurable resin composition. That is, as long as the self-crosslinking polymer (A), solvent (B), any selected crosslinking polymer or crosslinking compound (C), and other components are mixed in any proportion and in any order to form a homogeneous solution, it is acceptable. The photocurable resin composition in such a solution state is preferably filtered using a filter with a pore size of about 0.2 μm before use. When preparing a cured film with a thickness of approximately 300 nm using spin coating, the photocurable resin composition preferably has a viscosity of less than approximately 100 cps at 25°C. Furthermore, in this invention, the viscosity is the value measured using an E-type viscometer.

[0030] (1-6: Protective film forming components) The photocurable resin composition of the present invention has excellent etching resistance, and is therefore more suitable for use as a protective film forming composition for protecting the edge of a wafer used in semiconductor manufacturing (a protective film forming composition for the edge of a wafer used in semiconductor manufacturing, hereinafter also referred to as "protective film forming composition"). In addition to preventing the aforementioned metal contamination, the protective film covering the ends of semiconductor manufacturing substrates (wafers) should also possess the following properties: dry etching resistance, phosphoric acid resistance, tetramethylammonium hydroxide (TMAH) resistance, HF removal capability, scratch resistance, good embedding properties on stepped substrates, low sublimation content, affinity for hydrophobic substrates, absence of pits or foreign matter on the wafer side, good edge shape, and suppression of internal bulges (the phenomenon of nodular residues of film composition directly below the nozzle ejection orifice). Furthermore, one embodiment of the protective film forming composition of the present invention is photosensitive. For example, it can be a negative solvent-based imaging type. After coating the photosensitive protective film forming composition (negative type) on the surface end and any selected bevel portion and / or back end of the aforementioned substrate, by exposing and developing the portion to be cured, the bevel portion can be accurately covered with the aforementioned protective film. Due to its photosensitivity, the film thickness control of the protective film on the wafer end face becomes easier, internal protrusions can be removed, edge shape can be improved, and it has advantages such as the ability to correct the center position offset during spin coating.

[0031] (1-7: Polysiloxane) (1-7-1) One embodiment of the photocurable resin composition of the present invention may contain any selected polysiloxane. The polysiloxane may be a modified polysiloxane in which a portion of the silanol group is modified, such as a polysiloxane modified in which a portion of the silanol group is modified by an alcohol or protected by an acetal. Furthermore, polysiloxanes, as an example, can be hydrolyzed condensates of hydrolyzable silanes, or modified products in which at least a portion of the silanol groups of the hydrolyzed condensate are modified with alcohol or protected with acetal (hereinafter also referred to as "modified products of hydrolyzed condensates"). The hydrolyzable silanes in the hydrolyzed condensate may contain one or more hydrolyzable silanes. Polysiloxanes can have a main chain structure of any type, including cage-like, ladder-like, linear, and branched types. Furthermore, commercially available polysiloxanes can be used. Furthermore, the "hydrolysis condensates" of hydrolyzable silanes, that is, the products of hydrolysis condensation, include not only polyorganosiloxane polymers of condensates where condensation is fully completed, but also polyorganosiloxane polymers of partially hydrolyzed condensates where condensation is incomplete. These partially hydrolyzed condensates, like the fully condensed condensates, are polymers obtained through the hydrolysis and condensation of hydrolyzable silanes, but the hydrolysis is partial and stops, without condensation, thus leaving Si-OH groups. Examples of polysiloxanes include hydrolyzed condensates of hydrolyzed silanes or modified forms thereof, which contain at least one hydrolyzable silane as shown in formula (1) below. In formula (1), R1 is a group bonded to a silicon atom, which independently represents a substituted alkyl group, a substituted aryl group, a substituted aralkyl group, a substituted halogenated alkyl group, a substituted halogenated aryl group, a substituted halogenated aralkyl group, a substituted alkoxyalkyl group, a substituted alkoxyaryl group, a substituted alkoxyaralkyl group or a substituted alkenyl group, or an organogroup having an epoxy group, an organogroup having an acrylonitrile group, an organogroup having a methacrylonitrile group, an organogroup having a mercapto group, an organogroup having an amino group, an organogroup having an alkoxy group, an organogroup having a sulfonylurea group or an organogroup having a cyano group, or a combination of two or more of the above. Furthermore, R2 represents a group or atom bonded to a silicon atom, and each group independently represents an alkoxy, arylalkoxy, acetoxy, or halogen atom. a represents an integer from 0 to 3.

[0032] (1-7-2: Specific examples of hydrolyzable silanes shown in formula (1)) Specific examples of hydrolyzable silanes represented by formula (1) include tetramethoxysilane, tetrachlorosilane, tetraethoxysilane, tetraethoxysilane, tetran-propoxysilane, tetraisopropoxysilane, tetran-butoxysilane, methyltrimethoxysilane, methyltrichlorosilane, methyltriethoxysilane, methyltripropoxysilane, and methyltributoxysilane. Silane, methyltripentoxysilane, methyltriphenoxysilane, methyltribenzyloxysilane, methyltriphenethoxysilane, epoxypropoxymethyltrimethoxysilane, epoxypropoxymethyltriethoxysilane, α-epoxypropoxyethyltrimethoxysilane, α-epoxypropoxyethyltriethoxysilane, β-epoxypropoxyethyltrimethoxysilane, β-epoxypropoxyethyl β-glycidoxypropyltrimethoxysilane, α-glycidoxypropyltrimethoxysilane, α-glycidoxypropyltriethoxysilane, β-glycidoxypropyltrimethoxysilane, β-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltripropoxysilane, γ-glycidoxypropyltripropoxysilane, γ-glycidoxypropyltripropoxysilane Propyleneoxypropyltributoxysilane, γ-glycidoxypropyltriphenoxysilane, α-glycidoxybutyltrimethoxysilane, α-glycidoxybutyltriethoxysilane, β-glycidoxybutyltriethoxysilane, γ-glycidoxybutyltrimethoxysilane, γ-glycidoxybutyltriethoxysilane, δ-glycidoxybutyltrimethoxysilane, δ-Epoxypropoxybutyltriethoxysilane, (3,4-epoxycyclohexyl)methyltrimethoxysilane, (3,4-epoxycyclohexyl)methyltriethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltriethoxysilane, β-(3,4-epoxycyclohexyl)ethyltripropoxysilane, β-(3,4-epoxycyclohexyl)ethyltributoxysilane, β-(3,4-epoxycyclohexyl)ethyltriphenoxysilane, γ-(3,4-epoxycyclohexyl)propyltrimethoxysilane, γ-(3,4-epoxycyclohexyl)propyltriethoxysilane, δ-(3,4-epoxycyclohexyl)butyltrimethoxysilane, δ-(3,4-epoxycyclohexyl)butyltrimethoxysilane, δ-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, δ-(3,4-epoxycyclohexyl)ethyltriethoxysilane, β-(3,4-epoxycyclohexyl)ethyltriethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimeth ... 4-Epoxycyclohexyl)butyltriethoxysilane, epoxypropoxymethylmethyldimethoxysilane, epoxypropoxymethylmethyldiethoxysilane, α-epoxypropoxyethylmethyldimethoxysilane, α-epoxypropoxyethylmethyldiethoxysilane, β-epoxypropoxyethylmethyldimethoxysilane, β-epoxypropoxyethylethyldimethoxysilane, α-epoxypropoxypropylmethyldimethoxysilane, α-epoxypropoxypropylmethyldiethoxysilane, β-epoxypropoxypropylmethyldimethoxysilane, β-epoxypropoxypropylethyldimethoxysilane, β-epoxypropoxypropylethyldimethoxysilane, γ-epoxypropoxypropylmethyldimethoxysilane, γ-epoxypropoxypropylmethyldiethoxysilane, γ-epoxypropoxypropylmethyldipropoxysilaneγ-Glycidoxypropylmethyldibutoxysilane, γ-Glycidoxypropylmethyldiphenoxysilane, γ-Glycidoxypropylethyldimethoxysilane, γ-Glycidoxypropylethyldiethoxysilane, γ-Glycidoxypropylvinyldimethoxysilane, γ-Glycidoxypropylvinyldiethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltriethoxysilane, methylvinyldimethoxysilane, methylvinyldiethoxysilane, methylvinyldichlorosilane, dimethylvinylmethoxysilane, dimethylvinylethoxysilane, dimethylvinylchlorosilane, dimethylvinylchlorosilane Dimethylvinylethoxysilane, Divinyldimethoxysilane, Divinyldiethoxysilane, Divinyldichlorosilane, Divinyldiethoxysilane, γ-glycidoxypropylvinyldimethoxysilane, γ-glycidoxypropylvinyldiethoxysilane, Allyltrimethoxysilane, Allyltriethoxysilane, Allyltrichlorosilane, Allyl Triethoxysilane, allyl methyl dimethoxysilane, allyl methyl diethoxysilane, allyl methyl dichlorosilane, allyl methyl diethoxysilane, allyl dimethyl methoxysilane, allyl dimethyl ethoxysilane, allyl dimethyl chlorosilane, allyl dimethyl ethoxysilane, diallyl dimethoxysilane, diallyl diethoxysilane, Diallyl dichlorosilane, diallyl diethoxysilane, 3-allylaminopropyltrimethoxysilane, 3-allylaminopropyltriethoxysilane, p-styryltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltrichlorosilane, phenyltriethoxysilane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane, phenyl Methyldichlorosilane, phenylmethyldiacetoxysilane, phenyldimethylmethoxysilane, phenyldimethylethoxysilane, phenyldimethylchlorosilane, phenyldimethylacetoxysilane, diphenylmethylmethoxysilane, diphenylmethylethoxysilane, diphenylmethylchlorosilane, diphenylmethylacetoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, Diphenyl dichlorosilane, diphenyl diethoxysilane, triphenyl methoxysilane, triphenyl ethoxysilane, triphenyl ethoxysilane, triphenyl chlorosilane, 3-phenylaminopropyltrimethoxysilane, 3-phenylaminopropyltriethoxysilane, dimethoxymethyl-3-(3-phenoxypropylthiopropyl)silane, triethoxy((2-methoxy-4-(methyl))silane oxymethyl)phenoxy)methyl)silane, benzyltrimethoxysilane, benzyltriethoxysilane, benzylmethyldimethoxysilane, benzylmethyldiethoxysilane, benzyldimethylmethoxysilane, benzyldimethylethoxysilane, benzyldimethylchlorosilane, phenethyltrimethoxysilane, phenethyltriethoxysilane, phenethyltrichlorosilane, phenethyltriethoxysilane,Phenethylmethyl dimethoxysilane, phenethylmethyl diethoxysilane, phenethylmethyl dichlorosilane, phenethylmethyl diethoxysilane, methoxyphenyl trimethoxysilane, methoxyphenyl triethoxysilane, methoxyphenyl triethoxysilane, methoxyphenyl trichlorosilane, methoxybenzyl trimethoxysilane, methoxybenzyl triethoxysilane, methoxybenzyl tri... Ethyloxysilane, methoxybenzyltrichlorosilane, methoxyphenylethyltrimethoxysilane, methoxyphenylethyltriethoxysilane, methoxyphenylethyltriethoxysilane, methoxyphenylethyltrichlorosilane, ethoxyphenyltrimethoxysilane, ethoxyphenyltriethoxysilane, ethoxyphenyltriethoxysilane, ethoxyphenyltrichlorosilane, ethoxybenzyltrimethoxysilane Alkane, ethoxybenzyltriethoxysilane, ethoxybenzyltriethoxysilane, ethoxybenzyltrichlorosilane, isopropoxyphenyltrimethoxysilane, isopropoxyphenyltriethoxysilane, isopropoxyphenyltriethoxysilane, isopropoxyphenyltrichlorosilane, isopropoxybenzyltrimethoxysilane, isopropoxybenzyltriethoxysilane, isopropoxybenzyltriethoxysilane Silane, isopropoxybenzyltrichlorosilane, tributoxyphenyltrimethoxysilane, tributoxyphenyltriethoxysilane, tributoxyphenyltriethoxysilane, tributoxyphenyltrichlorosilane, tributoxyphenyltrichlorosilane, tributoxybenzyltrimethoxysilane, tributoxybenzyltriethoxysilane, tributoxybenzyltriethoxysilane, tributoxybenzyltrichlorosilane, methane γ-chloropropane, ... Acryloxysilane, 3,3,3-trifluoropropyltrimethoxysilane, γ-methylpropenyl acryloxypropyltrimethoxysilane, γ-conylpropyltrimethoxysilane, γ-conylpropyltriethoxysilane, β-cyanoethyltriethoxysilane, thiocyanate propyltriethoxysilane, chloromethyltrimethoxysilane, chloromethyltriethoxysilane, triethoxysilylpropyldiene Propylene isocyanate, bicyclo[2,2,1]pentenyltriethoxysilane, benzenesulfonylpropyltriethoxysilane, phenylaminopropyltriethoxysilane, dimethylaminopropyltrimethoxysilane, dimethyldimethoxysilane, phenylmethyldimethoxysilane, dimethyldiethoxysilane, phenylmethyldiethoxysilane, γ-chloropropylmethyldimethoxysilane, γ -Chloropropylmethyldiethoxysilane, dimethyldiethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-conylpropylmethyldimethoxysilane, γ-conylmethyldiethoxysilane, methylvinyldimethoxysilane, methylvinyldiethoxysilane, but not limited to these.

[0033] (1-8: Any other ingredients) Furthermore, the photocurable resin composition of one embodiment of the present invention may, as needed, include free radical polymerization initiators (photopolymerization initiators, etc.), acids (catalysts), thermal acid generators, photoacid generators, alkalis (catalysts), thermal alkali generators, photoalkali generators, antioxidants, polymerization inhibitors, crosslinking agents (polyfunctional acrylic acids, etc.), adhesion enhancers, adhesion aids (silane coupling agents), surfactants, defoamers, rheology modifiers, pigments, dyes, preservation stabilizers, solubilizers of polyphenols or polycarboxylic acids, sensitizers, etc. However, since the self-crosslinking polymer (A) contained in the photocurable resin composition of the present invention is self-crosslinking, at least for the curing of the self-crosslinking polymer (A), it is not necessary to add a photopolymerization initiator.

[0034] (1-8-1: Free radical polymerization initiator) Free radical polymerization initiators are any substances that release substances that initiate free radical polymerization upon exposure to light and / or heating. Examples of photoradioactive free radical polymerization initiators include benzophenone derivatives, imidazole derivatives, diimidazole derivatives, N-arylglycine derivatives, organic azide compounds, titanocene compounds, aluminate complexes, organic peroxides, N-alkoxypyridinium salts, and thioxanone derivatives. More specifically, examples include benzophenone, 1,3-bis(tert-butyldioxycarbonyl)benzophenone, 3,3',4,4'-tetra(tert-butyldioxycarbonyl)benzophenone, 3-phenyl-5-azolinone, 2-mercaptobenzimidazole, bis(2,4,5-triphenyl)imidazole, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexylphenyl ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butane-1-one, bis(n-5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrole-1-yl)-phenyl)titanium, etc., but are not limited to these. Commercially available products can also be used as photoradical polymerization initiators, such as BASF's IRGACURE (registered trademark) 651, 184, 369, and 784. Alternatively, other commercially available products can be used, specifically including BASF's IRGACURE (registered trademark) 500, 907, 379, 819, 127, 500, 754, 250, 1800, 1870, OXE01, DAROCUR (registered trademark) TPO, and 1173; Lambson's Speedcure (registered trademark) MBB, PBZ, ITX, CTX, and EDB; Lamberty's Esacure (registered trademark) ONE, KIP150, and KTO46; and Nippon Kayaku Co., Ltd.'s KAYACURE (registered trademark) DETX-S, CTX, BMS, and DMBI. Furthermore, examples of peroxides that can be used as initiators for thermal free radical polymerization include acetyl peroxide, benzoyl peroxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, hydrogen peroxide, tributyl hydroperoxide, cumene hydroperoxide, di-tert-butyl peroxide, diisopropylphenyl peroxide, dilauryl peroxide, tributyl peroxyacetate, tributyl peroxytrimethyl acetate, and tributyl peroxy-2-ethylhexanoate; 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylpentanonitrile), and (1-phenylethyl)azobis(phenyl) Azo compounds such as methyl methane, 2,2'-azobis(4-methoxy-2,4-dimethylpentanonitrile), dimethyl-2,2'-azobisisobutyrate, 2,2'-azobis(2-methylbutanonitrile), 1,1'-azobis(1-cyclohexanecarboxylonitrile), 2-(aminomethoxyazo)isobutanonitrile, 2,2'-azobis(2,4,4-trimethylpentane), 2-phenylazo-2,4-dimethyl-4-methoxypentanonitrile, and 2,2'-azobis(2-methylpropane); persulfates such as ammonium persulfate, sodium persulfate, and potassium persulfate, but not limited thereto. Examples of commercially available thermal free radical polymerization initiators include Peroyl (registered trademark) IB, NPP, IPP, SBP, TCP, OPP, SA, 355, L, Perbutyl (registered trademark) ND, NHP, MA, PV, 355, A, C, D, E, L, I, O, P, Z, Perbutyl (registered trademark) ND, PV, D, I, O, Z, Perocta (registered trademark) ND, Nyper (registered trademark) PMB, BMT, BW, Pertetra (registered trademark) A, Perhexa (registered trademark) MC, TMH, HC, 250, 25B, C, 25Z, 22, V, Perocta (registered trademark) O, and Percumyl (registered trademark). (Trademark) ND, D, Permenta (registered trademark) H, Nofmer (registered trademark) BC; Wako Pure Chemical Industries (Group) Co., Ltd. manufactures V-70, V-65, V-59, V-40, V-30, VA-044, VA-046B, VA-061, V-50, VA-057, VA-086, VF-096, VAm-110, V-601, V-501; BASF manufactures IRGACURE (registered trademark) 184, 369, 651, 500, 819, 907, 784, 2959, CGI1700, CGI1750, CGI1850, CG24-61, DAROCUR (registered trademark) 1116, 1173, LUCIRIN (registered trademark) TPO; Cytec Surface Specialties' UVECRYL (registered trademark) P36; Lamberti's Esacure (registered trademark) KIP150, KIP65LT, KIP100F, KT37, KT55, KTO46, KIP75 / B, etc., but not limited to these. Free radical polymerization initiators may be used in combination with one or more. The preferred content of the free radical polymerization initiator relative to 100 parts by mass of the polymer or compound having crosslinking groups is 1 part by mass or more, 2 parts by mass or more, 3 parts by mass or more, 50 parts by mass or less, 20 parts by mass or less, or 10 parts by mass or less.

[0035] (1-8-2: Polymerization Inhibitor) As polymerization inhibitors, hindered phenolic compounds can be used, specifically including 2,6-diisobutylphenol, 3,5-ditert-butylphenol, 3,5-ditert-butylcresol, hydroquinone, hydroquinone monomethyl ether, N-nitroso-N-phenylhydroxylamine aluminum, gallnutol, tert-butylcatechol, 4-methoxy-1-naphthol, 2,6-ditert-butyl-4-methylphenol, 2,5-ditert-butyl-hydroquinone, octadecyl-3-(3,5-ditert-butyl-4-hydroxyphenyl)propionate, isooctyl-3-(3,5-ditert-butyl-4-hydroxyphenyl)propionate, 4,4'-methylenebis(2,6-ditert-butylphenol), 4,4'-thiobis(3-methyl-6-tert-butylphenol), 4,4 '-Butylene-bis(3-methyl-6-tert-butylphenol), triethylene glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propionate], 2,2-thio-diethylidene-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylenebis(3,5-ditert-butyl-4-hydroxy-hydrocinnamic acid), 2,2'-methylene-bis(4-methyl-6-tert-butylphenol), 2,2'-methylene-bis(4-ethyl-6-tert-butylphenol), pentaerythritol-tetra[3-(3,5-ditert-butyl-4-hydroxyphenyl)propionate] , san-(3,5-ditert-butyl-4-hydroxybenzyl)-triisocyanate, 1,3,5-trimethyl-2,4,6-san-(3,5-ditert-butyl-4-hydroxybenzyl)benzene, 1,3,5-san-(3-hydroxy-2,6-dimethyl-4-isopropylbenzyl)-1,3,5-tris(2,4,6-(1H,3H,5H)-trione, 1,3,5-san-(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-tris(2,4,6-(1H,3H,5H)-trione, 1,3,5-san-(4-s-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-tris(2,4,6-(1H,3H,5H)-trione, 1, 3,5-Tris(4-(1-ethylpropyl)-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-tris(2,4,6-(1H,3H,5H)-trione, 1,3,5-Tris(4-triethylmethyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-tris(2,4,6-(1H,3H,5H)-trione, 1,3,5-Tris(3-hydroxy-2,6-dimethyl-4-phenylbenzyl)-1,3,5-tris(2,4,6-(1H,3H,5H)-trione), 1,3,5-Tris(4-tert-butyl-3-hydroxy-2,5,6-trimethylbenzyl)-1,3,5-tris(2,4,6-(1H,3H,5H)-trione), 1,3,5-Tris(4-tert-butyl-5-ethyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-tris(2,4,6-(1H,3H,5H)-trione), 1,3,5-Tris(4-tert-butyl-6-ethyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-tris(2,4,6-(1H,3H,5H)-trione), 1,3,5-Tris(4-tert-butyl-6-ethyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-tris(2,4,6-(1H,3H,5H)-trione), 1,3,5-Tris(4-tert-butyl-5,6-diethyl-3-hydroxy-2,6 ... Examples of triones include 2-methylbenzyl)-1,3,5-tris(2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-3-hydroxy-2-methylbenzyl)-1,3,5-tris(2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-tris(2,4,6-(1H,3H,5H)-trione), and 1,3,5-tris(4-tert-butyl-5-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-tris(2,4,6-(1H,3H,5H)-trione. Among hindered phenolic compounds, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-tris(2,4,6-(1H,3H,5H)-trione is preferred. The aforementioned polymerization inhibitors can be commercially available products, such as Irganox-3114 (manufactured by BASF Japan Co., Ltd.) as a specific example. The polymerization inhibitor may be used alone or in combination with two or more. The content of the polymerization inhibitor is preferably 0.01 to 1 part by mass, more preferably 0.01 to 0.5 parts by mass, relative to 100 parts by mass of the self-crosslinking polymer (A) and any selected crosslinking polymer or crosslinking compound (C).

[0036] (1-8-3: Surfactants) Examples of surfactants include polyoxyethylene alkyl ether compounds such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; polyoxyethylene alkyl allyl ether compounds such as polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether; polyoxyethylene-polyoxypropylene block copolymer compounds; sorbitan fatty acid ester compounds such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan trioleate, and sorbitan tristearate; and polyoxyethylene sorbitan fatty acid ester compounds such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, and polyoxyethylene sorbitan tristearate. Furthermore, examples include fluorinated surfactants such as Eftop EF301, EF303, EF352 (manufactured by TOHKEM PRODUCTS), Megafac F171, F173, R-08, R-30 (manufactured by Dai Nippon Ink), Fluorad FC430, FC431 (manufactured by Sumitomo 3M), and Asahiguard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass), as well as organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Industry). A single surfactant may be used, or two or more may be used in combination. The surfactant content is preferably 0.1 parts by mass or more, 0.5 parts by mass or more, 5 parts by mass or less, or 2 parts by mass or less, relative to 100 parts by mass of the self-crosslinking polymer (A) and any selected crosslinking polymers or crosslinking compounds.

[0037] (1-8-4: Other components such as acid-base catalysts, etc.) As an acid catalyst or base catalyst, acidic compounds, base compounds, or various compounds that produce acid or base due to heat or light can be used. As acidic compounds, sulfonic acid compounds or carboxylic acid compounds can be used. Examples of sulfonic acid or carboxylic acid compounds include p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium trifluoromethanesulfonate (=pyridinium trifluoromethanesulfonic acid), pyridinium p-toluenesulfonate, pyridinium-4-hydroxybenzenesulfonate, salicylic acid, camphorsulfonic acid, 5-sulfosalicylic acid, 4-chlorobenzenesulfonic acid, 4-phenolsulfonic acid, pyridinium-4-phenolsulfonate, benzenedisulfonic acid, 1-naphthalenesulfonic acid, 4-nitrobenzenesulfonic acid, citric acid, benzoic acid esters, and hydroxybenzoic acid esters. As an alkaline compound, amine compounds or ammonium hydroxide compounds can be used; as a compound that produces alkali due to heat, urea can be used. Examples of amine compounds include tertiary amines such as triethanolamine, tributanolamine, trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, tri-tert-butylamine, tri-n-octylamine, triisopropanolamine, phenyldiethanolamine, stearyldiethanolamine, and diazabicyclooctane, as well as aromatic amines such as pyridine and 4-dimethylaminopyridine. Also, examples of primary amines such as benzylamine and n-butylamine, and secondary amines such as diethylamine and di-n-butylamine, are also examples of amine compounds. Examples of ammonium hydroxide compounds include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, benzyltriethylammonium hydroxide, cetyltrimethylammonium hydroxide, phenyltrimethylammonium hydroxide, and phenyltriethylammonium hydroxide. As an acid generating agent, it can be used for both thermal acid generating agents and photoacid generating agents. Examples of sulfonic acid and carboxylic acid compounds that can be used as thermal acid generators include p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium p-toluenesulfonate (pyridinium p-toluenesulfonic acid), pyridinium p-hydroxybenzenesulfonic acid (pyridinium p-phenolsulfonate), pyridinium trifluoromethanesulfonic acid, salicylic acid, camphorsulfonic acid, 5-sulfosalicylic acid, 4-chlorobenzenesulfonic acid, 4-hydroxybenzenesulfonic acid, benzenedisulfonic acid, 1-naphthalenesulfonic acid, citric acid, benzoic acid, hydroxybenzoic acid, etc. As commercially available products, examples include K-PURE [registered trademark] CXC-1612, CXC-1614, TAG-2172, TAG-2179, TAG-2678, and TAG2689 (all manufactured by King Industries) and SI-45, SI-60, SI-80, SI-100, SI-110, and SI-150 (all manufactured by Sanshin Chemical Industry Co., Ltd.). As photoacid generating agents, there are strontium salts, iodonium salts, sulfonyldiazomethane, N-sulfonoxyimidine, benzoin sulfonate type photoacid generating agents, gallophenol trisulfonate type photoacid generating agents, uranium type photoacid generating agents, glyoxal dioxime derivative type photoacid generating agents, oxime-O-sulfonate type acid generating agents, and dioxime sulfonate type acid generating agents, etc. For example, bis(4-tert-butylphenyl)iodonium trifluoromethane sulfonate, triphenylstrontium trifluoromethane sulfonate, phenyl-bis(trichloromethyl)-S-trisulfonate, benzoin toluene sulfonate, and N-hydroxysuccinimide trifluoromethane sulfonate, etc. Examples of heat-generating alkalis include, for instance, amine carbamates such as 1-methyl-1-(4-biphenyl)ethylaminocarbamate and 2-cyano-1,1-dimethylethylaminocarbamate; ureas such as urea and N,N-dimethyl-N'-methylurea; guanidines such as guanidine trichloroacetate, guanidine phenylsulfonylacetate, and guanidine phenylpropynate; dihydropyridines such as 1,4-dihydronicotinamide; dimethylpiperidines such as N-(isopropoxycarbonyl)-2,6-dimethylpiperidine, N-(terbutoxycarbonyl)-2,6-dimethylpiperidine, and N-(benzyloxycarbonyl)-2,6-dimethylpiperidine; quaternary ammonium salts such as tetramethylammonium phenylsulfonylacetate and tetramethylammonium phenylpropynate; and dicyandiamide. Furthermore, examples include U-CAT (registered trademark) SA810, SA831, SA841, and SA851 (all manufactured by SUN-APRO) salts of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU). Examples of photoalkali generators include alkylamine photoalkali generators such as 9-anthraylmethyl-N,N-diethylaminocarbamate; cycloalkylamine photoalkali generators such as 9-anthrayl-N,N-dicyclohexylaminocarbamate, 1-(9,10-anthraquinone-2-yl)ethyl-N,N-dicyclohexylaminocarbamate, dicyclohexylammonium-2-(3-benzoylphenyl)propionate, 9-anthrayl-N-cyclohexylaminocarbamate, 1-(9,10-anthraquinone-2-yl)ethyl-N-cyclohexylaminocarbamate, cyclohexylammonium-2-(3-benzoylphenyl)propionate, and (E)-N-cyclohexyl-3-(2-hydroxyphenyl)propionamide; and 9-anthraylmethyl-piperidine-1-carboxylic acid ester, (E)-1-piperidine-3-(2-hydroxyphenyl)-2-propionamide. Piperidine-based photoalkali generators, such as propylene-1-one, (2-nitrophenyl)methyl-4-hydroxypiperidine-1-carboxylate, and (2-nitrophenyl)methyl-4-(methacryloxy)piperidine-1-carboxylate; guanidinium-2-(3-benzoylphenyl)propionate, 1,2-diisopropyl-3-(bis(dimethylamino)methylene)guanidinium-2-(3-benzoylphenyl)propionate. Guanidine photoalkali generators such as 1,2-dicyclohexyl-4,4,5,5-tetramethylbiguanidine-2-butyltriphenylborate and 1,5,7-triazabicyclo[4.4.0]dec-5-enon-2-(9-sideoxyxanthanyl-2-yl)propionate; and imidazole photoalkali generators such as 1-(9,10-anthraquinone-2-yl)ethyl-imidazolium-1-carboxylate. The above components can be used in combination of one or more, and are typically used at a concentration of less than 10% by mass, preferably less than 3% by mass, in the solid component of the photocurable resin composition of this case.

[0038] <2. Protective film [6] / Semiconductor manufacturing wafer

[10] > (2-1: Protective film[6]) The protective film [6] of the present invention is a hardened coating film formed from a semiconductor manufacturing wafer end protective film forming composition [5]. This protective film has excellent etching resistance and is used in semiconductor manufacturing to prevent metal contamination at the wafer ends. Furthermore, the thickness of the protective film can be set to, for example, 1~500nm, and for photocuring, light with a wavelength of 170~800nm ​​can be used, for example.

[0039] (2-2: Semiconductor manufacturing wafers

[10] ) The semiconductor manufacturing wafer of one embodiment of the present invention is a semiconductor manufacturing wafer with the wafer end protected. It is a semiconductor manufacturing wafer formed by coating the wafer end with a protective film forming composition of one embodiment of the present invention [5] (refer to the above <1. Photocurable resin composition [1] / Semiconductor manufacturing wafer end protective film forming composition [5]>).

[0040] <3. Manufacturing methods for semiconductor devices

[11] > A method for manufacturing a semiconductor device according to one aspect of the present invention includes: (A) The step of forming a resist film on a semiconductor substrate. (B) The steps of forming a resist pattern by irradiating the resist film with light or electron beams and subsequent imaging, and (C) A step of processing a semiconductor substrate by etching, or a step of processing a semiconductor substrate by etching using the aforementioned patterned resist; It includes: The step (X) involves forming a protective film composition of a protective film from one aspect of the present invention [5] on the surface end and any selected beveled portion and / or back end of a semiconductor manufacturing wafer. The following is an explanation in sequence.

[0041] (3-1:(A) Steps for forming a resist film on a semiconductor substrate) A resist film is formed on a semiconductor substrate. The semiconductor substrate is a wafer used for manufacturing semiconductor devices, etc. In addition to commonly used silicon wafers and germanium wafers, compound semiconductor wafers in which two or more elements can be bonded, such as gallium arsenide, indium phosphide, gallium nitride, indium nitride, and aluminum nitride, can also be used. These are usually disk-shaped, with sizes such as 4, 6, 8, and 12 inches, and commercially available products can be used. When using a semiconductor substrate on which an inorganic film is formed on its surface, the inorganic film can be formed, for example, by ALD (atomic layer deposition), CVD (chemical vapor deposition), reactive sputtering, ion plating, vacuum evaporation, or spin coating (SOG). Examples of such inorganic films include polycrystalline silicon films, silicon oxide films, silicon nitride films, BPSG (boro-phosphosilicate glass) films, titanium nitride films, titanium oxynitride films, tungsten films, gallium nitride films, and gallium arsenide films. On such a semiconductor substrate, a resist underlayer film and a resist film of a specific thickness are formed by appropriate coating methods such as spraying, spin coating, or coating. Generally, in the case of spin coating, the resist underlayer film formation composition and the resist film formation composition are each supplied from above the center of a rotating disk-shaped substrate through nozzles or the like. Typically, these films are baked using heating means such as a heating plate. As for the photoresist used in the formation of the resist film, there are no particular limitations as long as it is used for photosensitization in exposure. Either negative or positive photoresist can be used. Examples include positive photoresists made from phenolic varnish resin and 1,2-naphthoquinone diazidesulfonate; chemically amplified photoresists made from a binder having a group that increases the alkali solubility rate due to acid decomposition and a photoacid generator; chemically amplified photoresists made from a low-molecular-weight compound that increases the alkali solubility rate of the photoresist due to acid decomposition, an alkali-soluble binder, and a photoacid generator; chemically amplified photoresists made from a binder having a group that increases the alkali solubility rate of the photoresist due to acid decomposition, a low-molecular-weight compound that increases the alkali solubility rate of the photoresist due to acid decomposition, and a photoacid generator; and photoresists containing metal elements. For example, examples include JSR Corporation's product V146G, SHIPLEY Corporation's product APEX-E, Sumitomo Chemical Industries' product PAR710, and Shin-Etsu Chemical Industries' product AR2772 and SEPR430. Also, examples include fluorinated polymer photoresists described in Proc. SPIE. Vol. 3999, 330-334 (2000), Proc. SPIE. Vol. 3999, 357-364 (2000), or Proc. SPIE, Vol. 3999, 365-374 (2000). Negative photoresists are preferred. The resist film forming composition used in the formation of the resist film may contain more than one metal. In addition to elemental metals, other forms of metal include metal salts, metal complexes, and other metal-containing compounds. There are no particular limitations on the types of metals, but examples include tin, indium, antimony, bismuth, gallium, germanium, aluminum, zirconium, hafnium, cerium, lanthanum, and cesium. The baking conditions for the resist film can be appropriately selected from a baking temperature of 70℃ to 400℃ and a baking time of 0.3 minutes to 60 minutes. The preferred baking temperature is 80℃ to 350℃ and the baking time is 0.5 minutes to 30 minutes, and the more preferred baking temperature is 90℃ to 300℃ and the baking time is 0.8 minutes to 10 minutes. The lower limit of the average thickness of the resist film is preferably 1 nm, more preferably 3 nm, 5 nm, or 10 nm. The upper limit of the average thickness of the resist film is preferably 5,000 nm, 3,000 nm, or 2,000 nm, more preferably 1,000 nm, particularly preferably 200 nm, and even more preferably 50 nm.

[0042] (3-2: Step (X) for forming the protective film and any steps (Y) and (Z)) (3-2-1: Step X) At any point in time, a step (X) is performed on the surface end and any selected bevel and / or back end of a semiconductor manufacturing wafer to form a protective film composition of one embodiment of the present invention [5]. In step (X), a preferred procedure is to expose and develop a specific area after coating the protective film composition. Step (X) may be performed before step (A), between step (A) and step (B), or after step (B) or step (C). Furthermore, in this specification, the surface on which the resist film or the like of the substrate has the device portion is referred to as the surface, and the opposite side of it is referred to as the back surface. Also, the term "surface end" refers to a region typically 1 to 10 mm wide from the edge of the device portion on the substrate to the bevel portion; the term "bevel portion" refers to the curved region connecting the surface end and the back surface end; and the term "back surface end" refers to the region corresponding to the surface end on the back surface of the substrate. First, a protective film forming composition of one aspect of the present invention [5] is applied to a semiconductor substrate on which a resist film or the like has been formed (refer to the aforementioned <1. Photocurable resin composition [1] / Wafer end protective film forming composition for semiconductor manufacturing [5]>). There is no particular limitation on the method of applying the protective film forming composition, but well-known methods such as spin coating or spray coating can be used. For example, when using spin coating, the semiconductor substrate on which the resist film or the like has been formed is rotated at a specific rotation speed, and the protective film forming composition is supplied from above or near the surface end of the rotating disk-shaped substrate through a nozzle. Preferably, it is also supplied from various nearby areas through nozzles on the inclined surface and / or the back end of the substrate. The conditions for spin coating can be appropriately selected, but are not limited at all. Typical conditions are illustrated below. • Viscosity of the protective film forming components: approximately 100 cps or less • Wafer rotation speed: • When supplying the protective film forming components: 50~500 rpm • Drying and spin-drying: 700~2,000 rpm • Protective film thickness: 300nm Next, the protective film forming composition is exposed. Exposure can be performed on the protective film forming composition by irradiating it with active light sources such as ultraviolet light, visible light, and radiation (including i-rays, KrF excimer lasers, ArF excimer lasers, EUV (extreme ultraviolet light), and EB (electron beams)) through or without a mask. Furthermore, soft baking (SB) can be performed before exposure, and post-exposure heating (PEB) can be performed before development. The preferred temperature for post-exposure heating is 50°C to 150°C, and the preferred heating time is 1 minute to 10 minutes. Next, the protective film-forming composition after exposure is developed. Development can be performed by removing the exposed portion of the protective film-forming composition with a developing solution, and a suitable development temperature can be selected from 5°C to 50°C and a development time from 10 seconds to 300 seconds. Examples of organic solvents contained in the developing solution include alcohol-based solvents, ether-based solvents, ketone-based solvents, amide-based solvents, ester-based solvents, and hydrocarbon-based solvents. Preferably, the organic solvent in the developing solution includes ester-based solvents, ketone-based solvents, or combinations thereof. The developing solution may contain only one organic solvent or two or more. Examples of alcohol solvents include aliphatic monools with 1 to 18 carbon atoms, such as 4-methyl-2-pentanol and n-hexanol; alicyclic monools with 3 to 18 carbon atoms, such as cyclohexanol; and polyol partial ether solvents with 3 to 19 carbon atoms, such as propylene glycol monomethyl ether. Examples of ether solvents include dialkyl ethers such as diethyl ether, dipropyl ether, dibutyl ether, dipentyl ether, diisopentyl ether, dihexyl ether, and diheptyl ether; cyclic ether solvents such as tetrahydrofuran and tetrahydropyran; and ether solvents containing aromatic rings such as diphenyl ether and anisole. Examples of ketone solvents include chain ketone solvents such as acetone, methyl ethyl ketone, methyl n-propyl ketone, methyl n-butyl ketone, diethyl ketone, methyl isobutyl ketone, 2-heptanone, ethyl n-butyl ketone, methyl n-hexyl ketone, diisobutyl ketone, and trimethylnonanone; cyclic ketone solvents such as cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, and methylcyclohexanone; and 2,4-pentanediol, acetoacetone, and acetophenone. Examples of acetylamine solvents include cyclic acetylamine solvents such as N,N'-dimethylimidazolinone and N-methylpyrrolidone; and chain acetylamine solvents such as N-methylmethamide, N,N-dimethylmethamide, N,N-diethylmethamide, acetylamine, N-methylacetylamine, N,N-dimethylacetylamine, and N-methylpropionic acid. Examples of ester-based solvents include monocarboxylic acid ester solvents such as n-butyl acetate and ethyl lactate; polyol carboxylic acid ester solvents such as propylene glycol acetate; polyol partial ether carboxylic acid ester solvents such as propylene glycol monomethyl ether acetate; polycarboxylic acid diester solvents such as diethyl oxalate; and carbonate solvents such as dimethyl carbonate and diethyl carbonate. Examples of hydrocarbon solvents include aliphatic hydrocarbon solvents with 5 to 12 carbon atoms, such as n-pentane and n-hexane; and aromatic hydrocarbon solvents with 6 to 16 carbon atoms, such as toluene and xylene. Among these, ester solvents, ketone solvents, ether solvents, and combinations thereof are preferred, and combinations thereof are even more preferred. As an ester solvent, propylene glycol monomethyl ether acetate is preferred. As a ketone solvent, cyclohexanone is preferred. As an ether solvent, propylene glycol monomethyl ether is preferred. The lower limit for the content of organic solvent in the developing solution is preferably 80% by mass, more preferably 90% by mass, even more preferably 99% by mass, and particularly preferably 100% by mass. By setting the content of organic solvent in the developing solution within the above range, the dissolution contrast between the exposed and unexposed areas can be improved, resulting in a resist pattern with superior lithography performance. Examples of components other than organic solvents include water and silicone oil. The developing solution may contain nitrogen-containing compounds. Because the developing solution contains nitrogen-containing compounds, film loss in the formed resist pattern can be further reduced. The developing solution can be an aqueous solution instead of the organic solvent-based developing solution mentioned above. Specifically, it can be an aqueous solution of sodium hydroxide, potassium hydroxide, sodium silicate, ammonia, monoethylamine, diethylamine, triethylamine, triethanolamine, tetramethylammonium hydroxide, etc. The alkalinity of such aqueous solution is not particularly limited, but can be set to, for example, 0.1 to 10% by weight. Alternatively, alcohols or surfactants can be added to the above-mentioned developing solution. Preferably, each of these surfactants is formulated in a ratio of 0.01 to 10 parts by weight relative to 100 parts by weight of the developing solution, and more preferably in a ratio of 0.1 to 5 parts by weight. Examples of surfactants include ionic or nonionic fluorinated surfactants and silicone surfactants. Examples of imaging methods include immersing a substrate in a tank filled with developer for a certain period of time (immersion method), piling developer on the substrate surface by means of surface tension and allowing it to stand for a certain period of time for imaging (coating method), spraying developer onto the substrate surface (spraying method), and continuously dispensing developer onto a substrate rotating at a certain speed while scanning the developer nozzle at a certain speed (dynamic dispensing method). Next, the protective film composition after development is baked. The desired pattern can be formed by baking the pattern obtained after development. The heating temperature during the heat treatment is typically above 150°C and below 350°C, preferably in the range of 200~300°C. The heat treatment time is the time until the protective film composition hardens; for production purposes, it is preferably approximately 30 minutes. The lower limit of the average thickness of the protective film is preferably 1 nm, more preferably 3 nm. The upper limit of the average thickness of the protective film is preferably 500 nm, more preferably 300 nm.

[0043] (3-2-2: Steps Y and Z) Following step (X), in step (Y), a portion of the resist film on the protective film can be removed using a removal solution. At this time, similar to step (X) above, it is preferable to apply the removal solution to the surface end and any selected beveled portion and / or back end of the semiconductor manufacturing wafer. Examples of resist removal solutions include propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone, water, butyl acetate, tetramethylammonium aqueous solution, or mixtures thereof. Among these, from the viewpoint of resist film removal properties, propylene glycol monomethyl ether acetate and water are preferred. Following step (X) or step (Y), in step (Z), the protective film may be removed by ashing or by treatment with hydrofluoric acid, organic solvents, alkaline developing solutions, or semiconductor cleaning solutions. Subsequently, it is preferable to clean with any solvent or a conventional semiconductor cleaning solution. Steps (X), (Y), and (Z) can be performed simultaneously with steps (A), (B), and (C), or at any point before or after each step. For example, if step (X) precedes step (A), step (Y) of removing a portion of the resist film on the protective film can be performed between steps (A) and (B), and step (Z) of removing the protective film can be performed between steps (Y) and (B). Similarly, if step (X) is included between steps (A) and (B) or (C), step (Z) of removing the protective film can also be performed between steps (X) and (B) or (C).

[0044] (3-3: (B) The step of forming a resist pattern by irradiating the resist film with light or electron lines and the subsequent imaging, and (C) The step of processing the semiconductor substrate by etching) (3-3-1: Exposure in Step (B)) Exposure of the resist film is performed using a mask (marker) to form a specific pattern, such as using i-line, KrF excimer laser, ArF excimer laser, EUV (extreme ultraviolet) or EB (electron beam). Alternatively, soft baking (SB) can be performed before exposure, or post-exposure heating (PEB) can be performed before development. The preferred temperature for post-exposure heating is 50°C to 150°C, and the preferred heating time is 1 minute to 10 minutes.

[0045] (3-3-2: Imaging in step (B)) An alkaline developing solution is used in the developing process, with a suitable developing temperature ranging from 5°C to 50°C and a developing time from 10 seconds to 300 seconds. Examples of suitable alkaline developing solutions include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and ammonia; primary amines such as ethylamine and n-propylamine; secondary amines such as diethylamine and di-n-butylamine; tertiary amines such as triethylamine and methyldiethylamine; alkanolamines such as dimethylethanolamine and triethanolamine; quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide; and cyclic amines such as pyrrole and piperidine. The alkalinity of these aqueous solutions is not particularly limited, but can be set to, for example, 0.1 to 10% by weight. Furthermore, appropriate amounts of surfactants such as isopropanol and other alcohols, or nonionic surfactants, can be added to the aforementioned alkaline aqueous solutions. These surfactants can be formulated in proportions of 0.01 to 10 parts by weight relative to 100 parts by weight of the developing solution, more preferably in the range of 0.1 to 5 parts by weight. Among these, the developing solution is preferably a quaternary ammonium salt, more preferably tetramethylammonium hydroxide and choline. Furthermore, surfactants can also be added to these developing solutions. Instead of alkaline developing solutions, polyol solvents with 2 to 18 carbon atoms, such as 1,2-propanediol, and organic solvents such as butyl acetate can also be used for developing, thereby developing the portion of the photoresist whose alkaline dissolution rate has not been improved.

[0046] (3-3-3: Baking in step (B)) Step (B) may include baking the semiconductor substrate that has undergone the above exposure and development. There are no particular limitations on the baking method, but for example, a proximity baking oven that uses a plurality of substrate support pins between the substrate and the heating plate to ensure the gap may be used. Baking temperature is usually between 40℃ and 300℃, preferably between 200℃ and 300℃ for 1 to 30 minutes. However, if it is necessary to avoid damage to the resist pattern, the temperature can be set below 90℃. The baking system can be used on semiconductor substrates after exposure and before development. The baking methods and conditions are as described above, but if it is necessary to avoid damage to the resist pattern, the temperature can be set below 90°C.

[0047] (3-3-4: Etching in step (C)) Next, using the formed resist pattern as a mask, the aforementioned resist underlayer film is etched, preferably by dry etching, to form a patterned resist. At that time, if the aforementioned inorganic film is formed on the surface of the semiconductor substrate, the surface of the inorganic film is exposed; if the aforementioned inorganic film is not formed on the surface of the semiconductor substrate, the surface of the semiconductor substrate is exposed. Then, using the patterned resist, the semiconductor substrate is processed by a method known to the public (such as dry etching). Etching used to process the aforementioned semiconductor substrate can be a well-known method. For example, when the semiconductor substrate is a silicon substrate, in addition to using fluorine-based gases such as carbon tetrafluoride to perform shape processing by dry etching, a surface treatment step such as removing silicon nitride film present on the surface of the semiconductor substrate by hot phosphoric acid can also be included.

[0048] <4. Manufacturing methods for semiconductor wafers

[21] > (4-1) The semiconductor manufacturing wafer manufacturing method of one aspect of the present invention is a semiconductor device manufacturing method as described above, comprising the step of applying (or coating) the semiconductor manufacturing wafer end protective film forming composition of one aspect of the present invention

[10] to the surface end and any selected bevel portion and / or back end of the semiconductor manufacturing wafer precursor to manufacture a semiconductor manufacturing wafer with a protective film. Here, the term "wafer precursor for semiconductor manufacturing" refers to material obtained by supplying a semiconductor substrate to at least one step in a method for manufacturing a semiconductor device. For example, in the semiconductor device manufacturing method described above, material that has undergone steps such as forming an inorganic film, a resist underlayer film, and a resist film on a semiconductor substrate, and is supplied to the step of forming a resist pattern by irradiating the resist film with light or electron lines and subsequent imaging.

[0049] (4-2: Specific details of the manufacturing methods for semiconductor wafers) For the surface end and any selected bevel and / or back end of the semiconductor manufacturing wafer precursor obtained through one or more semiconductor device processes, coating is performed by spin-coating the semiconductor manufacturing wafer end protective film forming composition of one embodiment of the present invention [5]. Subsequently, the semiconductor substrate can be baked. At that time, there were no particular limitations on the baking method, but for example, a proximity baking oven that uses multiple substrate support pins between the substrate and the heating plate to ensure the gap can be used. The baking temperature is usually between 40°C and 300°C, preferably between 200°C and 300°C for 1 to 30 minutes. After the aforementioned protective film is coated to form the composition, the edge beads on the end face of the protective film are removed and the back side is cleaned, which are well-known processes in semiconductor manufacturing. [Example]

[0050] <Synthesis example 1> 1 g of 4-benzoylphenyl methacrylate, 10.3 g of 2-hydroxypropyl methacrylate, and 0.2 g of 2,2'-azobis(methyl isobutyrate) were dissolved in 29.5 g of ethyl lactate and 12.6 g of propylene glycol monomethyl ether acetate. The mixture was then heated to 80 °C and reacted for 24 hours to obtain the following formulas (I) and (II): A solution of a copolymer of 4-benzoylphenyl methacrylate and 2-hydroxypropyl methacrylate, which are repeating units, was prepared. GPC analysis of the resulting copolymer yielded a weight-average molecular weight of 35,000, converted to standard polystyrene.

[0051] <Synthesis example 2> 1.5 g of 4-benzoylphenyl methacrylate, 1.6 g of 2-hydroxypropyl methacrylate, 10 g of styrene, and 0.3 g of 2,2'-azobis(methyl isobutyrate) were dissolved in 37.5 g of ethyl lactate and 16.1 g of propylene glycol monomethyl ether acetate. The mixture was then heated to 80 °C and reacted for 24 hours to obtain the following products with the following formulas (I) to (III): A solution of a copolymerized polymer of 4-benzoylphenyl methacrylate, 2-hydroxypropyl methacrylate, and styrene was prepared. The resulting polymer solution was redeprecipitated in methanol and then dried in a vacuum oven to obtain a white polymer. GPC analysis of the obtained polymer showed a weight-average molecular weight of 34,000 converted to standard polystyrene.

[0052] <Synthesis Example 3> After dissolving 10 g of 2-hydroxypropyl methacrylate and 0.2 g of 2,2'-azobis(isobutyronitrile) in 28.9 g of ethyl lactate and 12.2 g of propylene glycol monomethyl ether acetate, the temperature was raised to 80 °C and the reaction was carried out for 24 hours to obtain a polymer compound of 2-hydroxypropyl methacrylate having a repeating unit of formula (II):

[0053] A solution of the polymer compound of 2-hydroxypropyl methacrylate with the repeating unit. GPC analysis of the obtained copolymerized polymer compound showed that the weight average molecular weight in terms of standard polystyrene was 35,000.

[0054] <Synthesis Example 4> In 30.00 g of an epoxy-containing novolak resin (product name: EPPN-201, epoxy value: 192 g / eq., manufactured by Nippon Kayaku Co., Ltd.), 11.26 g of acrylic acid, 1.99 g of tetrabutylphosphonium bromide, and 0.09 g of hydroquinone, 101.11 g of propylene glycol monomethyl ether acetate was added, and the mixture was heated and stirred at 100 °C for 18 hours under a nitrogen atmosphere. 43 g of an anion exchange resin (product name: AMBERJET[registered trademark]ESG4002(OH), ORGANO Co., Ltd.) and 43 g of a cation exchange resin (product name: Amberlite[registered trademark]15JWET, ORGANO Co., Ltd.) were added to the obtained solution, and ion exchange treatment was carried out at room temperature for 4 hours. After separating the ion exchange resins, a compound solution was obtained. The obtained compound corresponded to a polymer compound having a repeating unit of formula (XX): The polymer compound with the repeating unit, and the weight average molecular weight Mw measured by GPC in terms of polystyrene was 6,900.

[0055] <b. Preparation of Composition> <Composition 1> To 8 g of the reaction product obtained in Synthesis Example 1, 4.5 g of ethyl lactate and 1.9 g of propylene glycol monomethyl ether acetate were added, and then filtration was carried out using a polyethylene microfilter with a pore size of 0.10 μm to prepare a photocurable resin composition solution.

[0056] <Composition 2> To 4 g of the reaction product obtained in Synthesis Example 2, 16 g of propylene glycol monomethyl ether acetate was added, and then filtration was carried out using a polyethylene microfilter with a pore size of 0.10 μm to prepare a photocurable resin composition solution.

[0057] <Comparative Example 1> To 8 g of the reaction product obtained in Synthesis Example 3, 4.5 g of ethyl lactate and 1.9 g of propylene glycol monomethyl ether acetate were added, and then filtration was carried out using a polyethylene microfilter with a pore size of 0.10 μm to prepare a photocurable resin composition solution.

[0058] <Comparative Example 2> To 11.72 g of the resin solution (solid content: 23.73% by mass) obtained in Synthesis Example 4, 0.28 g of Irgacure Oxe01 (manufactured by BASF Japan Co., Ltd.) as a photoinitiator, 0.008 g of Megafac R-30 (manufactured by Dainippon Ink and Chemicals, Inc.) as a surfactant, 0.042 g of Irganox 3114 (manufactured by BASF Japan Co., Ltd.) as an antioxidant, 0.042 g of KBM-5103 (manufactured by Shin-Etsu Chemical Co., Ltd.) as an adhesion improver, and 17.91 g of propylene glycol monomethyl ether acetate were added, and filtration was carried out to prepare a photocurable resin composition solution.

[0059] <c. Dissolution Test in Photoresist Solvent> By a spinner, the photocurable resin composition solutions prepared in Composition Examples 1 to 2 and Comparative Example 1 were coated on a silicon wafer, baked on a hot plate at 80 °C for 1 minute, and then irradiated with light of 254 nm at 300 mJ / cm 2 by an aligner (PLA-501 CANON Co., Ltd.) to form a photocured film (film thickness: 0.10 μm). The photocured film was immersed in cyclohexanone, which is a solvent used for the photoresist. It was confirmed that the film was insoluble in the solvent in Composition Examples 1 to 2, but the film was dissolved by the solvent in Comparative Example 1.

[0060] <d. Solvent Resistance Test for Edge Exposure> Using a spinner, the photocurable resin composition solutions prepared in Examples 1-2 and Comparative Example 1 were coated onto a 12-inch silicon wafer. The wafer was heated to 80°C for 1 minute on a hot plate, and then the wafer edge was irradiated with a Lithiuspro (Tokyo Electron) WEE at 50 mJ / cm² to form a photocurable film (0.30 μm thick). This photocurable film was then immersed in OK73 thinner, the solvent used for the photoresist. In Examples 1-2, the film was confirmed to be insoluble in the solvent, but in Comparative Example 1, the film dissolved in the solvent.

[0061] <Determination of Dry Etching Rate> The photocurable resin composition solutions prepared in Composition Example 2 and Comparative Example 2 were coated onto a silicon wafer using a spinner. Subsequently, a photocurable film (0.10 μm thick) was formed by irradiating the wafer with 254 nm light at 300 mJ / cm² using an alignment device (PLA-501 CANON). Then, the dry etching rate (the decrease in film thickness per unit time) was measured using a SAMCO RIE system (RIE-10NR) under conditions using CF₄ as the dry etching gas. The dry etching rates of the photocurable resins formed from Composition Example 2 and Comparative Example 2 were compared. The results are shown in the table. In Table 1, the etching rate is represented when the dry etching rate of Comparative Example 2 is taken as 1.00.

[0062] [Table 1] Selection ratio Example 2 0.69 Comparative Example 2 1.00 It can be seen that, compared with Comparative Example 2, the photocurable film system obtained from the photocurable resin forming composition of one state of the present invention has greater dry etching resistance.

Claims

1. A semiconductor manufacturing wafer, comprising a wafer end-protected semiconductor manufacturing wafer, wherein a self-crosslinking polymer (A) and a solvent (B) are coated on the surface end and an arbitrarily selected bevel and / or back end of a wafer precursor, the self-crosslinking polymer (A) comprising: (a) a first monomer unit containing an aryl ketone residue in its side chain; and (b) a second monomer unit containing (b-1) an aliphatic hydrocarbon residue containing a carbon atom readily undergoing hydrogen abstraction reaction, and / or (b-2) an aromatic ring residue in its side chain, forming a semiconductor manufacturing wafer end-protected film forming composition; wherein the aforementioned surface end is a region of 1 to 10 mm width from the edge of a device portion disposed on a substrate to the aforementioned bevel; the aforementioned bevel is a curved region connecting the aforementioned surface end and the aforementioned back end; and the aforementioned back end is a region on the back side of the substrate corresponding to the aforementioned surface end, the aforementioned aryl ketone residue being a residue of benzophenone or a substituted derivative thereof. The aforementioned (b-1) aliphatic hydrocarbon residues containing carbon atoms that are prone to hydrogen abstraction reactions are aliphatic hydrocarbon residues containing carbon atoms selected from tertiary carbon atoms; secondary carbon atoms with hydroxyl groups; and carbon atoms in groups consisting of methyl, methylene, or methine groups directly attached to an aromatic ring.

2. A method for manufacturing a semiconductor device, comprising: (A) a step of forming a resist film on a semiconductor substrate; (B) a step of forming a resist pattern by irradiating the resist film with light or electron lines and subsequent imaging; and (C) a step of etching the semiconductor substrate; comprising (X) a step of forming a protective film of a semiconductor manufacturing wafer end protective film forming composition from a photocurable resin composition comprising a self-crosslinking polymer (A) and a solvent (B), wherein the self-crosslinking polymer (A) comprises: (a) a first monomer unit comprising an aryl ketone residue in the side chain; and (b) a second monomer unit comprising (b-1) an aliphatic hydrocarbon residue containing a carbon atom readily subjected to hydrogen abstraction reaction, and / or (b-2) an aromatic ring residue in the side chain; The aforementioned surface end portion is a region with a width of 1 to 10 mm extending from the edge of the device portion provided on the substrate to the aforementioned beveled portion; the aforementioned beveled portion is a curved region connecting the aforementioned surface end portion and the aforementioned back end portion; and the aforementioned back end portion is the region on the back of the substrate corresponding to the aforementioned surface end portion; the aforementioned aryl ketone residue is a residue of benzophenone or its substituted derivative; the aforementioned (b-1) aliphatic hydrocarbon residue containing carbon atoms that are prone to hydrogen abstraction reactions is an aliphatic hydrocarbon residue containing carbon atoms selected from tertiary carbon atoms; secondary carbon atoms having hydroxyl groups; and carbon atoms directly connected to a group consisting of methyl, methylene, or methine groups on an aromatic ring.

3. A method for manufacturing a semiconductor device as claimed in claim 2, wherein step (X) is included before step (A).

4. A method for manufacturing a semiconductor device as claimed in claim 2, wherein step (X) is included between step (A) and step (B).

5. A method for manufacturing a semiconductor device as claimed in claim 2, wherein step (X) is included after step (B) or step (C).

6. A method for manufacturing a semiconductor device as claimed in claim 2, wherein after step (X), a step (Y) is included to remove a portion of the resist film on the aforementioned protective film.

7. A method for manufacturing a semiconductor device as claimed in claim 2, wherein after step (X), a step (Z) is included to remove the aforementioned protective film.

8. A method for manufacturing a semiconductor device as claimed in claim 6, wherein after step (Y), a step (Z) is included to remove the aforementioned protective film.

9. A method for manufacturing a semiconductor device as claimed in claim 2, wherein the aforementioned resist film comprises a metal.

10. A method for manufacturing a semiconductor device as claimed in claim 2, wherein in the aforementioned step (X), a wafer end protective film forming composition comprising the aforementioned photocurable resin composition is coated, and a specific area is exposed and developed.

11. The method for manufacturing a semiconductor device as claimed in claim 7, wherein step (Z) is performed by ashing or treatment with a semiconductor cleaning solution.

12. A method for manufacturing a wafer for semiconductor manufacturing, comprising coating a surface end portion and an arbitrarily selected bevel portion and / or back end portion of a wafer precursor with a self-crosslinking polymer (A) and a solvent (B), wherein the self-crosslinking polymer (A) comprises: (a) a first monomer unit containing an aryl ketone residue in its side chain; and (b) a second monomer unit containing (b-1) an aliphatic hydrocarbon residue containing a carbon atom readily subjected to hydrogen abstraction, and / or (b-2) an aromatic ring residue in its side chain, thereby manufacturing a wafer with the aforementioned end protected; wherein the aforementioned surface end portion is a region of 1 to 10 mm in width from the edge of a device portion disposed on a substrate to the aforementioned bevel portion; the aforementioned bevel portion is a curved region connecting the aforementioned surface end portion and the aforementioned back end portion; and the aforementioned back end portion is a region on the back side of the substrate corresponding to the aforementioned surface end portion, wherein the aforementioned aryl ketone residue is a residue of benzophenone or a substituted derivative thereof. The aforementioned (b-1) aliphatic hydrocarbon residues containing carbon atoms that are prone to hydrogen abstraction reactions are aliphatic hydrocarbon residues containing carbon atoms selected from tertiary carbon atoms; secondary carbon atoms with hydroxyl groups; and carbon atoms in groups consisting of methyl, methylene, or methine groups directly attached to an aromatic ring.