Composition for forming protective film on edge of wafer for semiconductor manufacturing

Abstract

The present invention provides: a protective film-forming composition capable of forming, using a simple coating method during the manufacture of a semiconductor device, a protective film having a satisfactory film state, good film curability, and high dry etching resistance on the edge of a substrate (wafer) for semiconductor manufacturing; a protective film formed from the protective film-forming composition; a wafer for semiconductor manufacturing, said wafer manufactured using the protective film; and methods for manufacturing the wafer for semiconductor manufacturing and a semiconductor device.　This composition for forming a protective film on the edge of a wafer for semiconductor manufacturing contains: a polymer or a compound containing a polymerizable group and having a carbon content of 70% or more; and a solvent.

Description

Composition for forming wafer edge protection film for semiconductor manufacturing

[0001] The present invention relates to a protective film-forming composition for forming a protective film on the edge of a substrate (wafer) for semiconductor manufacturing in a semiconductor device manufacturing process, a protective film formed from the protective film-forming composition, a semiconductor manufacturing wafer manufactured using the protective film, and a method for manufacturing the semiconductor manufacturing wafer and the semiconductor device.

[0002] In the manufacture of semiconductor devices, as the manufacturing process becomes more complex, methods of applying a metal-containing chemical solution to a wafer have been considered, for example, for purposes such as improving etching selectivity. Furthermore, due to the increased resolution of resist patterns when exposed to extreme ultraviolet (EUV) light and the high etching resistance, the formation of resist films using inorganic metal-containing resists has been considered. Meanwhile, the deposition of metal on unintended portions of a wafer during the semiconductor device manufacturing process significantly affects the electrical characteristics of the semiconductor device. However, when forming a metal-containing coating film as described above, there is a concern that the chemical solution supplied to the wafer surface may flow around to the edge of the wafer (e.g., the outer periphery (edge ​​portion, etc.) of the front surface, the peripheral edge (bevel portion, etc.), and the outer periphery of the back surface, etc.), resulting in the formation of a coating film on the edge of the wafer at these unintended outer periphery and peripheral edge, which may result in metal contamination of these portions. Furthermore, contact of contaminated portions of a wafer with wafer processing equipment such as an exposure apparatus or an etching apparatus or a wafer transport mechanism may result in metal contamination of wafers transported and processed thereafter via these processing equipment or transport mechanisms, i.e., cross-contamination.

[0003] A technique has been disclosed for forming a coating film on the surface of a substrate so that the coating film does not come into contact with the peripheral edge surface or the outer periphery of the back surface of the substrate (Patent Document 1).

[0004] A method for manufacturing a semiconductor device that prevents a film from peeling off from the bevel portion of a substrate has been disclosed (Patent Document 2).

[0005] JP 2017-098333 A JP 2011-228340 A

[0006] The problem to be solved by the present invention is to provide a protective film-forming composition that can form a protective film that has good film condition, exhibits good film curing properties, and is also highly resistant to dry etching on the edge of a semiconductor manufacturing substrate (wafer) by a simple method of application in the manufacture of a semiconductor device; a protective film formed from the protective film-forming composition; a semiconductor manufacturing wafer manufactured using the protective film; and methods for manufacturing the semiconductor manufacturing wafer and the semiconductor device.

[0007] The present invention encompasses the following: [1] A composition for forming a wafer edge protective film for semiconductor manufacturing, comprising a polymer or compound containing a polymerizable group and having a carbon content of 70% or more, and a solvent. [2] The composition for forming a wafer edge protective film for semiconductor manufacturing according to [1], wherein the polymerizable group is a photopolymerizable group or a thermally polymerizable group. [3] The protective film forming composition according to [2], wherein the photopolymerizable group or the thermally polymerizable group is selected from the group consisting of an acrylic group, a methacrylic group, an acrylamide group, a methacrylamide group, a vinyl group, and an allyl group. [4] The composition for forming a wafer edge protective film for semiconductor manufacturing according to any one of [1] to [3], which is photosensitive. [5] A protective film which is a cured product of a coating film comprising the composition for forming a wafer edge protective film for semiconductor manufacturing according to any one of [1] to [4]. [6] The protective film according to [5], which is cured by irradiation with light having a wavelength of 170 to 800 nm. [7] The protective film according to [5] or [6], which is capable of forming a negative pattern using an organic solvent. [8] A semiconductor manufacturing wafer having a protected wafer edge, the semiconductor manufacturing wafer having a protective film formed by applying the composition for forming a wafer edge protective film for semiconductor manufacturing according to any one of [1] to [4] to the edge of a wafer precursor. [9] A method for manufacturing a semiconductor device, comprising: (A) forming a resist film on a semiconductor substrate; (B) forming a resist pattern by irradiating the resist film with light or an electron beam and then developing it; and (C) etching the semiconductor substrate using the resist pattern as a mask, the method comprising: step (X) of forming a protective film on the edge of the semiconductor manufacturing wafer using the composition for forming a wafer edge protective film for semiconductor manufacturing according to any one of [1] to [4].

[10] The method for manufacturing a semiconductor device according to [9], in which step (X) is performed before step (A).

[11] The method for manufacturing a semiconductor device according to [9], in which step (X) is performed between step (A) and step (B).

[12] The method for manufacturing a semiconductor device according to [9], in which step (X) is performed after step (B) or step (C).

[13] The method for manufacturing a semiconductor device according to [9], wherein step (X) is performed before step (A), and in step (A), the resist film is formed on at least a portion of the protective film, and the method includes step (Y) of removing the resist film on the portion of the protective film.

[14] The method for manufacturing a semiconductor device according to any one of [9] to

[13] , which includes step (Z) of removing the protective film.

[15] The method for manufacturing a semiconductor device according to

[13] , which includes step (Z) of removing the protective film after step (Y).

[16] The method for manufacturing a semiconductor device according to any one of [9] to

[15] , wherein the composition for forming a wafer edge protective film for semiconductor manufacturing is photosensitive, and the formation of the protective film in step (X) is performed by applying the composition for forming a wafer edge protective film for semiconductor manufacturing, exposing a predetermined region to light, and developing it.

[17] The method for manufacturing a semiconductor device according to

[14] , wherein the removal of the protective film in step (Z) is performed by ashing, or by treatment with hydrofluoric acid, an organic solvent, an alkaline developer, or a semiconductor cleaning liquid.

[18] The method for manufacturing a semiconductor device according to

[15] , wherein the removal of the protective film in the step (Z) is carried out by ashing, or by treatment with hydrofluoric acid, an organic solvent, an alkaline developer, or a cleaning liquid for semiconductors.

[19] A method for manufacturing a wafer for semiconductor manufacturing, comprising the steps of: applying the composition for forming a wafer edge protective film for semiconductor manufacturing according to any one of [1] to [4] to an edge of a wafer precursor, and manufacturing a wafer whose edge is protected by the formed protective film.

[0008] According to the present invention, a protective film having good film quality, good film hardening properties, and high dry etching resistance can be formed on the edge of a semiconductor manufacturing substrate (wafer) by a simple coating method, thereby preventing cross-contamination due to metal contamination in the subsequent semiconductor device manufacturing process and improving the yield of non-defective semiconductor manufacturing equipment.

[0009] 1 is a schematic diagram showing an example of an edge of a wafer for explaining the edge of a wafer, and FIG. 2 is a schematic diagram showing another example of an edge of a wafer for explaining the edge of a wafer.

[0010] (Composition for forming a wafer edge protective film for semiconductor manufacturing) The composition for forming a wafer edge protective film for semiconductor manufacturing of the present invention (hereinafter may be referred to as "protective film forming composition") is a composition for forming a protective film used to protect the edge of a wafer for semiconductor manufacturing. The protective film forming composition contains a polymerizable group and a polymer or compound with a carbon content of 70% or more, and a solvent.

[0011] The present inventors have conducted extensive research to form a protective film that is in good condition, exhibits good film curing properties, and has high dry etching resistance by a simple method of coating on the edge (surface edge and bevel) of a semiconductor manufacturing wafer. As a result, they have found that a protective film-forming composition containing a polymer or compound that contains a polymerizable group and has a carbon content of 70% or more, and a solvent, can be formed into a protective film that is in good condition, exhibits good film curing properties, and has high dry etching resistance by a simple method of coating on the edge (surface edge and bevel) of a semiconductor manufacturing wafer, thereby completing the present invention.

[0012] <Polymer or Compound Having a Polymerizable Group and a Carbon Content of 70% or More> The polymerizable group refers to a functional group that undergoes a polymerization reaction that begins upon application of light or heat in the presence of a photoinitiator or a thermal initiator. The polymerizable group may be either a photopolymerizable group or a thermally polymerizable group.

[0013] Examples of the photopolymerizable group or the thermally polymerizable group include a group selected from the group consisting of an acrylic group, a methacrylic group, an acrylamide group, a methacrylamide group, a vinyl group, and an allyl group. In this specification, the terms "polymer" and "compound" do not necessarily mean separate substances, and a substance containing a polymer may also be referred to as a "compound."

[0014] The polymer or compound containing a photopolymerizable group or a thermally polymerizable group according to the present invention is not particularly limited as long as it is a polymer or compound containing a photopolymerizable group or a thermally polymerizable group, but examples thereof include polymers or compounds containing at least one group selected from the group consisting of an acrylic group, a methacrylic group, an acrylamide group, a methacrylamide group, a vinyl group, and an allyl group. In this specification, an acrylic group and a methacrylic group are collectively referred to as a (meth)acrylic group. Furthermore, an acrylamide group and a methacrylamide group are collectively referred to as a (meth)acrylamide group.

[0015] As a preferred embodiment of the polymer or compound according to the present invention, for example, a polymer or compound having a polymerizable group of a (meth)acrylic group or an allyl group can be mentioned. As a preferred embodiment of the polymer or compound according to the present invention, for example, the polymer described in the first embodiment below can be mentioned.

[0016] <<First Embodiment>> Examples of the polymer of the first embodiment include polymers obtained by reacting a resin containing an epoxy group with an active proton compound having a polymerizable group (such as a carboxylic acid, a phenol, an amine, a thiol, or an imide). For example, examples of the polymer corresponding to the first embodiment include the polymers described in the following embodiments 1-1 to 1-5. Examples of the polymer of embodiment 1-1 include a polymer having a structural unit represented by the following formula (1-1). Examples of the polymer of embodiment 1-2 include a polymer having a structural unit represented by the following formula (1-2). Examples of the polymer of embodiment 1-3 include a polymer having a structural unit represented by the following formula (1-3). Examples of the polymer of embodiment 1-4 include a polymer having a structural unit represented by the following formula (1-4). Examples of the polymer of embodiment 1-5 include a polymer having a structural unit represented by the following formula (1-5). In the polymer having the structural units represented by the following formulae (1-1) to (1-5), the (meth)acrylic group in the polymerizable group means a (meth)acryloyloxy group. In the polymer having the structural unit represented by the following formula (1-1), a preferred embodiment of the allyl group in the polymerizable group is a (di)allylamino group.

[0017] <<<First-1st embodiment>>> (In formula (1-1), Ar represents a benzene ring, a naphthalene ring, or an anthracene ring, and R １ represents a hydroxy group, a mercapto group which may be protected by a methyl group, an amino group which may be protected by a methyl group, a halogeno group, or an alkyl group having 1 to 10 carbon atoms which may be substituted or interrupted by a heteroatom and which may be substituted by a hydroxy group; n1 represents an integer of 0 to 3; L １ represents a single bond or a divalent group which may have a substituent; n2 represents 1 or 2; A represents a group having a (meth)acryloyloxy group or a group having an allylamino group; T １When n2=1, represents a single bond or an alkylene group having 1 to 10 carbon atoms which may be interrupted by an ether bond, an ester bond or an amide bond; T １ represents a nitrogen atom or an amide bond when n2=2; and k represents an integer of 1 to 3.

[0018] L １ The divalent group represents, for example, an alkylene group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 25 carbon atoms, or a group in which two or more of these groups are combined.

[0019] L １ The alkylene group in L may be a linear, branched, or cyclic alkylene group. １ The aromatic hydrocarbon group may be a monocyclic or condensed ring aromatic hydrocarbon group, and may be a linked ring in which these aromatic hydrocarbon groups are linked.

[0020] L １ Examples of the substituent that may be substituted on the divalent group of L include a group containing a (meth)acryloyloxy group and an alkoxy group. １ A more preferred embodiment of the substituent on the alkylene group in the formula (I) is, for example, -Ar-T １ -(A)n2 (where Ar, T １ , A, n2 are Ar, T in the above formula (1-1). １ , A, n2.) Also, L １ A more preferred embodiment of the substituent substituted on the aromatic hydrocarbon group in the formula (I) is, for example, -T １ -(A)n2 and alkoxy groups (wherein, T １ , A, n2 are Ar, T in the above formula (1-1). １ , A, and n2.)

[0021] Examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a cyclopropyl group, an n-butyl group, an i-butyl group, an s-butyl group, a t-butyl group, a cyclobutyl group, a 1-methyl-cyclopropyl group, a 2-methyl-cyclopropyl group, an n-pentyl group, a 1-methyl-n-butyl group, a 2-methyl-n-butyl group, a 3-methyl-n-butyl group, a 1,1-dimethyl-n-propyl group, a 1,2-dimethyl-n-propyl group, a 2,2-dimethyl-n-propyl group, and a 1-ethyl-n-propyl group. Cyclopentyl group, 1-methylcyclobutyl group, 2-methylcyclobutyl group, 3-methylcyclobutyl group, 1,2-dimethylcyclopropyl group, 2,3-dimethylcyclopropyl group, 1-ethylcyclopropyl group, 2-ethylcyclopropyl group, n-hexyl group, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, 3-methyl-n-pentyl group, 4-methyl-n-pentyl group, 1,1-dimethyl-n-butyl group, 1,2-dimethyl-n-butyl group, 1,3-dimethyl-n-butyl group, 2,2- Dimethyl-n-butyl group, 2,3-dimethyl-n-butyl group, 3,3-dimethyl-n-butyl group, 1-ethyl-n-butyl group, 2-ethyl-n-butyl group, 1,1,2-trimethyl-n-propyl group, 1,2,2-trimethyl-n-propyl group, 1-ethyl-1-methyl-n-propyl group, 1-ethyl-2-methyl-n-propyl group, cyclohexyl group, 1-methyl-cyclopentyl group, 2-methyl-cyclopentyl group, 3-methyl-cyclopentyl group, 1-ethyl-cyclobutyl group, 2-ethyl-cyclobutyl group, 3 -ethyl-cyclobutyl group, 1,2-dimethyl-cyclobutyl group, 1,3-dimethyl-cyclobutyl group, 2,2-dimethyl-cyclobutyl group, 2,3-dimethyl-cyclobutyl group, 2,4-dimethyl-cyclobutyl group, 3,3-dimethyl-cyclobutyl group, 1-n-propyl-cyclopropyl group, 2-n-propyl-cyclopropyl group, 1-i-propyl-cyclopropyl group, 2-i-propyl-cyclopropyl group, 1,2,2-trimethyl-cyclopropyl group, 1,2,3-trimethyl-cyclopropyl group, 2,2,Examples of such groups include a 3-trimethyl-cyclopropyl group, a 1-ethyl-2-methyl-cyclopropyl group, a 2-ethyl-1-methyl-cyclopropyl group, a 2-ethyl-2-methyl-cyclopropyl group, a 2-ethyl-3-methyl-cyclopropyl group, a decyl group, a methoxy group, an ethoxy group, a methoxymethyl group, an ethoxymethyl group, a methoxyethyl group, an ethoxyethyl group, a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a methylamino group, a dimethylamino group, a diethylamino group, an aminomethyl group, a 1-aminoethyl group, a 2-aminoethyl group, a methylthio group, an ethylthio group, a mercaptomethyl group, a 1-mercaptoethyl group, and a 2-mercaptoethyl group.

[0022] Examples of the alkylene group having 1 to 20 carbon atoms include a methylene group, an ethylene group, an n-propylene group, an isopropylene group, a cyclopropylene group, an n-butylene group, an isobutylene group, an s-butylene group, a t-butylene group, a cyclobutylene group, a 1-methylcyclopropylene group, a 2-methylcyclopropylene group, an n-pentylene group, a 1-methyl-n-butylene group, a 2-methyl-n-butylene group, a 3-methyl-n-butylene group, a 1,1-dimethyl-n-propylene group, a 1,2-dimethyl-n-propylene group, a 2,2-dimethyl-n-propylene group, and a 1-ethyl-n-propylene group. cyclopentylene group, 1-methyl-n-pentylene group, 2-methyl-cyclobutylene group, 3-methyl-cyclobutylene group, 1,2-dimethyl-cyclopropylene group, 2,3-dimethyl-cyclopropylene group, 1-ethyl-cyclopropylene group, 2-ethyl-cyclopropylene group, n-hexylene group, 1-methyl-n-pentylene group, 2-methyl-n-pentylene group, 3-methyl-n-pentylene group, 4-methyl-n-pentylene group, 1,1-dimethyl-n-butylene group, 1,2-dimethyl-n-butylene group, 1,3-dimethyl-n-butylene group, 2,2-dimethyl-n-butylene group, 2,3-dimethyl-n-butylene group, 3,3-dimethyl-n-butylene group, 1-ethyl-n-butylene group, 2-ethyl-n-butylene group, 1,1,2-trimethyl-n-propylene group, 1,2,2-trimethyl-n-propylene group, 1-ethyl-1-methyl-n-propylene group, 1-ethyl-2-methyl-n-propylene group, cyclohexylene group, 1-methyl-cyclopentylene group, 2-methyl-cyclopentylene group, 3-methyl-cyclopentylene group, 1-ethyl-cyclobutylene group, 2-ethyl-cyclobutylene group, 3-ethyl-cyclobutylene group, 1,2-dimethyl-cyclobutylene group, 1,3-dimethyl-cyclobutylene group, 2,2-dimethyl-cyclobutylene group, 2,3-dimethyl-cyclobutylene group, 2,4-dimethyl-cyclobutylene group, 3,3-dimethyl-cyclobutylene group, 1-n-propyl-cyclopropylene group, 2-n-propyl-cyclopropylene group, 1-isopropyl-cyclopropylene group, 2-isopropyl-cyclopropylene group, 1,2,2-trimethyl-cyclopropylene group, 1,2,3-trimethyl-cyclopropylene group, 2,2,Examples of such cyclopropylene groups include a 3-trimethyl-cyclopropylene group, a 1-ethyl-2-methyl-cyclopropylene group, a 2-ethyl-1-methyl-cyclopropylene group, a 2-ethyl-2-methyl-cyclopropylene group, a 2-ethyl-3-methyl-cyclopropylene group, an n-heptylene group, an n-octylene group, an n-nonylene group, and an n-decanylene group.

[0023] R １ An example of the alkyl group having 1 to 10 carbon atoms substituted or interrupted by a heteroatom in the formula (I) is an alkoxy group having 1 to 10 carbon atoms.

[0024] Examples of the alkoxy group having 1 to 10 carbon atoms include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, an i-butoxy group, an s-butoxy group, a t-butoxy group, an n-pentoxy group, a 1-methyl-n-butoxy group, a 2-methyl-n-butoxy group, a 3-methyl-n-butoxy group, a 1,1-dimethyl-n-propoxy group, a 1,2-dimethyl-n-propoxy group, a 2,2-dimethyl-n-propoxy group, a 1-ethyl-n-propoxy group, an n-hexyloxy group, a 1-methyl-n-pentyloxy group, a 2-methyl-n-pentyloxy group, a 3-methyl-n-pentyloxy group, a 4-methyl-n-pentyloxy group, a 5-methyl-n-pentyloxy group, a 6-methyl-n-pentyloxy group, a 7-methyl-n-pentyloxy group, a 8-methyl-n-pentyloxy group, a 9-methyl-n-pentyloxy group, a 10-methyl-n-butoxy group, a 11-methyl-n-butoxy group, a 22-methyl-n-butoxy group, a 23-methyl-n-butoxy group, a 24-methyl-n-butoxy group, a 25-methyl-n-butoxy group, a 26-methyl-n-butoxy group, a 27-methyl-n-butoxy group, a 28-methyl-n-butoxy group, a 29-methyl-n-butoxy group, a 30-methyl-n-butoxy group, a 31-methyl-n-butoxy group, a 32-methyl-n-butoxy group, a 33-methyl-n-butoxy group, a 34-methyl-n-butoxy group, a 35-methyl-n-butoxy group, a 36-methyl-n- Examples of the alkyl group include an ethyl-n-pentyloxy group, a 1,1-dimethyl-n-butoxy group, a 1,2-dimethyl-n-butoxy group, a 1,3-dimethyl-n-butoxy group, a 2,2-dimethyl-n-butoxy group, a 2,3-dimethyl-n-butoxy group, a 3,3-dimethyl-n-butoxy group, a 1-ethyl-n-butoxy group, a 2-ethyl-n-butoxy group, a 1,1,2-trimethyl-n-propoxy group, a 1,2,2-trimethyl-n-propoxy group, a 1-ethyl-1-methyl-n-propoxy group, a 1-ethyl-2-methyl-n-propoxy group, an n-heptyloxy group, an n-octyloxy group, and an n-nonyloxy group.

[0025] Examples of A include a group having a (meth)acryloyloxy group represented by the following formula (A-1).

[0026] (In formula (A-1), R ａ is a hydrogen atom or a methyl group. * represents a bond.

[0027] Furthermore, as long as A is a group having a (meth)acryloyloxy group, it may be, for example, a group having a (meth)acryloyloxy group represented by the following formula (A-2).

[0028] (In formula (A-2), R ａ is a hydrogen atom or a methyl group. * represents a bond.

[0029] Furthermore, A may be, for example, a group having an allylamino group, represented by the following formula (A-3).

[0030] (In formula (A-3), * represents a bond.)

[0031] The structural unit represented by formula (1-1) may be one type or a combination of two or more types. For example, a copolymer having a plurality of structural units in which Ar is the same type may be used, and copolymers having a plurality of structural units in which Ar is different, such as a structural unit in which Ar has a benzene ring and a structural unit in which Ar has a naphthalene ring, are not excluded from the technical scope of the present application.

[0032] The above phrase "optionally interrupted" means, in the case of an alkylene group having 2 to 10 carbon atoms, that any carbon-carbon bond in the alkylene group is interrupted by a heteroatom (i.e., an ether bond in the case of oxygen, or a sulfide bond in the case of sulfur), an ester bond, or an amide bond; and in the case of an alkylene group having one carbon atom (i.e., a methylene group), that either one of the carbons of the methylene group has a heteroatom (i.e., an ether bond in the case of oxygen, or a sulfide bond in the case of sulfur), an ester bond, or an amide bond.

[0033] T １ When n2=1, represents a single bond, or an alkylene group having 1 to 10 carbon atoms which may be interrupted by an ether bond, an ester bond, or an amide bond, and is preferably a combination of an ether bond and a methylene group, a combination of an ester bond and a methylene group, or a combination of an amide bond and a methylene group.

[0034] The alkyl group having 1 to 10 carbon atoms which may be substituted with a heteroatom refers to an alkyl group having 1 to 10 carbon atoms in which one or more hydrogen atoms have been substituted with a heteroatom (preferably a halogeno group).

[0035] The halogeno group refers to a halogen-X (F, Cl, Br, I) that replaces hydrogen.

[0036] In formula (1-1), k is an integer of 1 to 3, and for example, -T １ The number of groups represented by -(A)n2 may not be one, but may be two or three.

[0037] The polymer having a structural unit represented by formula (1-1) can be obtained, for example, by reacting a polymer having a structural unit represented by the following formula (1-1') with (meth)acrylic acid.

[0038] (In formula (1-1'), Ar, R １ , n1, L １ , n2, k, and T １ represents Ar and R in formula (1-1). １ , n1, L １ , n2, k, and T １ and E is a group having an epoxy group.

[0039] The polymer having a structural unit represented by formula (1-1') is not particularly limited as long as it satisfies the structural unit of formula (1-1'). It may be produced by a method known per se. Commercially available products may also be used. Examples of commercially available products include EPPN-201, EOCN-104S, EOCN-103S, EOCN-102S, EOCN-1020-70, EOCN-1020-55, NC-2000-L, NC-3000-L, NC-3000-H, NC-3100, NC-7000L, NC-7000H, NC-3500, XD-1000, EPPN-502H, EPPN-502HY, EPPN-501H, and FAE-2500 (all manufactured by Nippon Kayaku Co., Ltd.), EPICLON (registered trademark) HP-5000, and EPICLON (registered trademark) HP-7200 (manufactured by DIC Corporation).

[0040] The weight average molecular weight of the polymer having the structural unit represented by formula (1-1') is 100 or more, 500 to 200,000, 600 to 50,000, or 700 to 10,000.

[0041] Examples of polymers having a structural unit represented by formula (1-1') include those having the following structural units.

[0042]

[0043]

[0044] <<<First and Second Embodiments>>> (In formula (1-2), A represents a group having a (meth)acryloyloxy group.)

[0045] In formula (1-2), A includes the same specific examples of formula (A-1) and formula (A-2) as those given as specific examples in formula (1-1).

[0046] The polymer having the structural unit represented by formula (1-2) can be obtained, for example, by reacting a polymer having the structural unit represented by the following formula (1-2') with (meth)acrylic acid.

[0047] (In formula (1-2'), E is a group having an epoxy group.)

[0048] The polymer having the structural unit represented by formula (1-2') may be one produced by a method known per se. Commercially available products may also be used. Examples of commercially available products include EHPE-3150 (manufactured by Daicel Corporation).

[0049] Examples of polymers having a structural unit represented by formula (1-2') include those having the following structural units.

[0050]

[0051] <<<First to Third Embodiments>>> (In formula (1-3), R b represents a hydrogen atom or a methyl group, T ３represents a single bond or an alkylene group having 1 to 10 carbon atoms which may be interrupted by a heteroatom, and A represents a group having a (meth)acryloyloxy group.

[0052] In formula (1-3), A includes the same specific examples of formula (A-1) and formula (A-2) as those given as specific examples in formula (1-1).

[0053] The polymer having a structural unit represented by formula (1-3) can be obtained, for example, by reacting a polymer having a structural unit represented by the following formula (1-3') with (meth)acrylic acid.

[0054] (In formula (1-3′), E is a group having an epoxy group, and R b , T ３ is R in formula (1-3). b , T ３ is synonymous with

[0055] The polymer having the structural unit represented by formula (1-3') may be produced by a method known per se.

[0056] Examples of polymers having a structural unit represented by formula (1-3') include those having the following structural units.

[0057]

[0058] <<<First to Fourth Embodiments>>> (In formula (1-4), R b , R c represent a hydrogen atom or a methyl group.

[0059] The polymer having the structural unit represented by formula (1-4) can be obtained, for example, by reacting a polymer having the structural unit represented by the following formula (1-4') with (meth)acrylic acid.

[0060] (In formula (1-4'), R b is R in formula (1-4). b is synonymous with

[0061] The polymer having the structural unit represented by formula (1-4') may be produced by a method known per se.

[0062] Examples of polymers having a structural unit represented by formula (1-4') include those having the following structural units.

[0063]

[0064] <<<First to fifth embodiments>>> (In formula (1-5), A ４ represents a group having a (meth)acryloyloxy group, and X represents an n-valent group.

[0065] A ４ The group having a (meth)acryloyloxy group is, for example, a group represented by the following formula (A-5), a group represented by the following formula (A-6), or a group represented by the following formula (A-7).

[0066] (In formula (A-5), R c is a hydrogen atom or a methyl group. * represents a bond.

[0067] (In formula (A-6), R c is a hydrogen atom or a methyl group. * represents a bond.

[0068] (In formula (A-7), R c is a hydrogen atom or a methyl group. * represents a bond.

[0069] The polymer having a structural unit represented by formula (1-5) can be obtained, for example, by reacting a polymer having a structural unit represented by the following formula (1-5') with (meth)acrylic acid.

[0070] (In formula (1-5'), E represents an epoxy group, and X represents an n-valent group.)

[0071] The epoxy group of E is, for example, a group represented by the following formula (A-8) or a group represented by the following formula (A-9).

[0072] (In formula (A-8), * represents a bond.)

[0073] (In formula (A-9), * represents a bond.)

[0074] The polymer having a structural unit represented by formula (1-5') may be one produced by a method known per se. Commercially available products may also be used. Examples of commercially available products include YH-434L (manufactured by Nippon Steel Chemical & Material Co., Ltd.), Sumiepoxy ELM-434L (manufactured by Sumitomo Chemical Co., Ltd.), Showfree (registered trademark) BATG (manufactured by Resonac Co., Ltd.), TEP-G (manufactured by Asahi Organic Chemicals Industries Co., Ltd.), jER (registered trademark)-1031S (manufactured by Mitsubishi Chemical Corporation), EPICLON HP-4700, NC-6000 (manufactured by DIC Corporation), Epolead GT-401 (manufactured by Daicel Corporation), Denacol (registered trademark) EX-521, Denacol (registered trademark) EX-411 (manufactured by Nagase ChemteX Corporation), and TEPIC (registered trademark)-SS (manufactured by Nissan Chemical Industries Co., Ltd.).

[0075] Examples of polymers having a structural unit represented by formula (1-5') include those having the following structural units.

[0076]

[0077]

[0078] A polymer or compound "containing a polymerizable group and having a carbon content of 70% or more" according to the present invention is, for example, a polymer or compound containing the polymer or compound of the first embodiment shown in the above-mentioned embodiments 1-1 to 1-5, and having a carbon content of 70% or more in the structural unit.

[0079] For example, an example of a polymer or compound "containing a polymerizable group and having a carbon content of 70% or more" is a polymer having a structural unit represented by the following formula (CR1-1). In the polymer having a structural unit represented by the following formula (CR1-1), the (meth)acrylic group referred to as the polymerizable group means a (meth)acryloyloxy group. In addition, in the polymer having a structural unit represented by the following formula (CR1-1), a preferred embodiment of the allyl group referred to as the polymerizable group is a (di)allylamino group.

[0080] (In formula (CR1-1), Ar represents a benzene ring, a naphthalene ring, or an anthracene ring, and R１ represents a hydroxy group, a mercapto group which may be protected by a methyl group, an amino group which may be protected by a methyl group, a halogeno group, or an alkyl group having 1 to 10 carbon atoms which may be substituted or interrupted by a heteroatom and which may be substituted by a hydroxy group; n1 represents an integer of 0 to 3; L １ represents an alkylene group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 25 carbon atoms, or a group formed by combining two or more of these groups, each of which may have a substituent; n2 represents 1 or 2; A represents a group having a (meth)acryloyloxy group or a group having an allylamino group; T １ When n2=1, represents a single bond or an alkylene group having 1 to 10 carbon atoms which may be interrupted by an ether bond, an ester bond or an amide bond; T １ represents a nitrogen atom or an amide bond when n2=2; and k represents an integer of 1 to 3.

[0081] In formula (CR1-1), Ar, R １ , T １ , A represents Ar, R in the above formula (1-1). １ , T １ , A is synonymous with A.

[0082] L １ The alkylene group having 1 to 20 carbon atoms refers to, for example, a linear alkylene group having 1 to 20 carbon atoms, a branched alkylene group having 3 to 20 carbon atoms, or a cyclic alkylene group having 3 to 20 carbon atoms. １ The aromatic hydrocarbon group may be a monocyclic or condensed ring aromatic hydrocarbon group, and may be a linked ring in which these aromatic hydrocarbon groups are linked.

[0083] L １ Examples of the cyclic alkylene group and aromatic hydrocarbon group in the formula (I) include the various groups having a cyclic structure shown below. １ In the formula (II), these cyclic groups and chain alkylene groups are appropriately combined to form various L １ The following exemplary groups may be formed.

[0084] In each cyclic group represented by (I), * represents a bond.

[0085] Each L represented by (II) １ In the exemplary groups, * indicates a bond.

[0086] L １ Examples of the substituent that may be substituted on the group include a group containing a (meth)acryloyloxy group and an alkoxy group. １ A more preferred embodiment of the substituent on the alkylene group in the formula (I) is, for example, -Ar-T １ -(A)n2 (where Ar, T １ , A, n2 are Ar, T in the above formula (1-1). １ , A, n2.) Also, L １ More preferred embodiments of the substituent substituted on the aromatic hydrocarbon group include, for example, -T １ -(A)n2 and alkoxy groups (wherein, T １ , A, n2 are Ar, T in the above formula (1-1). １ , A, and n2.)

[0087] The structural unit represented by formula (CR1-1) may be one type or a combination of two or more types. For example, a copolymer having a plurality of structural units in which Ar is the same type may be used, and copolymers having a plurality of structural units in which Ar is different types, such as a structural unit in which Ar has a benzene ring and a structural unit in which Ar has a naphthalene ring, are not excluded from the technical scope of the present application.

[0088] The above phrase "optionally interrupted" means, in the case of an alkylene group having 2 to 10 carbon atoms, that any carbon-carbon bond in the alkylene group is interrupted by a heteroatom (i.e., an ether bond in the case of oxygen, or a sulfide bond in the case of sulfur), an ester bond, or an amide bond; and in the case of an alkylene group having one carbon atom (i.e., a methylene group), that either one of the carbons of the methylene group has a heteroatom (i.e., an ether bond in the case of oxygen, or a sulfide bond in the case of sulfur), an ester bond, or an amide bond.

[0089] If the structural unit represented by formula (CR1-1) is present, various substituents may be added or the carbon chain length in the side chain may be extended in order to increase the carbon content of the structural unit. １ The aromatic hydrocarbon group in L may have a substituent. １ As described above, examples of the substituent that may be substituted on the aromatic hydrocarbon group include -T １ -(A)n2, where T １ , A, and n2 are T in the above formula (CR1-1). １ , A, and n2. In addition, preferred embodiments in the case of extending the carbon chain length in the side chain of the structural unit represented by formula (CR1-1) include, for example, (i) L in formula (CR1-1) １ or (ii) a combination of a structural unit represented by formula (CR1-1) with another structural unit having a higher carbon content than the structural unit represented by formula (CR1-1). The other structural unit in the case of (ii) above is, for example, a structural unit in which the A moiety in the structural unit represented by formula (CR1-1) is modified by bonding a group for increasing the carbon content to the A moiety.

[0090] The carbon content of the polymer or compound according to the present invention is 70% or more. Here, the carbon content of the polymer can be determined, for example, by calculating the carbon content per structural unit, which is a repeating unit forming the polymer. The carbon content can be determined, for example, by calculating the ratio of the atomic weight of carbon atoms (C) to the sum of the atomic weights of the constituent atoms per structural unit of the polymer.

[0091] Specific examples of polymers having a structural unit represented by formula (CR1-1) and having a carbon content of 70% or more in the structural unit include the following polymers (see exemplary structures 1 to 9). Specific examples of polymers having a carbon content of less than 70% in the structural unit are also shown below as comparative exemplary structures 1 and 2.

[0092]

[0093]

[0094]

[0095] As shown in the above exemplary structure 6, for example, the aromatic hydrocarbon group in L1 in formula (CR1-1) may be given a substituent represented by -T1-(A)n2. As shown in the above exemplary structure 7, for example, in formula (CR1-1), k=2, -T １ A plurality of groups represented by -(A)n2 may be bonded to Ar. As shown in the above exemplary structure 8, for example, L in formula (CR1-1) １ As shown in the above exemplary structure 9, for example, a structural unit represented by formula (CR1-1) may be combined with a structural unit in which a group for increasing the carbon content in the A moiety in the structural unit represented by formula (CR1-1) is bonded to the A moiety, separately from the structural unit represented by formula (CR1-1), to modify the A moiety.

[0096] The weight-average molecular weight of the polymer or compound containing a polymerizable group is not particularly limited, but is preferably from 1,000 to 50,000, more preferably from 2,500 to 25,000, and particularly preferably from 3,000 to 9,000. The weight-average molecular weight can be measured by gel permeation chromatography (GPC).

[0097] The content of the polymer or compound containing a polymerizable group in the protective film-forming composition is not particularly limited, but is preferably 1% by mass to 30% by mass, more preferably 5% by mass to 25% by mass, and particularly preferably 10% by mass to 20% by mass.

[0098] The content of the polymer or compound containing a polymerizable group in the composition for forming a protective film is not particularly limited, but is preferably 70% by mass to 99% by mass, more preferably 80% by mass to 97% by mass, and particularly preferably 85% by mass to 95% by mass, based on the film-constituting components. The film-constituting components are components remaining after excluding volatile components (solvents) from the composition for forming a protective film.

[0099] As will be shown in the examples described later, by using a composition for forming a protective film containing a polymer or compound having a photopolymerizable group and a high carbon content, a protective film that exhibits good photosensitivity (organic developability) and excellent dry etching resistance can be formed.

[0100] <Solvent> Examples of the solvent contained in the protective film-forming composition of the present invention include water, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexane, cyclohexane-1, cyclohexane-2, cyclohexane-3, cyclohexane-4, cyclohexane-5, cyclohexane-6, cyclohexane-7, cyclohexane-8, cyclohexane-9, cyclohexane-10, cyclohexane-11, cyclohexane-12, cyclohexane-13, cyclohexane-14, cyclohexane-15, cyclohexane-16, cyclohexane-17, cyclohexane-18, cyclohexane-19, cyclohexane-20, cyclohexane-21, cyclohexane-22, cyclohexane-23, cyclohexane-24, cyclohexane-25, cyclohexane-26, cyclohexane-27, cyclohexane-28, cyclohexane-39, cyclohexane-49, cyclohexane-59, cyclohexane-19, cyclohexane-29, cyclohexane-39, cyclohexane-49, cyclohexane-19, cyclohexane-2 ... Examples of the solvent include cyclopentanone, cyclohexanone, cycloheptanone, 4-methyl-2-pentanol, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, ethyl ethoxyacetate, 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.

[0101] The content of the solvent in the protective film-forming composition is not particularly limited, but is preferably 60% by mass to 99% by mass, more preferably 75% by mass to 98% by mass, and particularly preferably 80% by mass to 95% by mass.

[0102] <Other Components> Furthermore, the protective film-forming composition may contain, as necessary, a photocrosslinking agent, a thermal crosslinking agent, a photoradical initiator, a thermal radical initiator acid (catalyst), a thermal acid generator, a photoacid generator, a base (catalyst), a thermal base generator, a photobase generator, a polymerization inhibitor, a crosslinking agent (such as a polyfunctional acrylic), an adhesion improver, an adhesion aid (a silane coupling agent), a surfactant, an antifoaming agent, a rheology adjuster, a pigment, a dye, a storage stabilizer, a dissolution promoter such as a polyhydric phenol or a polyvalent carboxylic acid, a sensitizer, and the like.

[0103] Examples of the photocrosslinking agent include polyfunctional (meth)acrylate compounds, etc. In this specification, methacrylate and acrylate are collectively referred to as (meth)acrylate.

[0104] Examples of polyfunctional (meth)acrylate compounds include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, and polypropylene glycol di(meth)acrylate. , 1,4-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, dicyclopentanyl di(meth)acrylate, bisphenol A di(meth)acrylate, ethoxylated bisphenol A di(meth)acrylate, propoxylated bisphenol A di(meth)acrylate, bisphenol S di(meth)acrylate, phthalic acid di(meth)acrylate, 9,9 -bis[4-(2-(meth)acryloyloxyethoxy)phenyl]fluorene, glycerin di(meth)acrylate, glycerin tri(meth)acrylate, glycerin ethoxy tri(meth)acrylate, glycerin propoxy tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane ethoxy tri(meth)acrylate, trimethylolpropane propoxy tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol Examples of such an acrylate include erythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol ethoxy tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, sorbitol hexa(meth)acrylate, tris(2-(meth)acryloyloxyethyl)isocyanurate, and ε-caprolactone-modified tris-(2-(meth)acryloyloxyethyl)isocyanurate.

[0105] Examples of the polyfunctional (meth)acrylate compound include (meth)acrylates having a hydroxy group, such as 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, glycerin di(meth)acrylate, pentaerythritol tri(meth)acrylate, and dipentaerythritol penta(meth)acrylate, or polyfunctional (meth)acrylates having a hydroxy group, and 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, xylylene diisocyanate, 1,5-naphthalene diisocyanate, m-phenylenediisocyanate, and the like. and polyfunctional urethane (meth)acrylates synthesized by reacting a diisocyanate compound such as methylisocyanate, p-phenylene diisocyanate, diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-dibenzyl diisocyanate, isophorone diisocyanate, 1,6-hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,3-bis(isocyanatomethyl)benzene, or 1,3-bis(isocyanatomethyl)cyclohexane.

[0106] Further examples of polyfunctional (meth)acrylate compounds include polyfunctional epoxy (meth)acrylates synthesized by reacting (meth)acrylic acid with a homopolymer or copolymer obtained by radical polymerization of a (meth)acrylate monomer having an epoxy group, such as glycidyl (meth)acrylate, glycidyloxybutyl (meth)acrylate, or 3,4-epoxycyclohexylmethyl (meth)acrylate. Here, "copolymer" refers to a polymer obtained by polymerizing two or more types of monomers. The copolymer may be a copolymer obtained by polymerizing two or more types of (meth)acrylates having an epoxy group, or a copolymer obtained by polymerizing a (meth)acrylate having an epoxy group and another (meth)acrylate.

[0107] Commercially available polyfunctional (meth)acrylate compounds include, for example, the following products: Aronix (registered trademark) M-208, M-210, M-211B, M-215, M-220, M-225, M-233, M-240, M-245, M-260, M-270, M-303, M-305, M-306, M-309, M-310, M-313, M-315, M-321, M-350, M-360, M-400, M-402, M-403, M-404, M-405, and M-406. , M-408, M-450, M-452, M-460, M-510, M-520, M-1100, M-1200, M-1210, M-1310, M-1600, M-1960, M-6100, M-6200, M-6250, M-6500, M-7100, M-7300K, M-8030, M-8060, M-8100, M-8530, M-8560, and M-9050 (all manufactured by Toa Gosei Co., Ltd.).

[0108] KAYARAD (registered trademark) NPGDA, same as PEG400DA, same as FM-400, same as R-167, same as HX-220, same as HX-620, same as R-526, same as R-551, same as R-712, same as R-604, same as R-684, same as GPO-303, same as TMPTA, same as HDDA, same as TPGDA, same as KS-HDDA, same as KS-TPGDA, same as MANDA, same as THE-3 30, same as TPA-320, same as TPA-330, same as PET-30, same as T-1420, same as T-1420(T), same as RP-1040, same as DPHA, same as DPEA-12, same as D-310, same as D-330, same as DPCA-20, same as DPCA-30, same as DPCA-60, same as DPCA-120, same as FM-700, same as DN-0075, same as DN-2475, same as TC-120 S, same as R-115, same as R-130, same as R-381, same as EAM-2160, same as CCR-1291H, same as CCR-1235, same as ZAR-1035, same as ZAR-2000, same as ZFR-1401H, same as ZFA-1491H, same as ZCR-1569H, same as ZCR-1601H, same as ZCR-1797H, same as ZCR-1798H, same as UXE-3000, same as UXE-3 024, same as UX-3204, same as UX-4101, same as UXT-6100, same as UX-6101, same as UX-7101, same as UX-8101, same as UX-0937, same as UXF-4001-M35, same as UXF-4002, same as DPHA-40H, same as UX-5000, same as UX-5102D-M20, same as UX-5103D, same as UX-5005 (all manufactured by Nippon Kayaku Co., Ltd.).

[0109] NK Ester A-200, A-400, A-600, A-1000, A-1500, A-2000, ABE-300, A-BPE-4, A-BPE-6, A-BPE-10, A-BPE-20, A-BPE-30, A-BPEF, A-BPP-3, A-DCP, A-DOD-N, A-HD-N, A-NOD, A-GLY-3E, A-GLY-9E, A-GLY-20E, A-TMPT, A-TMPT-3EO, A- TMPT-9EO, ATM-4E, ATM-35E, APG-100, APG-200, APG-400, APG-700, A-PTMG-65, A-1000PER, A-B1206PE, 701A, A-9 300, A-9300-1CL, A-9300-6CL, A-9530, ADP-51EH, ATM-31EH, A-TMM-3, A-TMM-3L, A-TMM-3LM-N, AD-TMP, A-TMMT, A-9550, A-DPH, A-DPH-12E, 1G, 2G, 3G, 4G, 9G, 14G, 23G, BPE-80N, BPE-100, BPE-100N, BPE-200, BPE-500, BPE -900, BPE-1300N, DCP, DOD-N, HD-N, NOD-N, NPG, 1206PE, 701, 3PG, 9PG, TMPT, NK Economer A-PG5009E, A-PG5027E, A -PG5054E, NK Oligo U-2PPA, NK U-6LPA, NK U-10HA, U-10PA, UA-1100H, U-4H, U-6H, U-4HA, U-6HA, U-15HA, UA-32P, UA-33H, UA-53H, U-200PA, U-324A, UA-160TM, UA-290TM, UA-4200, UA-4400, UA-122P, UA-7100, UA-W2A (manufactured by Shin-Nakamura Chemical Co., Ltd.).

[0110] The content of the crosslinking agent is preferably 1 to 20 parts by mass, more preferably 2 to 10 parts by mass, per 100 parts by mass of the polymer or compound containing a polymerizable group.

[0111] The radical initiator may be any as long as it is capable of releasing a substance that initiates radical polymerization upon irradiation with light and / or heat. Examples of photoradical initiators include benzophenone derivatives, imidazole derivatives, bisimidazole derivatives, N-arylglycine derivatives, organic azide compounds, titanocene compounds, aluminate complexes, organic peroxides, N-alkoxypyridinium salts, and thioxanthone derivatives. More specifically, benzophenone, 1,3-di(tert-butyldioxycarbonyl)benzophenone, 3,3',4,4'-tetrakis(tert-butyldioxycarbonyl)benzophenone, 3-phenyl-5-isoxazolone, 2-mercaptobenzimidazole, bis(2,4,5-triphenyl)imidazole, 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, bis(η ５ Examples of suitable fluorocarbons include, but are not limited to, 2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium), and the like.

[0112] Commercially available products may also be used as the photoradical initiator. Examples of such products include IRGACURE (registered trademark) OXE01, OXE02, OXE03, and OXE04 (manufactured by BASF Japan Ltd.), Omnirad 651, 184, 369E, 1173, 127D, 2959, 907, 379EG, 819, and MBF (manufactured by IGM Resins), and ADEKA ACRUISE. Examples of such antiperspirants include N-1919T, NCI-831E, NCI-730, and NCI-930 (manufactured by ADEKA Corporation), Speedcure (registered trademark) MBB, PBZ, ITX, CTX, and EDB (manufactured by Lambson), Esacure (registered trademark) ONE, KIP150, and KTO46 (manufactured by Lamberti), and KAYACURE (registered trademark) DETX-S, CTX, BMS, and DMBI (manufactured by Nippon Kayaku Co., Ltd.).

[0113] Examples of thermal radical initiators include peroxides such as acetyl peroxide, benzoyl peroxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, hydrogen peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, di-tert-butyl peroxide, dicumyl peroxide, dilauroyl peroxide, tert-butyl peroxyacetate, tert-butyl peroxypivalate, and tert-butylperoxy-2-ethylhexanoate; 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), (1-phenylethyl)azobis(2,4-dimethylvaleronitrile), and (1-phenylethyl)azobis(2,4-dimethylvaleronitrile). Examples of the azo compounds include 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), dimethyl-2,2'-azobisisobutyrate, 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(1-cyclohexanecarbonitrile), 2-(carbamoylazo)isobutyronitrile, 2,2'-azobis(2,4,4-trimethylpentane), 2-phenylazo-2,4-dimethyl-4-methoxyvaleronitrile, and 2,2'-azobis(2-methylpropane); and persulfates such as ammonium persulfate, sodium persulfate, and potassium persulfate, but are not limited to these.

[0114] Commercially available thermal radical initiators include, for example, Perloyl (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, Perhexyl (registered trademark) ND, PV, D, I, O, Z, Perocta (registered trademark) ND, Nyper (registered trademark) PMB, and BMT. , BW, Pertetra (registered trademark) A, Perhexa (registered trademark) MC, TMH, HC, 250, 25B, C, 25Z, 22, V, Perocta (registered trademark) O, Percumyl (registered trademark) ND, D, Permenta (registered trademark) H, Nofmer (registered trademark) BC (all manufactured by NOF Corporation); V-70, V-65, V-59, V-40, V-30, VA-044, VA-046B, VA-0 61, V-50, VA-057, VA-086, VF-096, VAm-110, V-601, V-501 (all manufactured by Wako Pure Chemical Industries, Ltd.); IRGACURE (registered trademark) 184, 369, 651, 500, 819, 907, 784, 2959, CGI1700, CGI1750, CGI1850, CG24-61, DAROCUR (registered trademark) 1116, 1173, LU Examples of the anti-corrosive agent include, but are not limited to, CIRIN (registered trademark) TPO (manufactured by BASF Japan Ltd.); UVECRYL (registered trademark) P36 (manufactured by Cytec Surface Specialties); and Esacure (registered trademark) KIP150, KIP65LT, KIP100F, KT37, KT55, KTO46, and KIP75 / B (manufactured by Lamberti).

[0115] As the polymerization inhibitor (antioxidant), a hindered phenol compound may be used, specifically 2,6-diisobutylphenol, 3,5-di-t-butylphenol, 3,5-di-t-butylcresol, hydroquinone, hydroquinone monomethyl ether, N-nitroso-N-phenylhydroxylamine aluminum, pyrogallol, t-butylcatechol, 4-methoxy-1-naphthol, 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-butyl-hydroquinone, octadecyl-3-(3,5-di-t-butyl-4 -hydroxyphenyl)propionate, isooctyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 4,4'-methylenebis(2,6-di-t-butylphenol), 4,4'-thio-bis(3-methyl-6-t-butylphenol), 4,4'-butylidene-bis(3-methyl-6-t-butylphenol), triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] phenyl)propionate], 2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], N,N'hexamethylenebis(3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), 2,2'-methylene-bis(4-methyl-6-t-butylphenol), 2,2'-methylene-bis(4-ethyl-6-t-butylphenol), pentaerythrityl-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], tris-(3,5-di-t-butyl-4- hydroxybenzyl)-isocyanurate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-isopropylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-s-butyl-3-hydroxy-2,1,3,5-tris[4-(1-ethylpropyl)-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris[4-triethylmethyl-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(3-hydroxy-2,6- dimethyl-4-phenylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2,5,6-trimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-5-ethyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl- 1,3,5-tris(4-t-butyl-6-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-5,6-diethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-5,6-diethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-5,6-diethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, Examples of the hindered phenol compounds include 1,3,5-tris(4-t-butyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, and 1,3,5-tris(4-t-butyl-5-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione.5H)-trione is preferred. Commercially available polymerization inhibitors may be used, and a specific example is Irganox-3114 (manufactured by BASF Japan Ltd.).

[0116] 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, per 100 parts by mass of the polymer or compound containing a polymerizable group.

[0117] Examples of surfactants include polyoxyethylene alkyl ether compounds such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; polyoxyethylene alkyl aryl 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. Other examples include fluorine-based surfactants such as trade names EFTOP EF301, EF303, and EF352 (manufactured by Tochem Products Co., Ltd.), trade names MEGAFAC F171, F173, R-08, R-30, R-40, R-40-LM, R-41, and R-41-LM (manufactured by DIC Corporation), Fluorad FC430 and FC431 (manufactured by Sumitomo 3M Limited), and trade names Asahiguard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, and SC106 (manufactured by AGC Inc.), and organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0118] The surfactant may be used alone or in combination of two or more kinds. The content of the surfactant is preferably 0.1 parts by mass or more, 0.5 parts by mass or more, and 5 parts by mass or less, and 2 parts by mass or less, per 100 parts by mass of the polymer or compound having a polymerizable group.

[0119] As the acid catalyst, an acidic compound, a basic compound, or various compounds that generate an acid or a base by heat or light can be used.

[0120] The acidic compound may be a sulfonic acid compound or a carboxylic acid compound, such as 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, and hydroxybenzoic acid.

[0121] The basic compound can be an amine compound or an ammonium hydroxide compound, and urea can be used as a compound that generates a base when heated. Examples of the amine compound include tertiary amines such as triethanolamine, tributanolamine, trimethylamine, triethylamine, tri-normal propylamine, triisopropylamine, tri-normal butylamine, tri-tert-butylamine, tri-normal octylamine, triisopropanolamine, phenyldiethanolamine, stearyldiethanolamine, and diazabicyclooctane, and aromatic amines such as pyridine and 4-dimethylaminopyridine. Other examples of the amine compound include primary amines such as benzylamine and normal butylamine, and secondary amines such as diethylamine and di-normal butylamine. Examples of the ammonium hydroxide compound include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, benzyltriethylammonium hydroxide, cetyltrimethylammonium hydroxide, phenyltrimethylammonium hydroxide, and phenyltriethylammonium hydroxide.

[0122] As the acid generator, either a thermal acid generator or a photoacid generator can be used.

[0123] Examples of the thermal acid generator include sulfonic acid compounds and carboxylic acid compounds such as p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium-p-toluenesulfonate (pyridinium-p-toluenesulfonic acid), pyridinium-p-hydroxybenzenesulfonic acid (pyridinium p-phenolsulfonate salt), 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, and hydroxybenzoic acid. Commercially available products include, for example, 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.).

[0124] Examples of photoacid generators include sulfonium salts, iodonium salts, sulfonyldiazomethane, N-sulfonyloxyimide, benzoin sulfonate-type photoacid generators, pyrogallol trisulfonate-type photoacid generators, sulfone-type photoacid generators, glyoxime derivative-type photoacid generators, oxime-O-sulfonate-type photoacid generators, bisoxime sulfonate-type photoacid generators, etc. Examples include bis(4-tert-butylphenyl)iodonium trifluoromethanesulfonate, triphenylsulfonium trifluoromethanesulfonate, phenyl-bis(trichloromethyl)-s-triazine, benzoin tosylate, and N-hydroxysuccinimide trifluoromethanesulfonate.

[0125] Examples of the thermal base generator include carbamates such as 1-methyl-1-(4-biphenylyl)ethyl carbamate and 2-cyano-1,1-dimethylethyl carbamate; ureas such as urea and N,N-dimethyl-N'-methylurea; guanidines such as guanidine trichloroacetate, guanidine phenylsulfonylacetate, and guanidine phenylpropiolate; dihydropyridines such as 1,4-dihydronicotinamide; dimethylpiperidines such as N-(isopropoxycarbonyl)-2,6-dimethylpiperidine, N-(tert-butoxycarbonyl)-2,6-dimethylpiperidine, and N-(benzyloxycarbonyl)-2,6-dimethylpiperidine; quaternary ammonium salts such as tetramethylammonium phenylsulfonylacetate and tetramethylammonium phenylpropiolate; and dicyandiamide. Further examples include U-CAT (registered trademark) SA810, SA831, SA841, and SA851 (all manufactured by San-Apro Ltd.), which are salts of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU).

[0126] Examples of the photobase generator include alkylamine-based photobase generators such as 9-anthrylmethyl=N,N-diethylcarbamate; cycloalkylamine-based photobase generators such as 9-anthryl=N,N-dicyclohexylcarbamate, 1-(9,10-anthraquinone-2-yl)ethyl=N,N-dicyclohexylcarbamate, dicyclohexylammonium=2-(3-benzoylphenyl)propionate, 9-anthryl=N-cyclohexylcarbamate, 1-(9,10-anthraquinone-2-yl)ethyl=N-cyclohexylcarbamate, cyclohexylammonium=2-(3-benzoylphenyl)propionate, and (E)-N-cyclohexyl-3-(2-hydroxyphenyl)acrylamide; and 9-anthrylmethyl=piperidine-1-carboxylate and (E)-1-piperidino-3-(2-hydroxyphenyl)-2-propene. piperidine-based photobase generators such as 1,2-diisopropyl-3-(bis(dimethylamino)methylene)guanidinium 2-(3-benzoylphenyl)propionate, ... guanidine-based photobase generators such as 1,2-dicyclohexyl-4,4,5,5-tetramethylbiguanidinium n-butyltriphenylborate, and 1,5,7-triazabicyclo[4.4.0]dec-5-enium 2-(9-oxoxanthen-2-yl)propionate; and imidazole-based photobase generators such as 1-(9,10-anthraquinone-2-yl)ethyl imidazole-1-carboxylate.

[0127] The above components can be used alone or in combination of two or more. In this case, they are used in an amount of usually 10% by mass or less, preferably 3% by mass or less, based on the solid content of the protective film-forming composition.

[0128] The method for preparing the composition for forming a protective film is not particularly limited. That is, a polymer or compound containing a polymerizable group, a solvent, and other components may be mixed in any ratio and in any order to form a homogeneous solution. The composition for forming a protective film in a solution state thus prepared is preferably used after filtering using a filter having a pore size of about 0.2 μm or the like.

[0129] As will be described later, in order to form a protective film having a thickness of about 300 nm by a spin coating method, the protective film-forming composition preferably has a viscosity of about 100 cps or less at 25° C., more preferably 50 cps or less, and particularly preferably 10 cps or less. In the present invention, the viscosity is a value measured at 25° C. using an E-type viscometer.

[0130] The protective film-forming composition is preferably photosensitive. For example, it may be a negative solvent-developable composition. In the case of a photosensitive protective film-forming composition, the photosensitive protective film-forming composition (negative type) is applied to the edge of the substrate (e.g., the flat edge of the front surface, the peripheral edge (bevel portion, apex portion, etc.), and optionally the edge of the back surface), and then the portion where the film is to be cured is exposed and developed, thereby accurately covering the peripheral edge with the protective film. The photosensitivity has the advantages of facilitating film thickness control of the protective film at the wafer edge, eliminating inner humps, improving edge shape, and correcting center position deviation during spin coating. The "edge" of the wafer will be described in detail below.

[0131] (Protective Film) The protective film of the present invention is a cured product of a coating film made of the protective film-forming composition of the present invention. Examples of methods for forming the protective film include step (X) in the semiconductor device manufacturing method described below. The protective film is, for example, a protective film for preventing metal contamination at the edge of a wafer.

[0132] In this specification, the edge of a wafer refers to a region of the outer periphery of a wafer that cannot be used and is not suitable for producing semiconductor devices. The edge of a wafer includes not only the flat edge of the outer periphery of the wafer but also the chamfered peripheral edge (bevel, apex, etc.) of the edge of the outer periphery of the wafer. Furthermore, the edge of a wafer includes not only the edge of the front surface (front surface) but also the edge of the back surface (rear surface). The edge of a wafer refers to, for example, the flat edge of the outer periphery of the front surface, the bevel or apex of the peripheral edge, and the flat edge of the outer periphery of the rear surface.

[0133] The edge of a wafer will be described using FIG. 1A or FIG. 1B. FIGS. 1A and 1B are enlarged cross-sectional views showing the edge of a wafer (substrate). More specifically, FIG. 1A is a cross-sectional view of a so-called straight-type substrate, and FIG. 1B is a cross-sectional view of a so-called round-type substrate. In the wafer W (an example of a substrate) of FIG. 1A, the edge of the wafer is an unusable portion of the outer periphery of the wafer, a portion unsuitable for fabricating semiconductor devices. The edge of the wafer includes, for example, a flat edge Ed1 on the outer periphery of the front surface. The edge of the wafer also includes, for example, a peripheral edge surface V, which is a chamfered edge of the outer periphery of the wafer. The peripheral edge surface V is composed of an upper inclined portion (upper bevel portion) S, a side portion (apex) T, and a lower inclined portion (lower bevel portion) U. The upper bevel portion is also referred to as the front bevel portion, and the lower bevel portion is also referred to as the back bevel portion. The edge of the wafer also includes, for example, a flat edge Ed2 at the outer periphery of the back surface. In the wafer W of Fig. 1B, the edge of the wafer includes Ed1, Ed2, and a peripheral edge surface V having a curved cross section that constitutes the outermost peripheral surface of the wafer W. In Fig. 1B, the peripheral edge surface V is also referred to as a bevel portion.

[0134] The lower limit of the thickness of the protective film is, for example, 1 nm, 3 nm, 5 nm, 10 nm, 30 nm, 50 nm, 80 nm, 100 nm, 200 nm, 500 nm, 800 nm, 1,000 nm, 1,500 nm, or 1,700 nm, and the upper limit of the thickness of the protective film is, for example, 10,000 nm, 9,000 nm, 8,000 nm, 7,000 nm, 6,000 nm, 5,000 nm, 4,000 nm, 3,800 nm, 3,700 nm, 3,600 nm, 3,500 nm, 3,300 nm, 3,000 nm, 2,500 nm, 2,000 nm, 1,500 nm, 1,000 nm, 800 nm, 500 nm, or 300 nm.

[0135] The protective film is, for example, a protective film that is cured by being irradiated with light having a wavelength of 170 to 800 nm (for example, 254 nm).

[0136] The properties of the protective film that covers the edge of a substrate (wafer) used in semiconductor manufacturing (for example, the flat edge of the front surface, the peripheral edge surface (bevel portion, apex portion, etc.), and the flat edge of the back surface) desirably satisfy, in addition to the function of preventing metal contamination, dry etching resistance, phosphoric acid resistance, tetramethylammonium hydroxide (TMAH) resistance, HF removability, scratch resistance, good embedding ability for uneven substrates, low amount of sublimation, affinity for hydrophobic substrates, not leaving crater foreign matter on the wafer side (bevel portion or apex portion), good edge shape, and the function of suppressing inner hump (a phenomenon in which a film-forming composition remains in a lump shape directly below the nozzle injection hole).

[0137] (Method for manufacturing a semiconductor device) The method for manufacturing a semiconductor device according to the present invention comprises: (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 an electron beam and then developing it; and (C) a step of etching the semiconductor substrate using the resist pattern as a mask, and further comprises a step (X) of forming a protective film on an edge (e.g., a flat edge on the front surface, a peripheral edge surface (bevel portion, apex portion, etc.), and optionally a back surface edge) of a wafer for semiconductor manufacturing using the protective film-forming composition of the present invention.

[0138] The steps are explained below in order. <Step (A)> In step (A), a resist film is formed on a semiconductor substrate. The semiconductor substrate is a wafer used for manufacturing semiconductor devices and the like, and in addition to commonly used silicon wafers and germanium wafers, compound semiconductor wafers formed by combining two or more elements, such as gallium arsenide, indium phosphide, gallium nitride, indium nitride, and aluminum nitride, can be used. These are usually disk-shaped and have sizes of, for example, 4, 6, 8, or 12 inches. Commercially available products may be used.

[0139] When a semiconductor substrate having an inorganic film formed on its surface is used, the inorganic film can be formed by, for example, ALD (atomic layer deposition), CVD (chemical vapor deposition), reactive sputtering, ion plating, vacuum deposition, or spin coating (spin-on glass: SOG). Examples of the inorganic film include a polysilicon film, a silicon oxide film, a silicon nitride film, a BPSG (Boro-Phospho Silicate Glass) film, a titanium nitride film, a titanium nitride oxide film, a tungsten film, a gallium nitride film, and a gallium arsenide film.

[0140] A resist underlayer film, a resist film, etc. of a predetermined thickness are formed on such a semiconductor substrate by an appropriate coating method such as spraying, spinning, or coating. In general, in the case of a spin coating method, the resist underlayer film-forming composition, the resist film-forming composition, etc. are each supplied from above the center of a rotating disk-shaped substrate through a nozzle or the like. Usually, these films are baked using a heating means such as a hot plate.

[0141] The photoresist used to form the resist film is not particularly limited as long as it is sensitive to the light used for exposure. In this specification, electron beam resists are also considered to be photoresists. Both negative and positive photoresists can be used. Examples of such photoresists include a positive photoresist composed of a novolak resin and a 1,2-naphthoquinone diazide sulfonic acid ester; a chemically amplified photoresist composed of a binder having a group that decomposes in the presence of an acid to increase the alkaline dissolution rate and a photoacid generator; a chemically amplified photoresist composed of a low molecular weight compound that decomposes in the presence of an acid to increase the alkaline dissolution rate of the photoresist, an alkali-soluble binder, and a photoacid generator; a chemically amplified photoresist composed of a binder having a group that decomposes in the presence of an acid to increase the alkaline dissolution rate of the photoresist, a low molecular weight compound that decomposes in the presence of an acid to increase the alkaline dissolution rate of the photoresist, and a photoacid generator; and a resist containing a metal element. Examples of such photoresists include V146G (trade name) manufactured by JSR Corporation, APEX-E (trade name) manufactured by Shipley, PAR710 (trade name) manufactured by Sumitomo Chemical Co., Ltd., and AR2772 and SEPR430 (trade names) manufactured by Shin-Etsu Chemical Co., Ltd. Other examples include fluorine-containing polymer photoresists such as those described in Proc. SPIE, Vol. 3999, 330-334 (2000), Proc. SPIE, Vol. 3999, 357-364 (2000), and Proc. SPIE, Vol. 3999, 365-374 (2000). Negative photoresists are preferred.

[0142] The resist film-forming composition used to form the resist film may contain one or more metals. Examples of the form of the metal include a simple metal, a metal salt, a metal complex, and other metal-containing compounds. The type of metal is not particularly limited, but examples thereof include tin, indium, antimony, bismuth, gallium, germanium, aluminum, zirconium, hafnium, cerium, lanthanum, and cesium.

[0143] The resist film-forming composition used to form the resist film may also be a metal-containing resist. Metal-containing resists are also called metal oxide resists (MOR), and a representative example is a tin oxide-based resist. Examples of metal oxide resist materials include coating compositions containing metal oxo-hydroxo networks having organic ligands via metal-carbon bonds and / or metal carboxylate bonds, as described in JP-A-2019-113855. One example of a metal-containing resist uses a peroxo ligand as a radiation-sensitive stabilizing ligand. Details of peroxo-based metal oxo-hydroxo compounds are described, for example, in the patent document described in paragraph

[0011] of JP-A-2019-532489. Examples of such patent documents include U.S. Pat. No. 9,176,377 B2, U.S. Patent Application Publication No. 2013 / 0224652 A1, U.S. Pat. No. 9,310,684 B2, U.S. Patent Application Publication No. 2016 / 0116839 A1, and U.S. Patent Application Publication No. 15 / 291738.

[0144] The baking conditions for the resist film are appropriately selected from a baking temperature of 70°C to 400°C and a baking time of 0.3 to 60 minutes, preferably a baking temperature of 80°C to 350°C and a baking time of 0.5 to 30 minutes, and more preferably a baking temperature of 90°C to 300°C and a baking time of 0.8 to 10 minutes.

[0145] 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 5,000 nm, 3,000 nm, or 2,000 nm, preferably 1,000 nm, more preferably 200 nm, and more preferably 50 nm.

[0146] <Step (X) of forming a protective film> Step (X) of forming a protective film from the protective film-forming composition of the present invention on the edge of a semiconductor manufacturing wafer (for example, the flat edge of the front surface, the peripheral edge surface (bevel portion, apex portion, etc.), and optionally the edge of the back surface) is performed at any time. In step (X), preferably, the protective film-forming composition is applied, and a predetermined area is exposed and developed. Step (X) may be performed before step (A), between step (A) and step (B), or after step (B) or step (C).

[0147] As mentioned above, in this specification, the surface of a substrate on which a device portion such as a resist film is provided is referred to as the front surface, and the opposite surface is referred to as the back surface. Furthermore, the edge of the front surface refers to a region typically 1 to 10 mm wide extending from the edge of the device portion provided on the substrate to the bevel portion (or apex portion), the bevel portion (or apex portion) refers to a curved region (the side surface of the wafer, corresponding to the above-mentioned "peripheral edge") connecting the flat edge of the front surface and the flat edge of the back surface, and the edge of the back surface refers to a region corresponding to the front surface edge of the back surface of the substrate.

[0148] First, a protective film-forming composition is applied to a semiconductor substrate. The method for applying the protective film-forming composition is not particularly limited, but known methods such as spin coating and spraying can be used. For example, when spin coating is used, the semiconductor substrate is rotated at a predetermined rotation speed, and the protective film-forming composition is supplied through a nozzle from above or near the front edge of the rotating disk-shaped substrate. Preferably, the composition is also supplied through a nozzle from near the peripheral edge and / or back edge of the substrate.

[0149] The spin-coating conditions can be selected appropriately and are not limited in any way, but typical conditions are as follows: Viscosity of the protective film-forming composition: about 100 cps or less Wafer rotation speed: When supplying the protective film-forming composition: 50 to 500 rpm When shaking off the dried film: 700 to 2,000 rpm Protective film thickness: 300 nm

[0150] Next, in one embodiment, the protective film-forming composition is exposed to light. The exposure can be performed by irradiating the protective film-forming composition with actinic rays such as ultraviolet light, visible light, or radiation (including i-line, KrF excimer laser, ArF excimer laser, EUV (extreme ultraviolet)), or EB (electron beam)) through a mask or without a mask. Note that soft baking (SB) may be performed before exposure, and post-exposure baking (PEB) may be performed after exposure and before development. The post-exposure baking temperature is preferably 50°C to 150°C, and the post-exposure baking time is preferably 1 minute to 10 minutes.

[0151] Next, the composition for forming a protective film after exposure is developed. The development can be carried out by removing the exposed portion of the composition for forming a protective film after exposure with a developer, and the development temperature is appropriately selected from 5°C to 50°C, and the development time is appropriately selected from 10 seconds to 300 seconds.

[0152] Examples of organic solvents contained in the developer include alcohol solvents, ether solvents, ketone solvents, amide solvents, ester solvents, and hydrocarbon solvents. The organic solvent in the developer is preferably an ester solvent, a ketone solvent, or a combination thereof. The developer may contain one organic solvent alone or two or more organic solvents. Examples of alcohol solvents include aliphatic monoalcohol solvents having 1 to 18 carbon atoms, such as 4-methyl-2-pentanol and n-hexanol; alicyclic monoalcohol solvents having 3 to 18 carbon atoms, such as cyclohexanol; and polyhydric alcohol partial ether solvents having 3 to 19 carbon atoms, such as propylene glycol monomethyl ether. Examples of ether solvents include dialkyl ether solvents, such as diethyl ether, dipropyl ether, dibutyl ether, dipentyl ether, diisoamyl ether, dihexyl ether, and diheptyl ether; cyclic ether solvents, such as tetrahydrofuran and tetrahydropyran; and aromatic ring-containing ether solvents, 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, di-isobutyl ketone, and trimethylnonanone; cyclic ketone solvents such as cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, and methylcyclohexanone; 2,4-pentanedione, acetonylacetone, and acetophenone. Examples of amide solvents include cyclic amide solvents such as N,N'-dimethylimidazolidinone and N-methylpyrrolidone; and chain amide solvents such as N-methylformamide, N,N-dimethylformamide, N,N-diethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, and N-methylpropionamide.Examples of ester-based solvents include monocarboxylic acid ester-based solvents such as n-butyl acetate and ethyl lactate; polyhydric alcohol carboxylate-based solvents such as propylene glycol acetate; polyhydric alcohol partial ether carboxylate-based solvents such as propylene glycol monomethyl ether acetate; polycarboxylic acid diester-based solvents such as diethyl oxalate; and carbonate-based solvents such as dimethyl carbonate and diethyl carbonate. Examples of hydrocarbon-based solvents include aliphatic hydrocarbon-based solvents having 5 to 12 carbon atoms such as n-pentane and n-hexane; and aromatic hydrocarbon-based solvents having 6 to 16 carbon atoms such as toluene and xylene. Among these, alcohol-based solvents, ester-based solvents, ketone-based solvents, ether-based solvents, and combinations thereof are preferred, and alcohol-based solvents, ester-based solvents, and combinations thereof are more preferred. As an alcohol-based solvent, propylene glycol monomethyl ether is preferred. As an ester-based solvent, propylene glycol monomethyl ether acetate is preferred. As a ketone-based solvent, cyclohexanone is preferred.

[0153] The lower limit of the content of the organic solvent in the developer 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 the organic solvent in the developer within the above range, the dissolution contrast between the exposed area and the unexposed area can be improved.

[0154] The developer may contain a nitrogen-containing compound.

[0155] The developer may also be used by adding alcohols or surfactants. These may each be blended in an amount of preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the developer. Examples of surfactants include ionic and nonionic fluorine-based surfactants and silicone-based surfactants.

[0156] Examples of development methods include a method in which the substrate is immersed in a tank filled with developer for a certain period of time (dip method), a method in which developer is piled up on the surface of the substrate by surface tension and left to stand for a certain period of time (puddle method), a method in which developer is sprayed onto the surface of the substrate (spray method), and a method in which developer is continuously dispensed onto a substrate rotating at a constant speed while a developer dispensing nozzle is scanned at a constant speed (dynamic dispense method).

[0157] Next, the protective film-forming composition after development is baked. By baking the pattern obtained after development, a desired pattern can be formed. The heating temperature in the heat treatment is usually 150°C or higher and 350°C or lower, preferably in the range of 200 to 300°C. The heat treatment time is the time required for the protective film-forming composition to harden, and is preferably approximately less than 30 minutes in consideration of productivity. The lower limit of the protective film thickness is preferably 1 nm, more preferably 3 nm. The upper limit of the protective film thickness is preferably 500 nm, more preferably 300 nm.

[0158] For example, step (X) is performed before step (A). Then, for example, in step (A), a resist film is formed on at least a portion of the protective film. In this case, step (Y) is performed to remove the resist film on the protective film. In step (Y), the resist film on the protective film can be removed with a remover. In this case, similar to step (X), it is preferable to apply the remover to the front edge, peripheral edge, and optionally the back edge of the semiconductor manufacturing wafer. Examples of resist removers include propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone, water, butyl acetate, a tetramethylammonium aqueous solution, or a mixture of these. Among these, propylene glycol monomethyl ether acetate and water are preferred from the viewpoint of resist film removability.

[0159] After step (X) or step (Y), step (Z) of removing the protective film is carried out. In step (Z), the protective film is preferably removed by ashing, or by treatment with hydrofluoric acid, an organic solvent, an alkaline developer, or a semiconductor cleaning solution. Thereafter, washing with any solvent or a conventional semiconductor cleaning solution is preferred.

[0160] Steps (X), (Y), and (Z) can be performed simultaneously with steps (A), (B), and (C), or at any time before or after each step. For example, when step (X) is included before step (A), step (Y) of removing 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). Furthermore, when step (X) is included between step (A) and step (B) or step (C), step (Z) of removing the protective film can also be performed between step (X) and step (B) or step (C).

[0161] <Step (B)> In step (B), a resist pattern is formed by irradiating the resist film with light or an electron beam and then developing it.

[0162] The resist film is irradiated with light or electron beams through a mask (reticle) for forming a predetermined pattern, and for example, i-line, KrF excimer laser, ArF excimer laser, EUV (extreme ultraviolet), or EB (electron beam) is used. A soft bake (SB) may be performed before exposure, or a post-exposure bake (PEB) may be performed after exposure and before development. The post-exposure bake temperature is preferably 50°C to 150°C, and the post-exposure bake time is preferably 1 minute to 10 minutes.

[0163] For example, an alkaline developer is used for development, with the development temperature being appropriately selected from 5°C to 50°C and the development time being selected from 10 seconds to 300 seconds. Examples of alkaline developers that can be used include aqueous solutions of alkalis such as inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous 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; alcohol amines such as dimethylethanolamine and triethanolamine; quaternary ammonium salts such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline; and cyclic amines such as pyrrole and piperidine. The base concentration of these aqueous solutions is not particularly limited, but can be, for example, 0.1 to 10% by mass.

[0164] Furthermore, an appropriate amount of an alcohol such as isopropyl alcohol or a nonionic surfactant can be added to the aqueous alkali solution. These can each be blended in an amount of preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the developer. Among these, preferred developers are quaternary ammonium salts, more preferably tetramethylammonium hydroxide and choline. Furthermore, surfactants can also be added to these developers.

[0165] Instead of using an alkaline developer, development can be carried out with a polyhydric alcohol solvent having 2 to 18 carbon atoms, such as 1,2-propylene glycol, or an organic solvent, such as butyl acetate, to develop the portions of the resist where the alkaline dissolution rate has not improved.

[0166] The semiconductor substrate that has been exposed and developed is then baked. The baking method is not particularly limited, but a proximity bake furnace that uses multiple substrate support pins to secure a gap between the substrate and a hot plate is preferably used. The baking temperature is typically 40°C to 300°C, preferably 200°C to 300°C, for 1 to 30 minutes, but may be set to 90°C or less if it is necessary to avoid damage to the resist pattern.

[0167] Baking may be performed on the semiconductor substrate after exposure but before development. The baking method and conditions are as described above, but if it is necessary to avoid damage to the resist pattern, the baking temperature may be set to 90° C. or less.

[0168] <Step (C)> In step (C), the semiconductor substrate is processed by etching using the resist pattern as a mask.

[0169] For example, the semiconductor substrate is processed by etching using the formed resist pattern as a mask. Alternatively, for example, the resist underlayer film is etched, preferably dry etched, using the formed resist pattern as a mask to form a patterned resist. In this case, if the inorganic film is formed on the surface of the semiconductor substrate used, the surface of the inorganic film is exposed, and if the inorganic film is not formed on the surface of the semiconductor substrate used, the surface of the semiconductor substrate is exposed. Then, the semiconductor substrate is processed using the patterned resist by a method known per se (such as a dry etching method). The etching for processing the semiconductor substrate may be a known method. For example, when the semiconductor substrate is a silicon substrate, in addition to a step of shaping the substrate by dry etching using a fluorine-based gas such as carbon tetrafluoride, it also includes a surface treatment step such as removing a silicon nitride film present on the surface of the semiconductor substrate with hot phosphoric acid.

[0170] Through the above steps, a semiconductor device can be manufactured.

[0171] (Method for manufacturing a wafer for semiconductor manufacturing) The method for manufacturing a wafer for semiconductor manufacturing of the present invention includes a step of applying the protective film-forming composition of the present invention to an edge of a wafer precursor and manufacturing a wafer whose edge is protected by the formed protective film. The protective film-forming composition is applied, for example, to the edge of the wafer precursor (e.g., the flat edge of the front surface, the peripheral edge surface (bevel portion, apex portion, etc.), and optionally the edge of the back surface).

[0172] The wafer precursor refers to a material obtained by subjecting a semiconductor substrate to at least one step in a method for manufacturing a semiconductor device, such as a material that has undergone a step of forming an inorganic film, a resist underlayer film, a resist film, or the like on a semiconductor substrate in the method for manufacturing a semiconductor device, and is not yet subjected to a step of forming a resist pattern by irradiating the resist film with light or an electron beam and then developing it.

[0173] In one embodiment, the protective film-forming composition of the present invention is applied by spin coating to the edge (e.g., the flat edge of the front surface, the peripheral edge surface (bevel portion, apex portion, etc.), and optionally the back surface edge) of a wafer precursor obtained through one or more steps of a semiconductor device manufacturing process.

[0174] The semiconductor substrate may then be baked. In this case, the baking method is not particularly limited, but for example, a proximity bake furnace in which a gap is secured between the substrate and a hot plate using multiple substrate support pins is preferably used. The baking temperature is typically 40°C to 300°C, preferably 200 to 300°C, for 1 to 30 minutes. After applying the protective film-forming composition, the end surface of the protective film may be subjected to known treatments used in semiconductor manufacturing processes, such as edge bead removal and back rinsing.

[0175] (Semiconductor manufacturing wafer) The semiconductor manufacturing wafer of the present invention is a semiconductor manufacturing wafer whose wafer edge is protected, and is formed by applying the protective film-forming composition of the present invention to the wafer edge.

[0176] The present invention will be explained in more detail below with reference to synthesis examples and examples, but the present invention is not limited to the following examples.

[0177] In the examples, the apparatus and conditions used to analyze the physical properties of the samples are as follows:

[0178] (1) Molecular Weight Measurement The weight-average molecular weight (Mw) used in the present invention is a result of measurement by gel permeation chromatography (hereinafter abbreviated as GPC in this specification). The measurement was performed using a GPC apparatus (trade name HLC-8320GPC, manufactured by Tosoh Corporation), GPC columns (TSKgel Super-Multipore HZ-N (two columns)), a column temperature of 40°C, an eluent (elution solvent) of tetrahydrofuran, a flow rate (flow rate) of 0.35 mL / min, and a standard sample of polystyrene (manufactured by Sigma-Aldrich).

[0179] [1] Polymer Synthesis <Synthesis Example 1> 60.00 g of propylene glycol monomethyl ether acetate (PGMEA) was added to 30.85 g (107.12 mmol) of epoxy novolac resin (product name: NC-3000-H, epoxy equivalent: 288 g / eq., manufactured by Nippon Kayaku Co., Ltd.), 7.72 g (107.12 mmol) of acrylic acid, 1.36 g (4.02 mmol) of tetrabutylphosphonium bromide, and 0.07 g (0.54 mmol) of 4-methoxyphenol, and the mixture was heated and stirred at 100°C in air for 18 hours. The resulting reaction product corresponded to the following formula (P-1), and its weight average molecular weight (Mw) measured by GPC was 2,536. The carbon content of the structural unit represented by formula (P-1) can be determined as follows. Chemical formula per structural unit: C ２７ H ２８ O ４ Molecular weight per structural unit: 416.52 (proportion of atomic weight of carbon atoms: 77.86, proportion of atomic weight of hydrogen atoms: 6.78, proportion of atomic weight of oxygen atoms: 15.36) Therefore, the carbon content in formula (P-1) is approximately 78%.

[0180]

[0181] Synthesis Example 2 60.00 g of propylene glycol monomethyl ether acetate (PGMEA) was added to 28.40 g (135.87 mmol) of epoxy novolac resin (product name: NC-3500, epoxy equivalent: 209 g / eq., manufactured by Nippon Kayaku Co., Ltd.), 9.80 g (135.87 mmol) of acrylic acid, 1.73 g (5.10 mmol) of tetrabutylphosphonium bromide, and 0.08 g (0.68 mmol) of 4-methoxyphenol, and the mixture was heated and stirred in air at 100° C. for 18 hours. The resulting reaction product corresponded to the following formula (P-2), and its weight average molecular weight (Mw) measured by GPC was 3,111.

[0182]

[0183] Synthesis Example 3 60.00 g of propylene glycol monomethyl ether acetate (PGMEA) was added to 29.13 g (127.22 mmol) of epoxy novolac resin (product name: NC-7000H, epoxy equivalent: 229 g / eq., manufactured by Nippon Kayaku Co., Ltd.), 9.17 g (127.22 mmol) of acrylic acid, 1.62 g (4.77 mmol) of tetrabutylphosphonium bromide, and 0.08 g (0.64 mmol) of 4-methoxyphenol, and the mixture was heated and stirred in air at 100° C. for 18 hours. The resulting reaction product corresponded to the following formula (P-3), and its weight average molecular weight (Mw) as determined by GPC was 1,316.

[0184]

[0185] Comparative Synthesis Example 1 60.00 g of propylene glycol monomethyl ether acetate (PGMEA) was added to 27.69 g (144.19 mmol) of epoxy novolac resin (product name: EPPN-201, epoxy equivalent: 192 g / eq., manufactured by Nippon Kayaku Co., Ltd.), 10.39 g (144.19 mmol) of acrylic acid, 1.83 g (5.41 mmol) of tetrabutylphosphonium bromide, and 0.09 g (0.72 mmol) of 4-methoxyphenol, and the mixture was heated and stirred in air at 100°C for 18 hours. The resulting reaction product corresponded to the following formula (P-4), and its weight average molecular weight (Mw) measured by GPC was 8,609. The carbon content of the structural unit represented by formula (P-4) can be determined as follows. Chemical formula per structural unit: C １４ H １８ O ４ Molecular weight per structural unit: 250.29 (proportion of atomic weight of carbon atoms: 67.18, proportion of atomic weight of hydrogen atoms: 7.25, proportion of atomic weight of oxygen atoms: 25.57) Therefore, the carbon content in formula (P-4) is approximately 67%.

[0186]

[0187] Comparative Synthesis Example 2 60.00 g of propylene glycol monomethyl ether acetate (PGMEA) was added to 28.81 g (130.97 mmol) of epoxy novolac resin (product name: EOCN-104S, epoxy equivalent: 220 g / eq., manufactured by Nippon Kayaku Co., Ltd.), 9.44 g (130.97 mmol) of acrylic acid, 1.67 g (4.91 mmol) of tetrabutylphosphonium bromide, and 0.08 g (0.65 mmol) of 4-methoxyphenol, and the mixture was heated and stirred in air at 100° C. for 18 hours. The resulting reaction product corresponded to the following formula (P-5), and its weight average molecular weight (Mw) as determined by GPC was 5,806.

[0188]

[0189] Comparative Synthesis Example 3 35.00 g of propylene glycol monomethyl ether acetate (PGMEA) was added to 7.26 g (32.94 mmol) of epoxy novolac resin (product name: EOCN-104S, epoxy equivalent: 220 g / eq., manufactured by Nippon Kayaku Co., Ltd.), 7.32 g (32.94 mmol) of 9-anthracenecarboxylic acid, and 0.42 g (1.24 mmol) of tetrabutylphosphonium bromide, and the mixture was heated and stirred in air at 100° C. for 21 hours. The resulting reaction product corresponded to the following formula (P-6), and its weight average molecular weight (Mw) as determined by GPC was 4,998.

[0190]

[0191] [2] Preparation of protective film-forming composition Example 1 9.31 g of a solution (solid content: 31.22 wt %) containing the reaction product obtained in Synthesis Example 1, 0.29 g of IRGACURE OXE01 (manufactured by BASF Japan Ltd.) as a photoradical initiator, 0.04 g of IRGANOX 3114 (manufactured by BASF Japan Ltd.) as a stabilizer, 0.01 g of Megafac R-40 (manufactured by DIC Corporation) as a surfactant, and 15.35 g of propylene glycol monomethyl ether acetate as a solvent were mixed and dissolved, and then filtered using a polytetrafluoroethylene filter having a pore size of 0.2 μm, to prepare a protective film-forming composition.

[0192] Example 2 9.31 g of a solution containing the reaction product obtained in Synthesis Example 1 (solid content concentration: 31.22 wt %), 0.29 g of Omnirad 184 (manufactured by IGM Resins) as a photoradical initiator, 0.04 g of IRGANOX 3114 (manufactured by BASF Japan Ltd.) as a stabilizer, 0.01 g of Megafac R-40 (manufactured by DIC Corporation) as a surfactant, and 15.35 g of propylene glycol monomethyl ether acetate as a solvent were mixed and dissolved, and then filtered using a polytetrafluoroethylene filter having a pore size of 0.2 μm, to prepare a protective film-forming composition.

[0193] Example 3 9.44 g of the solution containing the reaction product obtained in Synthesis Example 2 (solid content concentration: 30.78 wt %), 0.29 g of IRGACURE OXE01 (manufactured by BASF Japan Ltd.) as a photoradical initiator, 0.04 g of IRGANOX 3114 (manufactured by BASF Japan Ltd.) as a stabilizer, 0.01 g of Megafac R-40 (manufactured by DIC Corporation) as a surfactant, and 15.21 g of propylene glycol monomethyl ether acetate as a solvent were mixed and dissolved, and then filtered using a polytetrafluoroethylene filter having a pore size of 0.2 μm, to prepare a protective film-forming composition.

[0194] Example 4 9.48 g of the solution containing the reaction product obtained in Synthesis Example 3 (solid content concentration: 30.68 wt %), 0.29 g of IRGACURE OXE01 (manufactured by BASF Japan Ltd.) as a photoradical initiator, 0.04 g of IRGANOX 3114 (manufactured by BASF Japan Ltd.) as a stabilizer, 0.01 g of Megafac R-40 (manufactured by DIC Corporation) as a surfactant, and 15.18 g of propylene glycol monomethyl ether acetate as a solvent were mixed and dissolved, and then filtered using a polytetrafluoroethylene filter having a pore size of 0.2 μm, to prepare a protective film-forming composition.

[0195] Comparative Example 1 6.41 g of a solution (solids concentration: 30.72 wt %) containing the reaction product obtained in Comparative Synthesis Example 1, 0.20 g of IRGACURE OXE01 (manufactured by BASF Japan Ltd.) as a photoradical initiator, 0.03 g of IRGANOX 3114 (manufactured by BASF Japan Ltd.) as a stabilizer, 0.01 g of Megafac R-40 (manufactured by DIC Corporation) as a surfactant, and 18.36 g of propylene glycol monomethyl ether acetate as a solvent were mixed and dissolved, and then filtered using a polytetrafluoroethylene filter having a pore size of 0.2 μm, to prepare a protective film-forming composition.

[0196] Comparative Example 2 6.35 g of a solution (solids concentration: 30.97% by weight) containing the reaction product obtained in Comparative Synthesis Example 2, 0.20 g of IRGACURE OXE01 (manufactured by BASF Japan Ltd.) as a photoradical initiator, 0.03 g of IRGANOX 3114 (manufactured by BASF Japan Ltd.) as a stabilizer, 0.01 g of Megafac R-40 (manufactured by DIC Corporation) as a surfactant, and 18.41 g of propylene glycol monomethyl ether acetate as a solvent were mixed and dissolved, and then filtered using a polytetrafluoroethylene filter having a pore size of 0.2 μm, to prepare a protective film-forming composition.

[0197] Comparative Example 3 8.17 g of the solution containing the reaction product obtained in Comparative Synthesis Example 3 (solid content concentration: 24.40 wt %), 0.18 g of IRGACURE OXE01 (manufactured by BASF Japan Ltd.) as a photoradical initiator, 0.03 g of IRGANOX 3114 (manufactured by BASF Japan Ltd.) as a stabilizer, 0.01 g of Megafac R-40 (manufactured by DIC Corporation) as a surfactant, and 12.46 g of propylene glycol monomethyl ether acetate as a solvent were mixed and dissolved, and then filtered using a polytetrafluoroethylene filter having a pore size of 0.2 μm, to prepare a protective film-forming composition.

[0198] [3] Evaluation of Photocurability (Photosensitivity) The protective film-forming compositions prepared in Examples 1 to 4 and Comparative Examples 1 to 3 were applied to a 12-inch silicon wafer using a spin coater (LITHIUS PRO, manufactured by Tokyo Electron Ltd.) to form a protective film with a thickness of 300 nm. Next, a wafer edge exposure module (WEE, manufactured by Tokyo Electron Ltd.) was used to apply ultraviolet light with a wavelength of 254 nm at 300 mJ / cm. ２ After that, the wafer edge (edge) was exposed to an exposure dose of 300 mJ / cm , and the wafer was developed for 15 seconds using an organic solvent as a developer, for example, a mixed solvent of propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate (product name: OK73 Thinner, manufactured by Tokyo Ohka Kogyo Co., Ltd.), and baked at 95°C for 60 seconds to remove the unexposed portion, thereby forming an exposure pattern on the wafer edge. ２) was measured using an interference film thickness meter (Lambda Ace VM-3210, manufactured by SCREEN Corporation) to calculate the ratio of the remaining film thickness in the unexposed and exposed areas (remaining film ratio (%)) using the following formula: Remaining film ratio (%) = [(film thickness in the unexposed area) or (film thickness in the exposed area)] / (film thickness immediately after film formation) × 100 In other words, if the remaining film ratio is 80%, it means that 80% of the film thickness immediately after film formation remains after development without being developed. The measurement results of the remaining film ratio after development are shown in Table 1.

[0199] [4] Calculation of Carbon Content For the reaction products of Synthesis Examples 1 to 3 and Comparative Synthesis Examples 1 to 3 used in Examples 1 to 4 and Comparative Examples 1 to 3, the carbon content per structural unit was calculated using the following formula: Carbon content (%) = (molecular weight of carbon per structural unit) / (molecular weight per structural unit) × 100 For example, in the case of hydroxystyrene (PHS), the molecular weight of carbon per structural unit is 96.08 and the molecular weight per structural unit is 120.15, so the carbon content is 80%. The calculation results of the carbon content per structural unit of the polymer are shown in Table 1.

[0200] [5] Evaluation of dry etching selectivity The protective film-forming compositions prepared in Examples 1 to 4 and Comparative Examples 1 to 3 were applied to silicon wafers and baked at 90°C for 60 seconds to form protective films with a thickness of 300 nm. Next, a dry etching apparatus (RIE-10NR, manufactured by Samco Corporation) was used to form CF ４ The dry etching rate for each gas was measured and compared with the dry etching rate of Comparative Example 1 to evaluate the dry etching selectivity. High dry etching resistance means a slow dry etching rate, i.e., a small dry etching selectivity. The results of the dry etching selectivity are shown in Table 1.

[0201] As can be seen from the results in Table 1, for the protective film-forming compositions of Examples 1 to 4 and Comparative Examples 1 and 2, the protective film in the unexposed areas was completely removed by organic solvent development, but the protective film in the exposed areas was not removed. That is, for the protective film-forming compositions of Examples 1 to 4 and Comparative Examples 1 and 2, the protective film exhibited photocurability (photosensitivity) upon exposure, and the protective film in the unexposed areas could be removed by development, allowing a protective film to be selectively formed only on the wafer edge (edge). Furthermore, the protective film-forming compositions of Examples 1 to 4 had lower dry etching selectivity than Comparative Examples 1 and 2. This means that the protective film-forming compositions of Examples 1 to 4 had higher etching resistance than Comparative Examples 1 and 2. On the other hand, the protective film-forming composition of Comparative Example 3, while having higher dry etching resistance than Comparative Examples 1 and 2, did not exhibit photocurability (photosensitivity) because not only the protective film in the unexposed areas but also the protective film in the exposed areas was removed by organic development.

Claims

1. A composition for forming a wafer edge protective film for semiconductor manufacturing, comprising a polymer or compound containing a coincident group and having a carbon content of 70% or more, and a solvent.

2. The composition for forming a wafer edge protective film for semiconductor manufacturing according to claim 1, wherein the polymerizable group is a photopolymerizable group or a thermopolymerizable group.

3. The protective film forming composition according to claim 2, wherein the photopolymerizable group or thermopolymerizable group is selected from the group consisting of an acrylic group, a methacrylic group, an acrylamide group, a methacrylamide group, a vinyl group, and an allyl group.

4. The composition for forming a wafer edge protective film for semiconductor manufacturing according to claim 1, which is photosensitive.

5. A protective film which is a cured product of a coating film composed of the composition for forming a wafer edge protective film for semiconductor manufacturing according to any one of claims 1 to 4.

6. The protective film according to claim 5, which is cured by irradiation with light having a wavelength of 170 to 800 nm.

7. The protective film according to claim 6, which can form a negative pattern with an organic solvent.

8. A semiconductor manufacturing wafer having its edge protected, wherein a protective film is formed by applying the composition for forming a wafer edge protective film for semiconductor manufacturing according to any one of claims 1 to 4 to the edge of a wafer precursor.

9. 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 an electron beam and then developing; (C) a step of processing the semiconductor substrate by etching using the resist pattern as a mask, and further comprising a step (X) of forming a protective film using the composition for forming a wafer edge protective film for semiconductor manufacturing according to any one of claims 1 to 4 at the edge of the semiconductor manufacturing wafer.

10. The method for manufacturing a semiconductor device according to claim 9, wherein the step (X) is performed before the step (A).

11. The method for manufacturing a semiconductor device according to claim 9, wherein the step (X) is performed between the step (A) and the step (B).

12. The method for manufacturing a semiconductor device according to claim 9, wherein the step (X) is performed after the step (B) or the step (C).

13. The step (X) is performed before the step (A). In the step (A), the resist film is formed on at least a part of the protective film, and the method for manufacturing a semiconductor device according to claim 9 includes a step (Y) of removing the resist film on the portion of the protective film.

14. The method for manufacturing a semiconductor device according to claim 9 includes a step (Z) of removing the protective film.

15. The method for manufacturing a semiconductor device according to claim 13 includes a step (Z) of removing the protective film after the step (Y).

16. The composition for forming an end protective film of a semiconductor manufacturing wafer is photosensitive, and the formation of the protective film in the step (X) is performed by applying the composition for forming an end protective film of a semiconductor manufacturing wafer, exposing a predetermined region, and developing the exposed region. The method for manufacturing a semiconductor device according to claim 9.

17. The removal of the protective film in the step (Z) is performed by ashing or by treatment with hydrofluoric acid, an organic solvent, an alkaline developer, or a semiconductor cleaning solution. The method for manufacturing a semiconductor device according to claim 14.

18. The removal of the protective film in the step (Z) is performed by ashing or by treatment with hydrofluoric acid, an organic solvent, an alkaline developer, or a semiconductor cleaning solution. The method for manufacturing a semiconductor device according to claim 15.

19. A method for manufacturing a semiconductor manufacturing wafer, including a step of applying the composition for forming an end protective film of a semiconductor manufacturing wafer according to any one of claims 1 to 4 to an end of a wafer precursor and manufacturing a wafer having an end protected by the formed protective film. The method for manufacturing a semiconductor manufacturing wafer.

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