Composition for forming protective film on wafer edge for semiconductor manufacturing

Abstract

This wafer edge protective film-forming composition for semiconductor manufacturing comprises a solvent and a cross-linkable group-containing polymer or compound, wherein the solvent includes a first solvent and a second solvent; and when the evaporation rate of n-butyl acetate is assumed to be 1, the evaporation rate of the first solvent is 0.10 or more, and the evaporation rate of the second solvent is 0.05 or less.

Description

[Technical field]

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

[0002] In the manufacture of semiconductor devices, as the manufacturing process becomes more complicated, a method of applying a chemical solution containing a metal to a wafer is being considered for the purpose of, for example, improving the etching selectivity. Furthermore, for example, in the case of performing exposure using extreme ultraviolet (EUV), the resolution of the resist pattern is increased, and since the resist has high etching resistance, it is being considered to form a resist film using a resist containing an inorganic metal. Meanwhile, adhesion of metal to unintended portions of a wafer in the manufacturing process of a semiconductor device greatly affects the electrical characteristics of the semiconductor device. However, when forming a coating film containing a metal as described above, there is a concern that the chemical solution supplied to the surface of the wafer will wrap around the peripheral edge and backside edge of the wafer, and the coating film will be formed on these unintended peripheral edge and backside edge portions, resulting in metal contamination of these portions. In addition, when the contaminated portion of the wafer comes into contact with a wafer processing device such as an exposure device or an etching device, or a wafer transport mechanism, the wafers transported and processed after the wafer will also be metal contaminated, that is, cross contamination may occur.

[0003] A technology has been disclosed that, when forming a coating film on the surface of a substrate, can form the coating film so that the peripheral edge surface and the peripheral edge portion of the back surface side of the substrate do not come into contact with the coating film (Patent Document 1).

[0004] A method for manufacturing a semiconductor device in which peeling of a film from a bevel portion of a substrate is suppressed has been disclosed (Patent Document 2). [Prior art documents] [Patent documents]

[0005] [Patent Document 1] JP 2017-098333 A [Patent Document 2] JP 2011-228340 A Summary of the Invention [Problem to be solved by the invention]

[0006] The problem that the present invention aims to solve is to provide a protective film-forming composition that can form a protective film in good condition without abnormal shapes (partial bulges or depressions) on the surface edge and bevel portions of a substrate (wafer) for semiconductor manufacturing by a simple method of application in the manufacture of semiconductor devices; a protective film formed from the protective film-forming composition; a wafer for semiconductor manufacturing manufactured using the protective film; and a method for manufacturing the wafer for semiconductor manufacturing and the semiconductor device. [Means for solving the problem]

[0007] The present invention encompasses the following: [1] A polymer or compound having a crosslinkable group and a solvent, the solvent comprises a first solvent and a second solvent; When the evaporation rate of n-butyl acetate is taken as 1, the evaporation rate of the first solvent is 0.10 or more, and the evaporation rate of the second solvent is 0.05 or less. A composition for forming a protective film on a wafer edge in semiconductor manufacturing. [2] The composition for forming a wafer edge protection film for semiconductor manufacturing according to [1], wherein a mass ratio (S1:S2) of the first solvent (S1) to the second solvent (S2) is 50:50 to 95:5. [3] The composition for forming a wafer edge protection film for semiconductor manufacturing according to [1] or [2], wherein the difference (V1-V2) between the evaporation rate (V1) of the first solvent and the evaporation rate (V2) of the second solvent is 0.10 or more. [4] The constituent elements of the first solvent are carbon, oxygen, and hydrogen; The constituent elements of the second solvent are carbon, oxygen, and hydrogen. The composition for forming a wafer edge protection film for semiconductor manufacturing according to any one of [1] to [3]. [5] The composition for forming a wafer edge protection film for semiconductor manufacturing according to any one of [1] to [4], wherein the content of the solvent is 70% by mass to 99% by mass. [6] A composition for forming a wafer edge protection film for semiconductor manufacturing according to any one of [1] to [5], having a viscosity of 100 cps or less at 25°C. [7] The composition for forming a wafer edge protection film for semiconductor manufacturing according to any one of [1] to [6], which is photosensitive. [8] The composition for forming a wafer edge protection film for semiconductor manufacturing according to any one of [1] to [7], wherein the crosslinkable group is selected from the group consisting of an epoxy group, a (meth)acrylic group, a vinyl group, a carboxyl group, a thiol group, a silanol group, a cinnamoyl group, and a hydroxyl group. [9] A protective film which is a cured product of a coating film made of the composition for forming a wafer edge protective film for semiconductor manufacturing according to any one of [1] to [8].

[10] The protective film according to [9], having a thickness of 1 to 10,000 nm.

[11] The protective film according to [9] or

[10] , which is a protective film for preventing metal contamination of the edge and bevel of the wafer surface.

[12] The protective film according to any one of [9] to

[11] , which is cured by exposure to light having a wavelength of 170 to 800 nm.

[13] A wafer for semiconductor manufacturing, in which the wafer surface edge and bevel portion are protected, the wafer for semiconductor manufacturing having a protective film formed by applying a composition for forming a wafer edge protection film for semiconductor manufacturing described in any one of [1] to [8] to the surface edge and bevel portion of a wafer precursor.

[14] (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; (C) etching a semiconductor substrate using the resist pattern as a mask; A method for manufacturing a semiconductor device comprising: The method includes a step (X) of forming a protective film on a front surface edge, a bevel portion, and optionally a back surface edge of a semiconductor manufacturing wafer using a composition for forming a protective film for a semiconductor manufacturing wafer according to any one of [1] to [8]. A method for manufacturing a semiconductor device.

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

[14] , wherein the step (X) is carried out before the step (A).

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

[14] , wherein the step (X) is carried out between the step (A) and the step (B).

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

[14] , wherein the step (X) is carried out after the step (B) or the step (C).

[18] The step (X) is carried out before the step (A), In the step (A), the resist film is formed on at least a portion of the protective film, A step (Y) of removing the resist film on the protective film; A method for manufacturing a semiconductor device according to

[14] .

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

[14] to

[18] , further comprising a step (Z) of removing the protective film.

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

[18] , further comprising the step (Z) of removing the protective film after the step (Y).

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

[14] to

[20] , wherein the resist film contains a metal.

[22] The composition for forming a wafer edge protection film for semiconductor manufacturing is photosensitive, The method for manufacturing a semiconductor device according to any one of

[14] to

[21] , wherein the formation of the protective film in the step (X) is carried out by applying the composition for forming a protective film for a wafer edge for semiconductor manufacturing, exposing a predetermined area to light, and developing the same.

[23] The method for manufacturing a semiconductor device described in any one of

[14] to

[22] , wherein the formation of the protective film in the step (X) is carried out by spin-coating the composition for forming a wafer edge protective film for semiconductor manufacturing.

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

[19] or

[20] , wherein 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 liquid.

[25] A method for manufacturing a semiconductor manufacturing wafer, comprising: A step of applying a composition for forming a wafer edge protection film for semiconductor production according to any one of [1] to [8] to an edge of a wafer precursor, and producing a wafer in which a surface edge and a bevel portion are protected by the formed protective film; A method for manufacturing a wafer for semiconductor manufacturing, comprising: Effect of the Invention

[0008] According to the present invention, in the manufacture of semiconductor devices, a protective film having good film quality and free of abnormal shapes (partial swelling or depression) can be formed on the surface edge and bevel of a substrate (wafer) for manufacturing semiconductor devices by a simple coating method. This makes it possible to prevent cross-contamination due to metal contamination in the subsequent semiconductor device manufacturing process, and improve the yield of non-defective semiconductor manufacturing equipment. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] (Composition for forming a protective film on a wafer edge for semiconductor manufacturing) The composition for forming a protective film on a wafer edge for semiconductor manufacturing of the present invention (hereinafter, sometimes referred to as "composition for forming a protective film") is a composition for forming a protective film used to protect the surface edge and bevel portion of a wafer for semiconductor manufacturing. The composition for forming a protective film contains a polymer or compound having a crosslinkable group and a solvent.

[0010] <Solvent> The solvent includes a first solvent and a second solvent. Here, the evaporation rate used in the present invention is the evaporation rate obtained by ASTM D 3539. However, the evaporation rate value used in the present invention is a relative value to the evaporation rate of n-butyl acetate. That is, the evaporation rate value used in the present invention is the value obtained by dividing the evaporation rate of the solvent by the evaporation rate of n-butyl acetate. When the evaporation rate of n-butyl acetate is taken as 1, the evaporation rate of the first solvent is 0.10 or more, and the evaporation rate of the second solvent is 0.05 or less.

[0011] The present inventors have conducted extensive research to form a protective film with good film quality on the edges (surface edges and bevel portions) of wafers used in semiconductor manufacturing using a simple method of coating. When various solvents were tried as the solvent for the composition for forming a protective film, it was found that the evaporation rate had an effect on the coverage of the surface edge and the film shape of the bevel portion. For example, it was found that when a solvent with a high evaporation rate (easy to evaporate) is used alone as the solvent for the protective film-forming composition, the coverage of the surface edge is good, but the film shape of the bevel portion is poor (for example, partial swelling or depression occurs). On the other hand, it was found that when a solvent with a low evaporation rate (difficult to evaporate) is used alone, the film shape of the bevel portion is good, but the coverage of the surface edge is poor (film thickness becomes thin). Furthermore, it was difficult to achieve both by using a solvent with an intermediate evaporation rate alone. That is, it was found that it is difficult to improve both the coverage of the surface edge and the film shape of the bevel portion with only one type of solvent. Therefore, the inventors discovered that by combining two or more solvents with different evaporation rates, a protective film with good film quality can be formed by a simple method of application to the edge (surface edge and bevel) of a wafer used in semiconductor manufacturing, which led to the completion of the present invention. The film shape of the edge (surface edge and bevel) of the wafer for semiconductor manufacturing can be observed, for example, with a scanning electron microscope (magnification, for example, 20 to 400x, 30 to 200x, 40 to 100x, 50x, 80x, 100x). The number of abnormal shapes is 10 or less, preferably 5 or less, more preferably 3 or less, even more preferably 1 or less, and most preferably no abnormal shapes are observed (zero (zero) abnormalities) in the field of view observed with the scanning electron microscope.

[0012] The first solvent and the second solvent are organic solvents.

[0013] The evaporation rate of the first solvent is 0.10 or more, preferably from 0.10 to 0.80, more preferably from 0.20 to 0.60, and particularly preferably from 0.30 to 0.50.

[0014] The evaporation rate of the second solvent is 0.05 or less, preferably 0.04 or less, and more preferably 0.03 or less.

[0015] The difference (V1-V2) between the evaporation rate (V1) of the first solvent and the evaporation rate (V2) of the second solvent is not particularly limited, but from the viewpoint of obtaining the effects of the present invention, it is preferably 0.10 or more, more preferably 0.15 or more, and particularly preferably 0.20 or more. Moreover, the difference (V1-V2) is preferably 0.70 or less, more preferably 0.60 or less, and particularly preferably 0.50 or less.

[0016] The mass ratio (S1:S2) of the first solvent (S1) to the second solvent (S2) is not particularly limited, but from the viewpoint of suitably obtaining the effects of the present invention, it is preferably 50:50 to 95:5, more preferably 60:40 to 93:7, and particularly preferably 70:30 to 90:10.

[0017] The constituent elements of the first solvent are, for example, carbon, oxygen, and hydrogen. The constituent elements of the second solvent are, for example, carbon, oxygen, and hydrogen.

[0018] The first solvent preferably does not contain nitrogen atoms and halogen atoms as constituent elements. The second solvent preferably does not contain nitrogen atoms and halogen atoms as constituent elements.

[0019] The first solvent includes, for example, at least one of an ether bond, an ester bond, and a carbonyl group. The second solvent includes, for example, at least one of an ether bond, an ester bond, and a carbonyl group.

[0020] Here, an example of the evaporation rate (the evaporation rate of n-butyl acetate is taken as 1) is shown below.

[0021] [Table 1]

[0022] The solvent may include an organic solvent other than the first solvent and the second solvent.

[0023] The total proportion of the first solvent and the second solvent in the solvent is not particularly limited, but is preferably 50% by mass to 100% by mass, more preferably 75% by mass to 100% by mass, and particularly preferably 90% by mass to 100% by mass.

[0024] The content of the solvent in the composition for forming a protective film is not particularly limited, but is preferably 70% 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.

[0025] The total content of the first solvent and the second solvent in the composition for forming a protective film is not particularly limited, but is preferably 50% by mass to 99% by mass, more preferably 60% by mass to 98% by mass, and particularly preferably 75% by mass to 95% by mass.

[0026] <Polymer or compound having crosslinkable group> The crosslinkable group means a group capable of forming a crosslinked structure by the action of light, an electron beam, other electromagnetic waves, radicals, acid, heat, water, oxygen, etc. Examples of the crosslinkable group include, but are not limited to, an epoxy group, a (meth)acrylic group, a vinyl group, a carboxyl group, a thiol group, a silanol group, a cinnamoyl group, a hydroxyl group (including a phenolic hydroxyl group), etc. In this specification, "polymer" and "compound" do not necessarily mean separate substances, and a substance containing a polymer may be referred to as a "compound". The protective film (cured film) using the above "polymer" and "compound" exhibits solubility in a developer such that, for example, in an evaluation similar to "(5) Evaluation of curability after exposure" in the Examples described later, the remaining film ratio of the cured film in the exposed portion is 80% or more, preferably 90% or more, relative to the film in the unexposed portion.

[0027] Examples of the polymer or compound having a crosslinkable group include, but are not limited to, the following. Epoxy (meth)acrylates (e.g., reaction products of glycidyl ethers of cresol novolac resins with (meth)acrylic acid), Cinnamic acid grafted epoxy novolac, Phenoplasts, which are thermosetting materials obtained by polycondensation of phenols and aldehydes with the elimination of water and the formation of three-dimensional networks; For example, melamine resins such as trimethylol melamine and hexamethylol melamine, urea resins such as dimethylol propylene urea, dimethylol ethylene urea, and dimethylol hydroxyl urea, and amino blast resins such as dimethylol uron resin, (Blocked) isocyanates, Vinyl ethers, ·Polysiloxane resin with (meth)acrylic groups Epoxy resin.

[0028] Here, an example of a polymer or compound having a crosslinkable group will be given. An example of the polymer or compound having a crosslinkable group is a polymer having a structural unit represented by the following formula (1-1). [ka] In formula (1-1), Ar represents a benzene ring, a naphthalene ring, or an anthracene ring; 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 an alkylene group having 1 to 10 carbon atoms, n2 represents 1 or 2, A represents a group having a (meth)acryloyloxy 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.

[0029] 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, a 1-ethyl-n-propyl group, Cyclopentyl, 1-methylcyclobutyl, 2-methylcyclobutyl, 3-methylcyclobutyl, 1,2-dimethylcyclopropyl, 2,3-dimethylcyclopropyl, 1-ethylcyclopropyl, 2-ethylcyclopropyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n-pentyl, 4-methyl-n-pentyl, 1,1-dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1,3-dimethyl-n-butyl, 2,2- Dimethyl-n-butyl, 2,3-dimethyl-n-butyl, 3,3-dimethyl-n-butyl, 1-ethyl-n-butyl, 2-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl, 1,2,2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl, 1-ethyl-2-methyl-n-propyl, cyclohexyl, 1-methyl-cyclopentyl, 2-methyl-cyclopentyl, 3-methyl-cyclopentyl, 1-ethyl-cyclobutyl, 2-ethyl-cyclobutyl, 3 -ethyl-cyclobutyl, 1,2-dimethyl-cyclobutyl, 1,3-dimethyl-cyclobutyl, 2,2-dimethyl-cyclobutyl, 2,3-dimethyl-cyclobutyl, 2,4-dimethyl-cyclobutyl, 3,3-dimethyl-cyclobutyl, 1-n-propyl-cyclopropyl, 2-n-propyl-cyclopropyl, 1-i-propyl-cyclopropyl, 2-i-propyl-cyclopropyl, 1,2,2-trimethyl-cyclopropyl, 1,2,3-trimethyl-cyclopropyl, 2,2,Examples of the cyclopropyl group include 3-trimethyl-cyclopropyl group, 1-ethyl-2-methyl-cyclopropyl group, 2-ethyl-1-methyl-cyclopropyl group, 2-ethyl-2-methyl-cyclopropyl group, 2-ethyl-3-methyl-cyclopropyl group, decyl group, methoxy group, ethoxy group, methoxymethyl group, ethoxymethyl group, methoxyethyl group, ethoxyethyl group, hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, methylamino group, dimethylamino group, diethylamino group, aminomethyl group, 1-aminoethyl group, 2-aminoethyl group, methylthio group, ethylthio group, mercaptomethyl group, 1-mercaptoethyl group, and 2-mercaptoethyl group.

[0030] Examples of the alkylene group having 1 to 10 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-methyl-cyclopropylene group, a 2-methyl-cyclopropylene 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, 1-methyl-cyclobutylene, 2-methyl-cyclobutylene, 3-methyl-cyclobutylene, 1,2-dimethyl-cyclopropylene, 2,3-dimethyl-cyclopropylene, 1-ethyl-cyclopropylene, 2-ethyl-cyclopropylene, n-hexylene, 1-methyl-n-pentylene, 2-methyl-n-pentylene, 3-methyl-n-pentylene, 4-methyl-n-pentylene, 1,1-dimethyl-n-butylene, 1,2-dimethyl-n-butylene, 1,3-dimethyl-n-butylene, 2,2-dimethyl-n-butylene, 2,3-dimethyl-n-butylene, 3,3-dimethyl-n-butylene, 1-ethyl-n-butylene, 2-ethyl-n-butylene, 1,1,2-trimethyl-n-propylene, 1,2,2-trimethyl-n-propylene, 1-ethyl-1-methyl-n-propylene, 1-ethyl-2-methyl-n-propylene, cyclohexylene, 1-methyl-cyclopentylene, 2-methyl-cyclopentylene, 3-methyl-cyclopentylene, 1-ethyl-cyclobutylene, 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 the cyclopropylene group 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.

[0031] R 1 An example of the alkyl group having 1 to 10 carbon atoms and substituted or interrupted by a heteroatom in the formula (I) is an alkoxy group having 1 to 10 carbon atoms.

[0032] 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-pentyloxy group, a 11-methyl-n-butoxy group, a 22-methyl-n-butoxy group, a 23-methyl-n-pentyloxy group, a 24-methyl-n-pentyloxy group, a 25-methyl-n-pentyloxy group, a 26-methyl-n-pentyloxy group, a 27-methyl-n-pentyloxy group, a 28-methyl-n-pentyloxy group, a 29-methyl-n-pentyloxy group, a 30-methyl-n-pentyloxy group, a 31-methyl-n-pentyloxy group, a 32-methyl-n-pentyloxy group, a 33-methyl-n-pentyloxy group, a 34-methyl-n-pentyloxy group, a 35-methyl-n- n-Heptyloxy group, n-octyloxy group, n-pentyloxy group, 1,1-dimethyl-n-butoxy group, 1,2-dimethyl-n-butoxy group, 1,3-dimethyl-n-butoxy group, 2,2-dimethyl-n-butoxy group, 2,3-dimethyl-n-butoxy group, 3,3-dimethyl-n-butoxy group, 1-ethyl-n-butoxy group, 2-ethyl-n-butoxy group, 1,1,2-trimethyl-n-propoxy group, 1,2,2-trimethyl-n-propoxy group, 1-ethyl-1-methyl-n-propoxy group, 1-ethyl-2-methyl-n-propoxy group, n-heptyloxy group, n-octyloxy group, and n-nonyloxy group.

[0033] A is, for example, a group represented by the following formula (A). [ka] (In formula (A), R ais a hydrogen atom or a methyl group. * represents a bond.

[0034] The unit structure represented by formula (1-1) may be one type or a combination of two or more types. For example, it may be a copolymer having a plurality of unit structures in which Ar is the same type, and copolymers having a plurality of unit structures in which Ar is different types, such as a unit structure in which Ar has a benzene ring and a unit structure in which Ar has a naphthalene ring, are not excluded from the technical scope of the present application.

[0035] The above phrase "optionally interrupted" means, in the case of an alkylene group having 2 to 10 carbon atoms, that any carbon-to-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 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.

[0036] 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.

[0037] An alkyl group having 1 to 10 carbon atoms which may be substituted with a heteroatom means that one or more hydrogen atoms in the alkyl group having 1 to 10 carbon atoms are substituted with a heteroatom (preferably a halogeno group).

[0038] L 1 represents a single bond or an alkylene group having 1 to 10 carbon atoms, and is preferably represented by the following formula (1-2). [ka] (In formula (1-2), R2 , R 3 each independently represents a hydrogen atom, 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, or a cyclobutyl group; R 2 , R 3 may be bonded to each other to form a ring having 3 to 6 carbon atoms). 2 , R 3 Both are hydrogen atoms (i.e. -(CR 2 R 3 )— is a methylene group)

[0039] A halogeno group refers to a halogen -X (F, Cl, Br, I) replacing hydrogen.

[0040] 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. [ka] (In formula (1-1'), Ar, R 1 , n1, L 1 , n2, and T 1 represents Ar and R in formula (1-1). 1 , n1, L 1 , n2, and T 1 and E is a group having an epoxy group.

[0041] The polymer having a structural unit represented by formula (1-1') is not particularly limited as long as it satisfies the unit structure of formula (1-1'). It may be produced by a method known per se. Commercially available products may be used. Examples of commercially available products include heat-resistant epoxy novolac resin EOCN (registered trademark) series (manufactured by Nippon Kayaku Co., Ltd.) and epoxy novolac resin DEN (registered trademark) series (manufactured by Dow Chemical Japan Co., Ltd.).

[0042] 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.

[0043] Examples of the polymer having the structural unit represented by formula (1-1') include those having the following unit structures. [ka] In the formula, Me represents a methyl group, and Et represents an ethyl group.

[0044] The weight average molecular weight of the polymer or compound having a crosslinkable group is not particularly limited, but is preferably from 2,000 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).

[0045] The content of the polymer or compound having a crosslinkable group in the composition for forming a protective film 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.

[0046] The content of the polymer or compound having a crosslinkable 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 constituent components. The film constituent components are components remaining after excluding volatile matters (solvent) from the composition for forming a protective film.

[0047] <Other ingredients> Furthermore, the protective film-forming composition may contain, as necessary, a radical polymerization initiator (such as a photopolymerization initiator), an 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 (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.

[0048] The radical polymerization initiator may be any one capable of releasing a substance that initiates radical polymerization by irradiation with light and / or heating. Examples of the photoradical polymerization initiator 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, examples of the compounds include 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 -2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium), and the like.

[0049] As the photoradical polymerization initiator, commercially available products can be used, for example, IRGACURE (registered trademark) 651, 184, 369, 784, etc., manufactured by BASF Japan Co., Ltd. In addition, commercially available products other than the above can also be used, specifically, IRGACURE (registered trademark) 500, 907, 379, 819, 127, 500, 754, 250, 1800, 1870, OXE01, DAROCUR (registered trademark) TPO, 1173, manufactured by BASF Japan Co., Ltd.; Speedcure (registered trademark) MBB, PBZ, ITX, CTX, EDB, manufactured by Lambson; Esacure (registered trademark) ONE, KIP150, KTO46, manufactured by Lamberti; KAYACURE (registered trademark) DETX-S, CTX, BMS, DMBI, etc., manufactured by Nippon Kayaku Co., Ltd.

[0050] Examples of the thermal radical polymerization initiator 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-butyl peroxy-2-ethylhexanoate; 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), and (1-phenylethyl) Examples of the azo-based compounds include azodiphenylmethane, 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.

[0051] Examples of commercially available thermal radical polymerization initiators include Perloil (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, Niper (registered trademark) PMB, BMT, BW, Pertetra (registered trademark) A, Perhexa (registered trademark) MC, TMH, HC, 250, 25B, C, 25Z, 22, V, Perocta (registered trademark) O, Percumyl (registered trademark) ND, D, Permenta (registered trademark) H, and Nofumar (registered trademark) BC, all of which are manufactured by NOF Corporation; and V-70, V-65, V-59, V-40, V-30, and VA-0, all of which are manufactured by Wako Pure Chemical Industries, Ltd. 44, VA-046B, VA-061, V-50, VA-057, VA-086, VF-096, VAm-110, V-601, V-501; IRGACURE (registered trademark) 184, 369, 651, 500, 819, 907, 784, 2959, CGI1700, CGI1750, CGI1850, CG24-61, DAROCUR (registered trademark) 1116, 1173, LUCIRIN (registered trademark) TPO manufactured by BASF Japan Ltd.; UVECRYL (registered trademark) P36 manufactured by Cytec Surface Specialties; Esacure (registered trademark) KIP150, KIP65LT, KIP100F, KT37, KT55, KTO46, KIP75 / B manufactured by Lamberti, etc., but are not limited thereto.

[0052] The radical polymerization initiator may be used alone or in combination of two or more. The content of the radical polymerization initiator is preferably 1 part by mass or more, 2 parts by mass or more, 3 parts by mass or more, and 50 parts by mass or less, 20 parts by mass or less, or 10 parts by mass or less, based on 100 parts by mass of the polymer or compound having a crosslinkable group.

[0053] 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-hydroxy 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- 6-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-6-ethyl-3-hydroxy-2,5-dimethylbenzyl)-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 tris(4-t-butyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione include 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. Among the hindered phenol compounds, 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione is preferred. As the polymerization inhibitor, a commercially available product may be used, and a specific example thereof is Irganox-3114 (manufactured by BASF Japan Ltd.).

[0054] The polymerization inhibitor may be used alone or in combination of two or more. The content of the polymerization inhibitor is preferably 0.01 to 1 part by mass, more preferably 0.01 to 0.5 part by mass, based on 100 parts by mass of the polymer or compound having a crosslinkable group.

[0055] Examples of surfactants include polyoxyethylene alkyl ether compounds such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; polyoxyethylene alkyl allyl ether compounds such as polyoxyethylene octyl phenol ether and polyoxyethylene nonyl phenol 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 F-TOP EF301, EF303, and EF352 (manufactured by Tochem Products Co., Ltd.), Megafac F171, F173, R-08, and R-30 (manufactured by Dainippon Ink Co., Ltd.), Fluorad FC430 and FC431 (manufactured by Sumitomo 3M Limited), and Asahiguard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, and SC106 (manufactured by Asahi Glass Co., Ltd.), and organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0056] The surfactant may be used alone or in combination of two or more. The content of the surfactant is preferably 0.1 parts by mass or more, 0.5 parts by mass or more, 5 parts by mass or less, and 2 parts by mass or less, based on 100 parts by mass of the polymer or compound having a crosslinkable group.

[0057] As the acid catalyst, an acidic compound, a basic compound, or various compounds that generate an acid or a base by the action of heat or light can be used.

[0058] As the acidic compound, a sulfonic acid compound or a carboxylic acid compound can be used. Examples of the sulfonic acid compound or carboxylic acid compound include p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium trifluoromethanesulfonate (=pyridinium trifluoromethanesulfonic acid), pyridinium-p-toluenesulfonate, pyridinium-4-hydroxybenzenesulfonate, salicylic acid, camphorsulfonic acid, 5-sulfosalicylic acid, 4-chlorobenzenesulfonic acid, 4-phenolsulfonic acid, pyridinium-4-phenolsulfonate, benzenedisulfonic acid, 1-naphthalenesulfonic acid, 4-nitrobenzenesulfonic acid, citric acid, benzoic acid, and hydroxybenzoic acid.

[0059] As the basic compound, an amine compound or an ammonium hydroxide compound can be used, and as the compound that generates a base by heat, urea can be used. Examples of the amine compound include tertiary amines such as triethanolamine, tributanolamine, trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, tri-tert-butylamine, tri-n-octylamine, triisopropanolamine, phenyldiethanolamine, stearyldiethanolamine, and diazabicyclooctane, and aromatic amines such as pyridine and 4-dimethylaminopyridine. Other examples of the amine compound include primary amines such as benzylamine and n-butylamine, and secondary amines such as diethylamine and di-n-butylamine. Examples of ammonium hydroxide compounds include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, benzyltriethylammonium hydroxide, cetyltrimethylammonium hydroxide, phenyltrimethylammonium hydroxide, and phenyltriethylammonium hydroxide.

[0060] As the acid generator, either a thermal acid generator or a photoacid generator can be used.

[0061] 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-phenolsulfonic acid 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. Examples of commercially available products include K-PURE (registered trademark) CXC-1612, CXC-1614, TAG-2172, TAG-2179, TAG-2678, and TAG2689 (all manufactured by King Industries), and SI-45, SI-60, SI-80, SI-100, SI-110, and SI-150 (all manufactured by Sanshin Chemical Industry Co., Ltd.).

[0062] 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 acid generators, bisoxime sulfonate-type acid generators, etc. Examples include bis(4-tert-butylphenyl)iodonium trifluoromethanesulfonate, triphenylsulfonium trifluoromethanesulfonate, phenyl-bis(trichloromethyl)-s-triazine, benzoin tosylate, and N-hydroxysuccinimide trifluoromethanesulfonate.

[0063] 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).

[0064] 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; 9-anthrylmethyl=piperidine-1-carboxylate, and (E)-1-piperidino-3-(2-hydroxyphenyl)-2-propene. -1-one, (2-nitrophenyl)methyl 4-hydroxypiperidine-1-carboxylate, (2-nitrophenyl)methyl 4-(methacryloyloxy)piperidine-1-carboxylate and other piperidine-based photobase generators; guanidinium 2-(3-benzoylphenyl)propionate, 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-tetramethylbiguanidium 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.

[0065] The above components can be used alone or in combination of two or more kinds. In that case, they are usually used in an amount of 10 mass % or less, preferably 3 mass % or less, based on the solid content of the composition for forming a protective film.

[0066] The method for preparing the composition for forming a protective film is not particularly limited. That is, a polymer or compound having a crosslinkable group, a solvent, and other components may be mixed in any ratio and in any order to prepare 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.

[0067] As described later, in order to prepare a protective film having a thickness of about 300 nm by a spin coating method, the composition for forming the protective film 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.

[0068] In addition, the protective film forming composition is preferably photosensitive. For example, it may be a negative type solvent development type. In the case of a photosensitive protective film forming composition, the photosensitive protective film forming composition (negative type) is applied to the front end, bevel portion, and optionally the back end of the substrate, and then the portion where the film is to be cured is exposed and developed, so that the bevel portion can be accurately covered with the protective film. The photosensitivity has the advantages of facilitating film thickness control at the wafer end of the protective film, making it possible to remove inner humps, improving edge shape, and correcting deviation of the center position during spin coating.

[0069] The composition for forming a protective film may be a composition containing a compound (E) containing at least one partial structure selected from the partial structures (I) represented by the following formulas (1-1) to (1-7), as described in WO2018 / 190380. The compound (E) is a polymer or compound having a crosslinkable group.

[0070] [ka] (In the formula, R 1 , R 1a , R 3 , R 5a , and R 6aeach independently represents an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 40 carbon atoms (the alkylene group and the arylene group may be optionally substituted with one or more amide groups or amino groups), an oxygen atom, a carbonyl group, a sulfur atom, -C(O)-NR a -, -NR b - or a divalent group consisting of a combination thereof, R 5 each independently represents a nitrogen atom, or a nitrogen atom and an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 40 carbon atoms (the alkylene group and the arylene group may be optionally substituted with one or more amido groups or amino groups), an oxygen atom, a carbonyl group, a sulfur atom, -C(O)-NR a - and -NR b - represents a trivalent group consisting of a combination of at least one group selected from the group consisting of R 2 , R 2a , R 4 , and R 6 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a hydrogen atom and an alkylene group having 1 to 10 carbon atoms, an oxygen atom, a carbonyl group, or -C(O)-NR a - and -NR b - represents a monovalent group consisting of a combination of at least one group selected from the group consisting of R a represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R b represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkylcarbonyl group having 1 to 10 carbon atoms, n represents the number of repeating units from 1 to 10; and The dotted lines represent chemical bonds to adjacent atoms.)

[0071] The entire disclosure of WO2018 / 190380 is incorporated by reference into this application.

[0072] The protective film-forming composition may contain a polysiloxane. The polysiloxane may be a modified polysiloxane in which a portion of the silanol groups is modified, for example, a modified polysiloxane in which a portion of the silanol groups is alcohol-modified or acetal-protected. The polysiloxane may be, for example, a hydrolysis condensation product of a hydrolysis condensation product, or a modified product in which at least a portion of the silanol groups of the hydrolysis condensation product have been alcohol-modified or acetal-protected (hereinafter, sometimes referred to as a "modification product of the hydrolysis condensation product"). The hydrolysis silane related to the hydrolysis condensation product may contain one or more hydrolysis silanes. The polysiloxane may have any of a cage type, ladder type, straight chain type, and branched type main chain structure. Furthermore, commercially available polysiloxanes may be used.

[0073] In the present invention, the "hydrolysis condensate" of hydrolyzable silane, i.e., the product of hydrolysis condensation, includes not only polyorganosiloxane polymers that are condensates in which condensation is completely completed, but also polyorganosiloxane polymers that are partial hydrolysis condensates in which condensation is not completely completed.Similar to the condensates in which condensation is completely completed, such partial hydrolysis condensates are also polymers obtained by hydrolysis and condensation of hydrolyzable silane, but they are only partially hydrolyzed and not condensed, and therefore Si-OH groups remain. The polysiloxane of the present invention may be, for example, a hydrolyzed condensate of hydrolyzable silane containing at least one hydrolyzable silane represented by the following formula (1) or a modified product thereof.

[0074] <<Formula (1)>> [ka]

[0075] In formula (1), R 1are groups bonded to silicon atoms and independently represent an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted aralkyl group, an optionally substituted halogenated alkyl group, an optionally substituted halogenated aryl group, an optionally substituted halogenated aralkyl group, an optionally substituted alkoxyalkyl group, an optionally substituted alkoxyaryl group, an optionally substituted alkoxyaralkyl group, or an optionally substituted alkenyl group, or represent an organic group having an epoxy group, an organic group having an acryloyl group, an organic group having a methacryloyl group, an organic group having a mercapto group, an organic group having an amino group, an organic group having an alkoxy group, an organic group having a sulfonyl group, or an organic group having a cyano group, or a combination of two or more thereof. Also R 2 are groups or atoms bonded to a silicon atom, and each independently represent an alkoxy group, an aralkyloxy group, an acyloxy group, or a halogen atom. a represents an integer of 0 to 3.

[0076] R in formula (1) 1 Specific examples of each group and atom in the formula (A-1) and the preferred carbon numbers thereof include R 3 The groups and carbon numbers mentioned above for the formula can be mentioned. R in formula (1) 2 Specific examples of the groups and atoms in and their suitable carbon numbers include the groups, atoms, and carbon numbers described above for X in formulas (A-1) and (A-2).

[0077] <<<Specific examples of hydrolyzable silanes represented by formula (1)>>> Specific examples of hydrolyzable silanes represented by formula (1) include tetramethoxysilane, tetrachlorosilane, tetraacetoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane, methyltrimethoxysilane, methyltrichlorosilane, methyltriacetoxysilane, methyltriethoxysilane, methyltripoxysilane, methyltributoxysilane, methyltriamyloxysilane, methyltriphenoxysilane, methyltribenzyloxysilane, and methyltriphenoxysilane. Netyloxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, α-glycidoxyethyltrimethoxysilane, α-glycidoxyethyltriethoxysilane, β-glycidoxyethyltrimethoxysilane, β-glycidoxyethyltriethoxysilane, α-glycidoxypropyltrimethoxysilane, α-glycidoxypropyltriethoxysilane, β-glycidoxypropyltrimethoxysilane, β-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane Glycidoxypropyltriethoxysilane, γ-glycidoxypropyltripropoxysilane, γ-glycidoxypropyltributoxysilane, γ-glycidoxypropyltriphenoxysilane, α-glycidoxybutyltrimethoxysilane, α-glycidoxybutyltriethoxysilane, β-glycidoxybutyltriethoxysilane, γ-glycidoxybutyltrimethoxysilane, γ-glycidoxybutyltriethoxysilane, δ-glycidoxybutyltrimethoxysilane, δ-glycidoxybutyltriethoxysilane, (3,4-epoxysilane cyclohexyl)methyltrimethoxysilane, (3,4-epoxycyclohexyl)methyltriethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltriethoxysilane, β-(3,4-epoxycyclohexyl)ethyltripropoxysilane, β-(3,4-epoxycyclohexyl)ethyltributoxysilane, β-(3,4-epoxycyclohexyl)ethyltriphenoxysilane, γ-(3,4-epoxycyclohexyl)propyltrimethoxysilane,γ-(3,4-epoxycyclohexyl)propyltriethoxysilane, δ-(3,4-epoxycyclohexyl)butyltrimethoxysilane, δ-(3,4-epoxycyclohexyl)butyltriethoxysilane, glycidoxymethylmethyldimethoxysilane, glycidoxymethylmethyldiethoxysilane, α-glycidoxyethylmethyldimethoxysilane, α-glycidoxyethylmethyldiethoxysilane, β-glycidoxyethylmethyldimethoxysilane, β-glycidoxyethylethyldimethoxysilane, α-glycidoxypropylmethyldimethoxysilane Silane, α-glycidoxypropyl methyl diethoxysilane, β-glycidoxypropyl methyl dimethoxysilane, β-glycidoxypropyl ethyl dimethoxysilane, γ-glycidoxypropyl methyl dimethoxysilane, γ-glycidoxypropyl methyl diethoxysilane, γ-glycidoxypropyl methyl dipropoxysilane, γ-glycidoxypropyl methyl dibutoxysilane, γ-glycidoxypropyl methyl diphenoxysilane, γ-glycidoxypropyl ethyl dimethoxysilane, γ-glycidoxypropyl ethyl diethoxysilane, γ-glycidoxypropyl methyl diphenoxysilane Glycidoxypropylvinyldimethoxysilane, γ-glycidoxypropylvinyldiethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltriacetoxysilane, methylvinyldimethoxysilane, methylvinyldiethoxysilane, methylvinyldichlorosilane, methylvinyldiacetoxysilane, dimethylvinylmethoxysilane, dimethylvinylethoxysilane, dimethylvinylchlorosilane, dimethylvinylacetoxysilane, divinyldimeth silane, divinyldiethoxysilane, divinyldichlorosilane, divinyldiacetoxysilane, gamma-glycidoxypropylvinyldimethoxysilane, gamma-glycidoxypropylvinyldiethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, allyltrichlorosilane, allyltriacetoxysilane, allylmethyldimethoxysilane, allylmethyldiethoxysilane, allylmethyldichlorosilane, allylmethyldiacetoxysilane, allyldimethylmethoxysilane, allyldimethylethoxysilane, allyldimethylchlorosilane,Allyldimethylacetoxysilane, diallyldimethoxysilane, diallyldiethoxysilane, diallyldichlorosilane, diallyldiacetoxysilane, 3-allylaminopropyltrimethoxysilane, 3-allylaminopropyltriethoxysilane, p-styryltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltrichlorosilane, phenyltriacetoxysilane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane, phenylmethyldichlorosilane, phenylmethyldiacetoxysilane , Phenyldimethylmethoxysilane, Phenyldimethylethoxysilane, Phenyldimethylchlorosilane, Phenyldimethylacetoxysilane, Diphenylmethylmethoxysilane, Diphenylmethylethoxysilane, Diphenylmethylchlorosilane, Diphenylmethylacetoxysilane, Diphenyldimethoxysilane, Diphenyldiethoxysilane, Diphenyldichlorosilane, Diphenyldiacetoxysilane, Triphenylmethoxysilane, Triphenylethoxysilane, Triphenylacetoxysilane, Triphenylchlorosilane, 3-Phenyl aminopropyltrimethoxysilane, 3-phenylaminopropyltriethoxysilane, dimethoxymethyl-3-(3-phenoxypropylthiopropyl)silane, triethoxy((2-methoxy-4-(methoxymethyl)phenoxy)methyl)silane, benzyltrimethoxysilane, benzyltriethoxysilane, benzylmethyldimethoxysilane, benzylmethyldiethoxysilane, benzyldimethylmethoxysilane, benzyldimethylethoxysilane, benzyldimethylchlorosilane, phenethyltrimethoxysilane, phenethyltriethoxysilane Silane, phenethyltrichlorosilane, phenethyltriacetoxysilane, phenethylmethyldimethoxysilane, phenethylmethyldiethoxysilane, phenethylmethyldichlorosilane, phenethylmethyldiacetoxysilane, methoxyphenyltrimethoxysilane, methoxyphenyltriethoxysilane, methoxyphenyltriacetoxysilane, methoxyphenyltrichlorosilane, methoxybenzyltrimethoxysilane, methoxybenzyltriethoxysilane, methoxybenzyltriacetoxysilane, methoxybenzyltrichlorosilane,Methoxyphenethyltrimethoxysilane, Methoxyphenethyltriethoxysilane, Methoxyphenethyltriacetoxysilane, Methoxyphenethyltrichlorosilane, Ethoxyphenyltrimethoxysilane, Ethoxyphenyltriethoxysilane, Ethoxyphenyltriacetoxysilane, Ethoxyphenyltrichlorosilane, Ethoxybenzyltrimethoxysilane, Ethoxybenzyltriethoxysilane, Ethoxybenzyltriacetoxysilane, Ethoxybenzyltrichlorosilane, i-Propoxyphenyltrimethoxysilane, i-Propoxy i-Propoxyphenyltriethoxysilane, i-Propoxyphenyltriacetoxysilane, i-Propoxyphenyltrichlorosilane, i-Propoxybenzyltrimethoxysilane, i-Propoxybenzyltriethoxysilane, i-Propoxybenzyltriacetoxysilane, i-Propoxybenzyltrichlorosilane, t-Butoxyphenyltrimethoxysilane, t-Butoxyphenyltriethoxysilane, t-Butoxyphenyltriacetoxysilane, t-Butoxyphenyltrichlorosilane, t-Butoxybenzyltrimethoxysilane, t-Butoxy Benzyltriethoxysilane, t-butoxybenzyltriacetoxysilane, t-butoxybenzyltrichlorosilane, methoxynaphthyltrimethoxysilane, methoxynaphthyltriethoxysilane, methoxynaphthyltriacetoxysilane, methoxynaphthyltrichlorosilane, ethoxynaphthyltrimethoxysilane, ethoxynaphthyltriethoxysilane, ethoxynaphthyltriacetoxysilane, ethoxynaphthyltrichlorosilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, γ-chloropropyltrichlorosilane Triacetoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, β-cyanoethyltriethoxysilane, thiocyanatepropyltriethoxysilane, chloromethyltrimethoxysilane, chloromethyltriethoxysilane, triethoxysilylpropyldiallylisocyanurate, bicyclo[2,2,1]heptenyltriethoxysilane, benzenesulfonylpropyltriethoxysilane,Examples of the silane include, but are not limited to, benzenesulfonamidopropyltriethoxysilane, dimethylaminopropyltrimethoxysilane, dimethyldimethoxysilane, phenylmethyldimethoxysilane, dimethyldiethoxysilane, phenylmethyldiethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-chloropropylmethyldiethoxysilane, dimethyldiacetoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptomethyldiethoxysilane, methylvinyldimethoxysilane, and methylvinyldiethoxysilane.

[0078] The composition for forming a protective film is described in JP 2016-003160 A. (A) a multifunctional epoxy (meth)acrylate compound, (B) a polyfunctional thiol compound, and (C) It may contain a radical polymerization initiator. (A) The polyfunctional epoxy (meth)acrylate compound is a polymer or compound having a crosslinkable group.

[0079] The molecular weight of the component (A) may be 300 to 20,000. The component (A) may be a bisphenol-type polyfunctional epoxy (meth)acrylate compound. The component (B) may be liquid at 25°C. Furthermore, (D) a polymerization inhibitor may be contained. The viscosity at 25°C may be 2,000 to 100,000 mPa·s.

[0080] The entire disclosure of JP2016-003160A is incorporated by reference into this application.

[0081] The protective film-forming composition may be a film-forming composition containing a photopolymerizable substance and a photopolymerization initiator as described in WO 2009 / 104643. The photopolymerizable substance is a polymer or compound having a crosslinkable group. The photopolymerizable substance may be a compound having at least one reactive group capable of cationic polymerization, and the cationic polymerization initiator may be a photocationic polymerization initiator. The photopolymerizable substance may be a compound having at least one reactive group capable of radical polymerization, and the photopolymerization initiator may be a photoradical polymerization initiator.

[0082] The photopolymerizable substance may be a sugar compound. The sugar compound may be a monosaccharide or a disaccharide compound. The sugar compound has the formula (10):

[0083] [ka]

[0084] (However, G 1 represents a sugar skeleton, T represents a divalent linking group, R 1 represents a vinyl group or a glycidyl group, R 2 represents a hydrogen atom or a hydroxyl group. n and L each represent an integer of 0 or 1, and p is an integer that is the total number of hydroxyl groups in the sugar. m is an integer that satisfies 1≦m≦(pm).

[0085] The photopolymerizable substance may be an alicyclic epoxy compound or an alicyclic oxetane compound. The alicyclic epoxy compound may be a cycloalkylene oxide derivative. The alicyclic epoxy compound is represented by formula (2) or (3):

[0086] [ka]

[0087] (However, G 2 represents a monovalent to pentavalent linking group having an alkylene group, a carbonyloxy group, a heterocycle, an aromatic ring, or a combination thereof; G 3represents an alkyl group, an alkylcarbonyl group, a heterocycle, an aromatic ring, or an organic group having a combination thereof, and n and m each represent an integer of 1 to 5.

[0088] The entire disclosure of WO2009 / 104643 is incorporated by reference into this application.

[0089] (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. An example of a method for forming the protective film is step (X) in the method for producing a semiconductor device, which will be described later.

[0090] The protective film is, for example, a protective film for preventing metal contamination of the edge and bevel of the wafer surface.

[0091] 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, and 1,700 nm. 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, and 300 nm.

[0092] The protective film is, for example, a protective film that has been cured by being irradiated with light having a wavelength of 170 to 800 nm (for example, 254 nm).

[0093] The properties of the protective film that covers the surface edge and bevel portion of a substrate (wafer) used in semiconductor manufacturing should 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, no crater foreign matter remaining on the wafer side (bevel 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).

[0094] (Method of manufacturing a semiconductor device) The method for manufacturing a semiconductor device according to the present invention includes the steps of: (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; (C) etching the semiconductor substrate using the resist pattern as a mask; A method for manufacturing a semiconductor device comprising: The method includes the step (X) of forming a protective film on a front surface edge, a bevel portion, and optionally a back surface edge of a semiconductor manufacturing wafer using the protective film-forming composition of the present invention; A method for manufacturing a semiconductor device.

[0095] The following explains each in order. <Process (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, for example, 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.

[0096] When using a semiconductor substrate having an inorganic film formed on its surface, the inorganic film is 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 polysilicon film, silicon oxide film, silicon nitride film, BPSG (Boro-Phospho Silicate Glass) film, titanium nitride film, titanium nitride oxide film, tungsten film, gallium nitride film, and gallium arsenide film.

[0097] On such a semiconductor substrate, a resist underlayer film, a resist film, etc., of a predetermined thickness are formed by an appropriate coating method such as spray, spinner, coater, etc. 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, etc. Usually, these films are baked using a heating means such as a hot plate.

[0098] 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 resist is also included in the photoresist. Both negative photoresists and positive photoresists can be used. There are positive photoresists made of novolac resin and 1,2-naphthoquinone diazide sulfonic acid ester, chemically amplified photoresists made of a binder having a group that decomposes with acid to increase the alkaline dissolution rate and a photoacid generator, chemically amplified photoresists made of a low molecular compound that decomposes with acid to increase the alkaline dissolution rate of the photoresist, an alkali-soluble binder, and a photoacid generator, chemically amplified photoresists made of a binder having a group that decomposes with acid to increase the alkaline dissolution rate, a low molecular compound that decomposes with acid to increase the alkaline dissolution rate of the photoresist, and a photoacid generator, and resists containing metal elements. Examples of the photoresist include V146G (trade name) manufactured by JSR Corporation, APEX-E (trade name) manufactured by Shipley Co., Ltd., PAR710 (trade name) manufactured by Sumitomo Chemical Co., Ltd., and AR2772 and SEPR430 (trade names) manufactured by Shin-Etsu Chemical Co., Ltd. In addition, examples of the photoresist include fluorine atom-containing polymer photoresists as 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.

[0099] The resist film forming composition used for forming the resist film can contain one or more metals. The form of the metal can be a simple metal, a metal salt, a metal complex, or other metal-containing compounds. The metal species is not particularly limited, and examples thereof include tin, indium, antimony, bismuth, gallium, germanium, aluminum, zirconium, hafnium, cerium, lanthanum, and cesium.

[0100] The resist film forming composition used to form the resist film may 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 comprising metal oxo-hydroxo networks having organic ligands via metal carbon bonds and / or metal carboxylate bonds, as described in JP 2019-113855 A. An example of a metal-containing resist uses a peroxo ligand as a radiation-sensitive stabilizing ligand. Peroxo-based metal oxo-hydroxo compounds are described in detail in, for example, the patent document described in paragraph

[0011] of Publication 2019-532489. Such patent documents include, for example, U.S. Pat. No. 9,176,377 B2, U.S. Pat. Appl. Pub. No. 2013 / 0224652 A1, U.S. Pat. No. 9,310,684 B2, U.S. Pat. Appl. Pub. No. 2016 / 0116839 A1, and U.S. Pat. Appl. Pub. No. 15 / 291738.

[0101] The bake conditions for the resist film are appropriately selected from a bake temperature of 70° C. to 400° C. and a bake time of 0.3 to 60 minutes, preferably a bake temperature of 80° C. to 350° C. and a bake time of 0.5 to 30 minutes, and more preferably a bake temperature of 90° C. to 300° C. and a bake time of 0.8 to 10 minutes.

[0102] 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.

[0103] <Process (X) of forming protective film> Step (X) of forming a protective film from the protective film-forming composition of the present invention on the front end, bevel, and optionally the back end of a wafer for semiconductor manufacturing is performed at any time. In step (X), the protective film-forming composition is preferably 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).

[0104] In this specification, the surface of the substrate on which a device portion such as a resist film is provided is called the front surface, and the opposite surface is called the back surface. The front surface edge refers to a region that is usually 1 to 10 mm wide from the edge of the device portion provided on the substrate to the bevel portion, the bevel portion refers to a curved region (wafer side) that connects the front surface edge and the back surface edge, and the back surface edge refers to a region that corresponds to the front surface edge on the back surface of the substrate.

[0105] First, the composition for forming a protective film is applied to the semiconductor substrate. The method for applying the composition for forming a protective film is not particularly limited, but for example, known means such as a spin coating method (spin coating method) or a spray method can be adopted. For example, when the spin coating method is adopted, the composition for forming a protective film is supplied through a nozzle from above or near the front end of the rotating disk-shaped substrate while rotating the semiconductor substrate at a predetermined rotation speed. Preferably, the composition is also supplied through a nozzle from the vicinity of the bevel portion and / or the rear end of the substrate.

[0106] The spin-coating conditions can be appropriately selected and are not limited in any way. Typical conditions are as follows: Viscosity of protective film forming composition: Approximately 100 cps or less Wafer rotation speed: ·When supplying the composition for forming a protective film: 50~500rpm When shaking off the dry air: 700 to 2,000 rpm Protective film thickness: 300nm

[0107] Next, in one embodiment, the composition for forming a protective film is exposed to light. The exposure can be performed by irradiating the composition for forming a protective film with actinic rays such as ultraviolet rays, visible rays, and radiation (including i-rays, KrF excimer laser, ArF excimer laser, EUV (extreme ultraviolet), and EB (electron beam)) through a mask or without a mask. Note that a soft bake (SB) may be performed before exposure, and a post-exposure bake (PEB) may be performed before development after exposure. The temperature of the post-exposure bake is preferably 50°C to 150°C, and the time of the post-exposure bake is preferably 1 minute to 10 minutes.

[0108] 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.

[0109] Examples of the organic solvent contained in the developer include alcohol-based solvents, ether-based solvents, ketone-based solvents, amide-based solvents, ester-based solvents, and hydrocarbon-based solvents. The organic solvent in the developer is preferably an ester-based solvent, a ketone-based solvent, or a combination thereof. The developer may contain one organic solvent alone or two or more organic solvents. Examples of the alcohol solvent 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-iso-butyl ketone, 2-heptanone, ethyl-n-butyl ketone, methyl-n-hexyl ketone, di-iso-butyl ketone, and trimethylnonanone; cyclic ketone solvents such as cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, and methylcyclohexanone; 2,4-pentanedione, acetonylacetone, and acetophenone. Examples of the 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; polyvalent carboxylic acid diester-based solvents such as diethyl oxalate; and carbonate-based solvents such as dimethyl carbonate and diethyl carbonate. Examples of the hydrocarbon solvent include aliphatic hydrocarbon solvents having 5 to 12 carbon atoms, such as n-pentane and n-hexane; and aromatic hydrocarbon solvents having 6 to 16 carbon atoms, such as toluene and xylene. Among these, ester solvents, ketone solvents, ether solvents and combinations thereof are preferred, and ester solvents, ketone solvents and combinations thereof are more preferred. As the ester solvent, propylene glycol monomethyl ether acetate is preferred. As the ketone solvent, cyclohexanone is preferred. As the ether solvent, propylene glycol monomethyl ether is preferred.

[0110] The lower limit of the content of the organic solvent in the developer is preferably 80% by mass, more preferably 90% by mass, further 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.

[0111] The developer may contain a nitrogen-containing compound.

[0112] The developer may be an aqueous developer instead of the organic solvent developer. Specifically, the developer may be an aqueous alkali solution such as sodium hydroxide, potassium hydroxide, sodium silicate, ammonia, monoethylamine, diethylamine, triethylamine, triethanolamine, or tetramethylammonium hydroxide. The base concentration of these aqueous solutions is not particularly limited, but may be, for example, 0.1 to 10% by mass.

[0113] 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 silicon-based surfactants.

[0114] Development methods include, for example, 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 the developer is piled up on the substrate surface by surface tension and left to stand for a certain period of time (paddle method), a method in which the developer is sprayed onto the substrate surface (spray method), and a method in which the developer is continuously dispensed by scanning a developer dispensing nozzle at a constant speed over a substrate rotating at a constant speed (dynamic dispense method).

[0115] Next, the composition for forming a protective film 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 more and 350° C. or less, preferably in the range of 200 to 300° C. The heat treatment time is the time until the composition for forming a protective film is cured, and is preferably approximately less than 30 minutes in consideration of productivity. The lower limit of the thickness of the protective film is preferably 1 nm, more preferably 3 nm, and the upper limit of the thickness of the protective film is preferably 500 nm, more preferably 300 nm.

[0116] For example, step (X) is performed before step (A). Then, for example, in step (A), a resist film is formed on at least a part 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 by a remover. At this time, similar to step (X), it is preferable to apply the remover to the front end, the bevel, and optionally the back end of the semiconductor manufacturing wafer. Examples of the resist remover include propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone, water, butyl acetate, tetramethylammonium aqueous solution, or a mixture of these. Among these, propylene glycol monomethyl ether acetate and water are preferable from the viewpoint of removability of the resist film.

[0117] After step (X) or step (Y), step (Z) of removing the protective film is performed. In step (Z), the protective film is preferably removed by ashing, or the protective film is preferably removed by treatment with hydrofluoric acid, an organic solvent, an alkaline developer, or a semiconductor cleaning solution. After that, it is preferable to wash with any solvent or a conventional semiconductor cleaning solution.

[0118] 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). In addition, 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).

[0119] <Process (B)> In step (B), the resist film is irradiated with light or an electron beam, and then developed to form a resist pattern.

[0120] 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. Note that soft baking (SB) may be performed before exposure, and post-exposure baking (PEB) may be performed after exposure and before development. The temperature of post-exposure baking is preferably 50°C to 150°C, and the time of post-exposure baking is preferably 1 minute to 10 minutes.

[0121] For example, an alkaline developer is used for development, 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. As the alkaline developer, for example, an aqueous solution of an alkaline such as inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and ammonia water, 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 can be used. The base concentration of these aqueous solutions is not particularly limited, but can be, for example, 0.1 to 10 mass%.

[0122] Furthermore, the aqueous solution of the above alkalis may be used by adding an appropriate amount of alcohols such as isopropyl alcohol, or a nonionic surfactant. Each of these may be blended in a range 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 and the like may be added to these developers.

[0123] Alternatively, instead of using an alkaline developer, development may be carried out using 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 is not improved.

[0124] The semiconductor substrate that has been exposed and developed is then baked. The baking method is not particularly limited, but for example, a proximity bake furnace that uses a plurality of substrate support pins to ensure a gap between the substrate and a hot plate is preferably used. The baking temperature is usually 40° C. to 300° C., preferably 200 to 300° C. for 1 to 30 minutes, but may be set to 90° C. or lower when it is necessary to avoid damage to the resist pattern.

[0125] Baking may be performed on the semiconductor substrate after exposure and before development. The baking means and conditions are as described above, but the temperature may be set to 90° C. or less if it is necessary to avoid damage to the resist pattern.

[0126] <Process (C)> In step (C), the semiconductor substrate is processed by etching using the resist pattern as a mask.

[0127] 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. After that, the semiconductor substrate is processed by a method known per se (such as a dry etching method) using the patterned resist. The etching for processing the semiconductor substrate may be a known method. For example, when the semiconductor substrate is a silicon substrate, the etching method includes a process of processing the shape by dry etching using a fluorine-based gas such as carbon tetrafluoride, as well as a surface treatment process such as removing a silicon nitride film present on the surface of the semiconductor substrate with hot phosphoric acid.

[0128] Through the above steps, a semiconductor device can be manufactured.

[0129] (Method of manufacturing wafers 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 producing a wafer in which the surface edge and bevel portion are protected by the formed protective film. The protective film forming composition is applied, for example, to the front surface edge, the bevel portion, and optionally the back surface edge of the wafer precursor.

[0130] The wafer precursor refers to a material obtained by subjecting a semiconductor substrate to at least one step of a method for producing a semiconductor device. For example, in the method for producing a semiconductor device as described above, the wafer precursor refers to a material that has been subjected to a step of forming an inorganic film, a resist underlayer film, a resist film, etc. on a semiconductor substrate, 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.

[0131] In one embodiment, the protective film forming composition of the present invention is applied by spin coating to the front surface edge, bevel portion, and optionally the back surface edge of a wafer precursor obtained by one or more steps of a semiconductor device manufacturing process.

[0132] Thereafter, the semiconductor substrate may be baked. In this case, the baking means 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 a plurality of substrate support pins is preferably used. The baking temperature is usually 40°C to 300°C, preferably 200°C to 300°C, for 1 to 30 minutes. After the protective film-forming composition is applied, the end face of the protective film may be subjected to known treatments in the semiconductor manufacturing process, such as edge bead removal and back rinsing.

[0133] (Wafer for semiconductor manufacturing) The wafer for semiconductor production of the present invention is a wafer for semiconductor production having a protected wafer edge, which is formed by applying the protective film-forming composition of the present invention to the wafer edge. EXAMPLES

[0134] The present invention will be described in more detail below with reference to Synthesis Examples and Examples, but the present invention is not limited to the following Examples.

[0135] In the examples, the apparatus and conditions used for analyzing the physical properties of the samples are as follows.

[0136] (1) Molecular weight measurement The molecular weight used in the present invention is a molecular weight obtained by GPC analysis in terms of polystyrene. The GPC measurements were performed using a GPC apparatus (product name HLC-8320GPC, manufactured by Tosoh Corporation), GPC columns (TSKgel Super-MultiporeHZ-N (2 columns)), a column temperature of 40°C, an eluent (elution solvent) of tetrahydrofuran, a flow rate (flow velocity) of 0.35 mL / min, and polystyrene (manufactured by Sigma-Aldrich) as the standard sample.

[0137] (2) Evaporation rate The evaporation rate used in the present invention is the evaporation rate obtained by ASTM D 3539. However, the evaporation rate value used in the present invention is a relative value to the evaporation rate of n-butyl acetate. That is, the evaporation rate value used in the present invention is the value obtained by dividing the evaporation rate of the solvent by the evaporation rate of n-butyl acetate. The evaporation rates of the solvents used in the following examples (n-butyl acetate=1) are as follows: Propylene glycol monomethyl ether (evaporation rate 0.71) Propylene glycol monomethyl ether acetate (evaporation rate 0.34) Ethyl lactate (evaporation rate 0.23) Dipropylene glycol methyl ether (evaporation rate 0.03) 1,3-butylene glycol diacetate (evaporation rate 0.01 or less)

[0138] [1] Polymer synthesis <Synthesis Example 1> 162.54 g of propylene glycol monomethyl ether acetate (PGMEA) was added to 50.00 g of EOCN-104S (manufactured by Nippon Kayaku Co., Ltd.), 16.60 g of acrylic acid, 2.93 g of tetrabutylphosphonium bromide, and 0.13 g of hydroquinone, and the mixture was heated and stirred at 100° C. for 18 hours under a nitrogen atmosphere. 70 g of anion exchange resin (product name: Dowex [registered trademark] 550A, Muromachi Technos Co., Ltd.) and 70 g of cation exchange resin (product name: Amberlite [registered trademark] 15JWET, Organo Co., Ltd.) were added to the obtained solution, and the mixture was subjected to ion exchange treatment at room temperature for 4 hours. After separating the ion exchange resin, a compound solution was obtained. The repeating unit of the obtained compound corresponds to the following formula, and the weight average molecular weight measured by GPC in terms of standard polystyrene was 5100. [ka]

[0139] <Synthesis Example 2> 15.00 g of EOCN-104S (manufactured by Nippon Kayaku Co., Ltd.), 4.98 g of acrylic acid, 0.88 g of tetrabutylphosphonium bromide, and 0.04 g of hydroquinone were added with 48.76 g of propylene glycol monomethyl ether (PGME), and the mixture was heated and stirred at 100° C. for 18 hours under a nitrogen atmosphere. 20 g of anion exchange resin (product name: Dowex [registered trademark] 550A, Muromachi Technos Co., Ltd.) and 20 g of cation exchange resin (product name: Amberlite [registered trademark] 15JWET, Organo Co., Ltd.) were added to the obtained solution, and the mixture was subjected to ion exchange treatment at room temperature for 4 hours. After separating the ion exchange resin, a compound solution was obtained. The repeating unit of the obtained compound corresponds to the following formula, and the weight average molecular weight measured by GPC in terms of standard polystyrene was 6100. [ka]

[0140] <Synthesis Example 3> 15.00 g of EOCN-104S (manufactured by Nippon Kayaku Co., Ltd.), 4.98 g of acrylic acid, 0.88 g of tetrabutylphosphonium bromide, and 0.04 g of hydroquinone were added with 48.46 g of dipropylene glycol methyl ether (DPM), and the mixture was heated and stirred at 100°C for 18 hours under a nitrogen atmosphere. 20 g of anion exchange resin (product name: Dowex [registered trademark] 550A, Muromachi Technos Co., Ltd.) and 20 g of cation exchange resin (product name: Amberlite [registered trademark] 15JWET, Organo Co., Ltd.) were added to the obtained solution, and the mixture was subjected to ion exchange treatment at room temperature for 4 hours. After separating the ion exchange resin, a compound solution was obtained. The repeating unit of the obtained compound corresponds to the following formula, and the weight average molecular weight measured by GPC in terms of standard polystyrene was 7600. [ka]

[0141] <Synthesis Example 4> 15.00 g of EOCN-104S (manufactured by Nippon Kayaku Co., Ltd.), 4.98 g of acrylic acid, 0.88 g of tetrabutylphosphonium bromide, and 0.04 g of hydroquinone were added with 48.46 g of ethyl lactate (EL), and the mixture was heated and stirred at 100° C. for 18 hours under a nitrogen atmosphere. 20 g of anion exchange resin (product name: Dowex [registered trademark] 550A, Muromachi Technos Co., Ltd.) and 20 g of cation exchange resin (product name: Amberlite [registered trademark] 15JWET, Organo Co., Ltd.) were added to the obtained solution, and the mixture was subjected to ion exchange treatment at room temperature for 4 hours. After separating the ion exchange resin, a compound solution was obtained. The obtained compound corresponds to the following formula, and the weight average molecular weight measured by GPC in terms of standard polystyrene was 4100. [ka]

[0142] [2] Preparation of protective film-forming composition <Preparation Example 1> To 13.79 g of the resin solution obtained in Synthesis Example 1 (solid content: 24.26% by mass), 0.33 g of Irgacure Oxe01 (manufactured by BASF Japan Ltd.) as a photopolymerization initiator, 0.10 g of a 10% by mass solution of Megafac R-30 (manufactured by Dainippon Ink and Chemicals Co., Ltd.) in PGMEA as a surfactant, 0.05 g of Irganox3114 (manufactured by BASF Japan Ltd.) as an antioxidant, and 5.72 g of PGMEA were added and mixed, and the solution was filtered using a polytetrafluoroethylene microfilter with a pore size of 0.2 μm to obtain a composition for forming a protective film.

[0143] <Preparation Example 2> To 13.37 g of the resin solution obtained in Synthesis Example 2 (solid content: 25.02% by mass), 0.33 g of Irgacure Oxe01 (manufactured by BASF Japan Ltd.) as a photopolymerization initiator, 0.10 g of a 10% by mass PGME solution of Megafac R-30 (manufactured by Dainippon Ink and Chemicals Co., Ltd.) as a surfactant, 0.05 g of Irganox3114 (manufactured by BASF Japan Ltd.) as an antioxidant, and 6.14 g of PGME were added and mixed, and the solution was filtered using a polytetrafluoroethylene microfilter with a pore size of 0.2 μm to obtain a composition for forming a protective film.

[0144] <Preparation Example 3> To 13.13 g of the resin solution obtained in Synthesis Example 3 (solid content: 25.47% by mass), 0.33 g of Irgacure Oxe01 (manufactured by BASF Japan Ltd.) as a photopolymerization initiator, 0.10 g of a 10% by mass DPM solution of Megafac R-30 (manufactured by Dainippon Ink and Chemicals Co., Ltd.) as a surfactant, 0.05 g of Irganox3114 (manufactured by BASF Japan Ltd.) as an antioxidant, and 6.38 g of DPM were added and mixed, and the solution was filtered using a polytetrafluoroethylene microfilter with a pore size of 0.2 μm to obtain a composition for forming a protective film.

[0145] <Preparation Example 4> To 13.79 g of the resin solution obtained in Synthesis Example 1 (solid content: 24.26% by mass), 0.33 g of Irgacure Oxe01 (manufactured by BASF Japan Ltd.) as a photopolymerization initiator, 0.10 g of a 10% by mass solution of Megafac R-30 (manufactured by Dainippon Ink and Chemicals Co., Ltd.) in PGMEA as a surfactant, 0.05 g of Irganox3114 (manufactured by BASF Japan Ltd.) as an antioxidant, 2.47 g of PGMEA, and 3.25 g of DPM were added and mixed, and the solution was filtered using a polytetrafluoroethylene microfilter with a pore size of 0.2 μm to obtain a composition for forming a protective film.

[0146] <Preparation Example 5> To 13.14 g of the resin solution obtained in Synthesis Example 4 (solid content: 26.56% by mass), 0.34 g of Irgacure Oxe01 (manufactured by BASF Japan Ltd.) as a photopolymerization initiator, 0.10 g of a 10% by mass EL solution of Megafac R-30 (manufactured by Dainippon Ink and Chemicals Co., Ltd.) as a surfactant, 0.05 g of Irganox3114 (manufactured by BASF Japan Ltd.) as an antioxidant, and 6.36 g of EL were added and mixed, and the solution was filtered using a polytetrafluoroethylene microfilter with a pore size of 0.2 μm to obtain a composition for forming a protective film.

[0147] <Preparation Example 6> 13.79 g of the resin solution (solid content 24.26% by mass) obtained in Synthesis Example 1 was mixed with 0.33 g of Irgacure Oxe01 (manufactured by BASF Japan Ltd.) as a photopolymerization initiator, 0.10 g of a 10% by mass solution of Megafac R-30 (manufactured by Dainippon Ink and Chemicals Co., Ltd.) in PGMEA as a surfactant, 0.05 g of Irganox3114 (manufactured by BASF Japan Ltd.) as an antioxidant, 2.47 g of PGMEA, and 3.25 g of 1,3-butylene glycol diacetate (1,3-BGDA), and the solution was filtered using a polytetrafluoroethylene microfilter with a pore size of 0.2 μm to obtain a composition for forming a protective film.

[0148] [3] Observation of the wafer edge side (bevel part) after coating In Comparative Examples 1 to 4 and Examples 1 to 2, the protective film-forming compositions prepared in Preparation Examples 1 to 6 were spin-coated on silicon substrates to a thickness of 900 nm to form protective films. The edge side (bevel portion) of the silicon substrate was observed (magnification: 50x) for the shape of the protective film on the edge side of the silicon substrate using a scanning electron microscope (S-4800) manufactured by Hitachi High-Technologies Corporation. Cases in which no abnormal shape (partial swelling or depression) was observed in the protective film were evaluated as "good", and cases in which an abnormal shape (partial swelling or depression) was observed in the protective film were evaluated as "poor". The results are shown in Table 2 below.

[0149] [4] Observation of the wafer edge (surface end) after coating In Comparative Examples 1 to 4 and Examples 1 to 2, the protective film-forming compositions prepared in Preparation Examples 1 to 6 were spin-coated on silicon substrates to a thickness of 900 nm to form protective films. The film shape of the edge portion (surface end portion) of the silicon substrate was observed using a DEKTAK XT-A manufactured by BRUKER, and the coating properties of the coating film were evaluated. When the coating properties were good, they were marked with "◯", when the coating properties were slightly poor, they were marked with "△", and when the coating properties were poor, they were marked with "×". The results are shown in Table 2 below. Here, good coverage means that the thickness of the protective film at a point 500 μm inward from the edge of the wafer surface is 80% or more of the thickness of the protective film at a point 1500 μm inward from the edge. "Slightly poor coverage" means that the thickness of the protective film at a point 500 μm inward from the edge of the wafer surface is 30% to less than 80% of the thickness of the protective film at a point 1500 μm inward from the edge. Poor coverage means that the thickness of the protective film at a point 500 μm inward from the edge of the wafer surface is less than 30% of the thickness of the protective film at a point 1500 μm inward from the edge.

[0150] [5] Evaluation of curing properties after exposure In Comparative Examples 1 to 4 and Examples 1 to 2, the protective film-forming compositions prepared in Preparation Examples 1 to 6 were spin-coated onto silicon wafers, and then exposed to mercury lamp light at 130 mJ / cm using a wafer edge exposure module (WEE) of a coater / developer LithiusPro manufactured by Tokyo Electron Co., Ltd. 2 The edge of the wafer was exposed to light (wavelength 254 nm). After exposure, development was performed for 30 seconds using OK73 thinner (manufactured by Tokyo Ohka Kogyo Co., Ltd.) as a developing solution to form a pattern on the edge of the wafer. The film thickness after coating and the film thickness of the pattern remaining after development were measured using an optical interference type film thickness measuring device (VM-3210) manufactured by Screen Co., Ltd., and the remaining film ratio after development (film thickness after development / film thickness after coating) was calculated. The results are shown in Table 2.

[0151] [6] Viscosity measurement The viscosity of each protective film-forming composition was measured at 25° C. using an E-type viscometer (TVE-22L (manufactured by Toki Sangyo Co., Ltd.), sample amount 1.1 mL, cone rotor 1°34′, R24). The results are shown in Table 2.

[0152] [Table 2] N / A indicates that the film thickness after application was too thin to be evaluated.

Claims

1. A polymer or compound having a crosslinkable group and a solvent, the crosslinkable group is selected from the group consisting of an epoxy group, a (meth)acrylic group, a vinyl group, a carboxyl group, a thiol group, a silanol group, a cinnamoyl group, and a hydroxyl group; the solvent comprises a first solvent and a second solvent; the evaporation rate of the first solvent is 0.10 or more and the evaporation rate of the second solvent is 0.05 or less, based on the evaporation rate of n-butyl acetate as determined by ASTM D 3539 being 1; the first solvent is at least one of propylene glycol monomethyl ether, methyl 2-hydroxoisobutyrate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethyl lactate, cyclohexanone, and propylene glycol n-propyl ether; The second solvent is at least one of propylene glycol diacetate, dipropylene glycol methyl ether, dipropylene glycol methyl ether acetate, diethylene glycol monoethyl ether acetate, 1,4-butanediol diacetate, 1,3-butylene glycol diacetate, diethylene glycol monobutyl ether acetate, and 1,6-hexanediol diacetate; A composition for forming a protective film on a wafer edge in semiconductor manufacturing.

2. The composition for forming a wafer edge protection film for semiconductor manufacturing according to claim 1, wherein the mass ratio (S1:S2) of the first solvent (S1) to the second solvent (S2) is 50:50 to 95:

5.

3. The composition for forming a wafer edge protection film for semiconductor manufacturing according to claim 1, wherein the difference (V1-V2) between the evaporation rate (V1) of the first solvent and the evaporation rate (V2) of the second solvent is 0.10 or more.

4. 2. The composition for forming a wafer edge protection film for semiconductor manufacturing according to claim 1, wherein the content of the solvent is 70% by mass to 99% by mass.

5. The composition for forming a wafer edge protection film for semiconductor manufacturing according to claim 1 , which has a viscosity of 100 cps or less at 25° C.

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

7. A method for forming a protective film, comprising the step of forming a protective film which is a cured product of a coating film made of the composition for forming a wafer edge protective film for semiconductor manufacturing according to claim 1.

8. The method for forming a protective film according to claim 7, wherein the protective film has a thickness of 1 to 10,000 nm.

9. The method for forming a protective film as described in claim 7, wherein the protective film is a protective film for preventing metal contamination of the edge and bevel portions of the wafer surface.

10. The method for forming a protective film according to claim 7, wherein the protective film is a protective film that has been hardened by exposure to light having a wavelength of 170 to 800 nm.

11. (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; (C) etching a semiconductor substrate using the resist pattern as a mask; A method for manufacturing a semiconductor device comprising: The method includes a step (X) of forming a protective film on the front end, the bevel portion, and optionally the back end of a semiconductor manufacturing wafer using the composition for forming a protective film for a semiconductor manufacturing wafer according to any one of claims 1 to 6, A method for manufacturing a semiconductor device.

12. The method for manufacturing a semiconductor device according to claim 11, wherein the step (X) is performed before the step (A).

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

14. The method for manufacturing a semiconductor device according to claim 11, wherein the step (X) is performed after the step (B) or the step (C).

15. The step (X) is carried out before the step (A); In the step (A), the resist film is formed on at least a portion of the protective film, A step (Y) of removing the resist film on the protective film; The method for manufacturing a semiconductor device according to claim 11 .

16. The method for manufacturing a semiconductor device according to claim 11, further comprising the step (Z) of removing the protective film.

17. The method for manufacturing a semiconductor device according to claim 15, further comprising the step (Z) of removing the protective film after the step (Y).

18. The method for manufacturing a semiconductor device according to claim 11 , wherein the resist film contains a metal.

19. The composition for forming a wafer edge protection film for semiconductor manufacturing is photosensitive, The method for manufacturing a semiconductor device according to claim 11, wherein the formation of the protective film in the step (X) is carried out by applying the composition for forming a wafer edge protective film for semiconductor manufacturing, exposing a predetermined area to light, and developing the composition.

20. The method for producing a semiconductor device according to claim 11, wherein the formation of the protective film in the step (X) is carried out by spin-coating the composition for forming a wafer edge protective film for semiconductor production.

21. 17. The method for manufacturing a semiconductor device according to claim 16, wherein 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 cleaning liquid for semiconductors.

22. A method for manufacturing a wafer for semiconductor manufacturing, comprising the steps of: A process for producing a wafer having a surface edge and a bevel portion protected by a protective film formed by applying a composition for forming a wafer edge protective film for semiconductor production according to any one of claims 1 to 6 to an edge of a wafer precursor; A method for manufacturing a wafer for semiconductor manufacturing, comprising:

Images