Wafer edge protective film-forming composition for semiconductor manufacturing

Abstract

To provide a protective-film forming composition for forming a protective film of a front surface end portion and a bevel portion of a substrate (wafer) for semiconductor manufacturing in a semiconductor device manufacturing process, a protective film formed of the protective-film forming composition, a wafer for semiconductor manufacturing fabricated using the protective film, and methods for manufacturing the wafer for semiconductor manufacturing and a semiconductor device.SOLUTION: A wafer end protective-film forming composition for semiconductor manufacturing includes: a polymer or compound having a crosslinkable group, and a solvent. The solvent contains a first solvent and a second solvent. When an evaporation rate of n-butyl acetate is set as 1, an evaporation rate of the first solvent is 0.10 or more and an evaporation rate of the second solvent is 0.05 or less.SELECTED DRAWING: None

Description

Technical Field

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

Background Art

[0002] In the manufacture of semiconductor devices, with the complication of the manufacturing process, for example, for the purpose of improving the etching selectivity, a method of applying a chemical solution containing a metal to a wafer has been studied. Further, for example, since the resolution of a resist pattern is high when exposure is performed using extreme ultraviolet light (EUV), and it has high etching resistance, forming a resist film using a resist containing an inorganic metal has been studied. By the way, the adhesion of metal to an unintended part of a wafer in the semiconductor device manufacturing process greatly affects the electrical characteristics of the semiconductor device. However, when forming a coating film containing a metal as described above, the chemical solution supplied to the surface of the wafer flows into the peripheral end faces and the peripheral edge parts of the back surface of the wafer, and a coating film is formed even on these unintended peripheral end faces and back surface peripheral edge parts, so there is a concern that these parts will be metal-contaminated. And when the contaminated part of the wafer comes into contact with a wafer processing apparatus such as an exposure apparatus or an etching apparatus or a wafer transfer mechanism, the wafers to be transferred and processed after the said wafer via these processing apparatuses and transfer mechanisms are also metal-contaminated, that is, there is a risk of cross-contamination.

[0003] A technique is disclosed that can form the coating film so that the peripheral end faces and the back surface side peripheral edge parts, which are the peripheral edge parts of the substrate, do not come into contact with the coating film when forming a coating film on the surface of the substrate (Patent Document 1).

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

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0006] The problem to be solved by the present invention is to provide a protective film-forming composition capable of forming a protective film with a good film state and no abnormal shape (partial swelling or dent) on the surface end portion and bevel portion of a semiconductor manufacturing substrate (wafer) by a simple method of coating in the manufacture of a semiconductor device, a protective film formed by the protective film-forming composition, a semiconductor manufacturing wafer manufactured using the protective film, the semiconductor manufacturing wafer, and a method for manufacturing a semiconductor device.

Means for Solving the Problems

[0007] The present invention includes the following. [1] A composition for forming a protective film at the end of a semiconductor manufacturing wafer, comprising a polymer or compound having a crosslinkable group and a solvent, wherein the solvent includes a first solvent and a second solvent, when the evaporation rate of n-butyl acetate is set to 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 at the end of a semiconductor manufacturing wafer. [2] The composition for forming a protective film at the end of a semiconductor manufacturing wafer according to [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 protective film at the end of a semiconductor manufacturing wafer 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, and the constituent elements of the second solvent are carbon, oxygen, and hydrogen. The composition for forming a wafer edge protective film for semiconductor manufacturing according to any one of [1] to [3]. [5] The composition for forming a wafer edge protective 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] The composition for forming a wafer edge protective 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 protective film for semiconductor manufacturing according to any one of [1] to [6], which is photosensitive. [8] The composition for forming a wafer edge protective 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 composed 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 wafer surface edge and bevel portion.

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

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

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

[14] (A) A step of forming a resist film on a semiconductor substrate, (B) A step of forming a resist pattern by irradiating the resist film with light or an electron beam and then developing it, (C) A step of processing the semiconductor substrate by etching using the resist pattern as a mask, In a method for manufacturing a semiconductor device including A step (X) of forming a protective film on the surface end portion, bevel portion, and optionally the back surface end portion of the semiconductor manufacturing wafer using the composition for forming a semiconductor manufacturing wafer end protective film 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 performed before the step (A).

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

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

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

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

[18] The step (X) is performed before the step (A), In the step (A), the resist film is formed on at least a part of the protective film, The method for manufacturing a semiconductor device according to

[14] , including a step (Y) of removing the resist film on the portion above the protective film.

[14] The 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] , including a step (Z) of removing the protective film.

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

[18] , including a 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 semiconductor manufacturing wafer end protective film 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 performed by applying the composition for forming a semiconductor manufacturing wafer end protective film, exposing to light in a predetermined region, and developing.

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

[14] to

[22] , wherein the formation of the protective film in the step (X) is performed by spin coating the composition for forming an end protective film for a semiconductor manufacturing wafer.

[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, to an end portion of a wafer precursor, the composition for forming an end protective film for a semiconductor manufacturing wafer according to any one of [1] to [8], and manufacturing a wafer in which a surface end portion and a bevel portion are protected by the formed protective film; A method for manufacturing a semiconductor manufacturing wafer, comprising the above step. [Advantages of the Invention]

[0008] According to the present invention, in the manufacture of a semiconductor device, a protective film having a good film state and no abnormal shape (partial bulge or dent) can be formed on the surface end portion and bevel portion of a semiconductor manufacturing substrate (wafer) by a simple method of coating. Thereby, in a subsequent semiconductor device manufacturing process, cross-contamination due to metal contamination can be prevented, and the yield of semiconductor manufacturing device good products can be improved. [Embodiments for Carrying Out the Invention]

[0009] (Composition for Forming End Protective Film for Semiconductor Manufacturing Wafer) The composition for forming an end protective film for a semiconductor manufacturing wafer of the present invention (hereinafter sometimes referred to as "composition for forming a protective film") is a composition for forming a protective film used for protecting the surface end portion and bevel portion of a semiconductor manufacturing wafer. The composition for forming a protective film contains a polymer or compound having a crosslinkable group and a solvent.

[0010] [Solvent] The solvent contains 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 numerical value of the evaporation rate used in the present invention is a relative value with respect to the evaporation rate of n-butyl acetate. That is, the numerical value of the evaporation rate 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. And when the evaporation rate of n-butyl acetate is set to 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 inventors of the present invention have intensively studied to form a protective film with a good film state by a simple method of coating on the wafer end portions (surface end portions and bevel portions) for semiconductor manufacturing. As solvents for the composition for forming a protective film, various solvents were tried, and it was found that the evaporation rate affects the coating property of the surface end portion and the film shape of the bevel portion. For example, when a solvent with a high evaporation rate (easy to evaporate) is used alone as the solvent for the composition for forming a protective film, the coating property of the surface end portion becomes good, but the film shape of the bevel portion deteriorates (for example, partial swelling or dents occur). On the other hand, when a solvent with a low evaporation rate (difficult to evaporate) is used alone, the film shape of the bevel portion becomes good, but the coating property of the surface end portion deteriorates (the film thickness becomes thin). Furthermore, it was difficult to achieve both even when a solvent with an intermediate evaporation rate was used alone. That is, it was found that it is difficult to improve both the coating property of the surface end portion and the film shape of the bevel portion with only one type of solvent. Therefore, by using two or more solvents having different evaporation rates in combination, it was found that a protective film with a good film state can be formed by a simple method of coating on the wafer end portions (surface end portions and bevel portions) for semiconductor manufacturing, and the present invention was completed. Note that the film shape of the wafer end portion (surface end portion and bevel portion) for semiconductor manufacturing can be observed, for example, with a scanning electron microscope (magnification is, for example, 20 to 400 times, 30 to 200 times, 40 to 100 times, 50 times, 80 times, 100 times). The abnormal shape is 10 or less, preferably 5 or less, more preferably 3 or less, even more preferably 1 or less, and most preferably no abnormal shape is observed (0 (zero) abnormal locations) in the field of view in the scanning electron microscope observation.

[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 0.10 to 0.80, more preferably 0.20 to 0.60, and particularly preferably 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 preferably obtaining the effects of the present invention, 0.10 or more is preferable, 0.15 or more is more preferable, and 0.20 or more is particularly preferable. Also, 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 preferably obtaining the effects of the present invention, 50:50 to 95:5 is preferable, 60:40 to 93:7 is more preferable, and 70:30 to 90:10 is particularly preferable.

[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 a nitrogen atom and a halogen atom in its constituent elements. The second solvent preferably does not contain a nitrogen atom and a halogen atom in its constituent elements.

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

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

[0021]

Table 1

[0022] The solvent may contain 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 50% by mass to 100% by mass is preferable, 75% by mass to 100% by mass is more preferable, and 90% by mass to 100% by mass is particularly preferable.

[0024] The content of the solvent in the composition for forming a protective film is not particularly limited, but 70% by mass to 99% by mass is preferable, 75% by mass to 98% by mass is more preferable, and 80% by mass to 95% by mass is particularly preferable.

[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 50% by mass to 99% by mass is preferable, 60% by mass to 98% by mass is more preferable, and 75% by mass to 95% by mass is particularly preferable.

[0026] <Polymer or compound having a crosslinkable group> The crosslinkable group means a group capable of forming a crosslinked structure by the action of light, electron beam, other electromagnetic waves, radicals, acids, heat, water, oxygen, etc. For example, epoxy group, (meth)acrylic group, vinyl group, carboxyl group, thiol group, silanol group, cinnamoyl group, hydroxyl group (including phenolic hydroxyl group), etc. can be mentioned, but it is not limited thereto. In this specification, "polymer" and "compound" do not necessarily mean separate substances, and a substance containing a polymer may sometimes be referred to as a "compound". The protective film (cured film) using the above "polymer" and "compound" exhibits solubility in a developer such that, in an evaluation according to, for example, "[5] Curing property evaluation 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, with respect to the film in the unexposed portion.

[0027] Examples of the polymer or compound having a crosslinkable group can be given as follows, but it is not limited thereto. · Epoxy (meth)acrylate (for example, the reaction product of a glycidyl etherified product of cresol novolak resin and (meth)acrylic acid), · Cinnamic acid grafted epoxy novolak, · Phenoplast, which is a thermosetting material obtained by polycondensation accompanied by water removal of phenol and aldehyde and formation of a three-dimensional network, · For example, melamine resins such as trimethylol melamine and hexamethylol melamine, urea resins such as dimethylolpropylene urea, dimethylolethylene urea, and dimethylolhydroxyethylene urea, aminoplast resins such as dimethylol urea resin, · (Block) isocyanate, · Vinyl ether, · Polysiloxane resin having a (meth)acrylic group · Epoxy resin.

[0028] Here, an example of a polymer or compound having a crosslinkable group is given. An example of a polymer or compound having a crosslinkable group is a polymer having a structural unit represented by the following formula (1-1). [Chemical formula] (In formula (1-1), Ar represents a benzene ring, a naphthalene ring or an anthracene ring, and R 1 represents a hydroxy group, a mercapto group which may be protected by a methyl group, an amino group which may be protected by a methyl group, a halogeno group, or an alkyl group having 1 to 10 carbon atoms which may be substituted or interrupted by a hetero atom and 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 when n2 = 2, represents a nitrogen atom or an amide bond.)

[0029] Examples of the alkyl group having 1 to 10 carbon atoms include methyl group, ethyl group, n-propyl group, i-propyl group, cyclopropyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group, cyclobutyl group, 1-methyl-cyclopropyl group, 2-methyl-cyclopropyl group, n-pentyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl-n-propyl group, 1,2-dimethyl-n-propyl group, 2,2-dimethyl-n-propyl group, 1-ethyl-n-propyl group, cyclopentyl group, 1-methyl-cyclobutyl group, 2-methyl-cyclobutyl group, 3-methyl-cyclobutyl group, 1,2-dimethyl-cyclopropyl group, 2,3-dimethyl-cyclopropyl group, 1-ethyl-cyclopropyl group, 2-ethyl-cyclopropyl group, n-hexyl group, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, 3-methyl-n-pentyl group, 4-methyl-n-pentyl group, 1,1-dimethyl-n-butyl group, 1,2-dimethyl-n-butyl group, 1,3-dimethyl-n-butyl group, 2,2-dimethyl-n-butyl group, 2,3-dimethyl-n-butyl group, 3,3-dimethyl-n-butyl group, 1-ethyl-n-butyl group, 2-ethyl-n-butyl group, 1,1,2-trimethyl-n-propyl group, 1,2,2-trimethyl-n-propyl group, 1-ethyl-1-methyl-n-propyl group, 1-ethyl-2-methyl-n-propyl group, cyclohexyl group, 1-methyl-cyclopentyl group, 2-methyl-cyclopentyl group, 3-methyl-cyclopentyl group, 1-ethyl-cyclobutyl group, 2-ethyl-cyclobutyl group, 3-ethyl-cyclobutyl group, 1,2-dimethyl-cyclobutyl group, 1,3-dimethyl-cyclobutyl group, 2,2-dimethyl-cyclobutyl group, 2,3-dimethyl-cyclobutyl group, 2,4-dimethyl-cyclobutyl group, 3,3-dimethyl-cyclobutyl group, 1-n-propyl-cyclopropyl group, 2-n-propyl-cyclopropyl group, 1-i-propyl-cyclopropyl group, 2-i-propyl-cyclopropyl group, 1,2,2-trimethyl-cyclopropyl group, 1,2,3-trimethyl-cyclopropyl group, 2,2,3-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, 2-mercaptoethyl group, and the like can be mentioned.,

[0030] Examples of the alkylene group having 1 to 10 carbon atoms include methylene group, ethylene group, n-propylene group, isopropyl group, cyclopropylene group, n-butylene group, isobutylene group, s-butylene group, t-butylene group, cyclobutylene group, 1-methyl-cyclopropylene group, 2-methyl-cyclopropylene group, n-pentylene group, 1-methyl-n-butylene group, 2-methyl-n-butylene group, 3-methyl-n-butylene group, 1,1-dimethyl-n-propylene group, 1,2-dimethyl-n-propylene group, 2,2-dimethyl-n-propylene, 1-ethyl-n-propylene group, cyclopentylene group, 1-methyl-cyclobutylene group, 2-methyl-cyclobutylene group, 3-methyl-cyclobutylene group, 1,2-dimethyl-cyclopropylene group, 2,3-dimethyl-cyclopropylene group, 1-ethyl-cyclopropylene group, 2-ethyl-cyclopropylene group, n-hexylene group, 1-methyl-n-pentylene group, 2-methyl-n-pentylene group, 3-methyl-n-pentylene group, 4-methyl-n-pentylene group, 1,1-dimethyl-n-butylene group, 1,2-dimethyl-n-butylene group, 1,3-dimethyl-n-butylene group, 2,2-dimethyl-n-butylene group, 2,3-dimethyl-n-butylene group, 3,3-dimethyl-n-butylene group, 1-ethyl-n-butylene group, 2-ethyl-n-butylene group, 1,1,2-trimethyl-n-propylene group, 1,2,2-trimethyl-n-propylene group, 1-ethyl-1-methyl-n-propylene group, 1-ethyl-2-methyl-n-propylene group, cyclohexylene group, 1-methyl-cyclopentylene group, 2-methyl-cyclopentylene group, 3-methyl-cyclopentylene group, 1-ethyl-cyclobutylene group, 2-ethyl-cyclobutylene group, 3-ethyl-cyclobutylene group, 1,2-dimethyl-cyclobutylene group, 1,3-dimethyl-cyclobutylene group, 2,2-dimethyl-cyclobutylene group, 2,3-dimethyl-cyclobutylene group, 2,4-dimethyl-cyclobutylene group, 3,3-dimethyl-cyclobutylene group, 1-n-propyl-cyclopropylene group, 2-n-propyl-cyclopropylene group, 1-isopropyl-cyclopropylene group, 2-isopropyl-cyclopropylene group, 1,2,2-trimethyl-cyclopropylene group, 1,2,3-trimethyl-cyclopropylene group, 2,2,Examples thereof 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 or an n-decylene group.,

[0031] R 1 An example of an alkyl group having 1 to 10 carbon atoms which is substituted or interrupted by a hetero atom in 1 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 1,1-dimethyl-n-butoxy group, a 1,2-dimethyl-n-butoxy group, a 1,3-dimethyl-n-butoxy group, a 2,2-dimethyl-n-butoxy group, a 2,3-dimethyl-n-butoxy group, a 3,3-dimethyl-n-butoxy group, a 1-ethyl-n-butoxy group, a 2-ethyl-n-butoxy group, a 1,1,2-trimethyl-n-propoxy group, a 1,2,2,-trimethyl-n-propoxy group, a 1-ethyl-1-methyl-n-propoxy group, a 1-ethyl-2-methyl-n-propoxy group, an n-heptyloxy group, an n-octyloxy group and an n-nonyloxy group, etc.,

[0033] A is, for example, a group represented by the following formula (A).

Chemical formula

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

[0035] The above “may be interrupted” means that in the case of an alkylene group having 2 to 10 carbon atoms, any carbon-carbon atom in the alkylene group is interrupted by a heteroatom (i.e., an ether bond in the case of oxygen, a sulfide bond in the case of sulfur), an ester bond or an amide bond. In the case of a methylene group having 1 carbon atom, it means having a heteroatom (i.e., an ether bond in the case of oxygen, a sulfide bond in the case of sulfur), an ester bond or an amide bond on either one of the carbons of the methylene group.

[0036] T 1 When n2 = 1, it 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. 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 is preferable.

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

[0038] L 1 represents a single bond or an alkylene group having 1 to 10 carbon atoms, and is preferably the following formula (1-2).

Chemical formula

[0039] The halogeno group refers to halogen - X (F, Cl, Br, I) substituted for hydrogen.

[0040] The polymer having a structural unit represented by formula (1-1) is obtained, for example, by reacting a polymer having a unit structure represented by the following formula (1-1’) with (meth)acrylic acid.

Chemical formula

[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.), epoxy novolac resin D.E.N (registered trademark) series (manufactured by Dow Chemical Japan Co., Ltd.), etc.

[0042] The weight-average molecular weight of the polymer having the structural unit represented by the 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 the formula (1-1’) include those having the following unit structures. [Chemical formula] 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 2,000 to 50,000, more preferably 2,500 to 25,000, and particularly preferably 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 with respect to the film constituent components. The film constituent components are the components obtained by removing the volatile components (solvents) from the composition for forming a protective film.

[0047] [Other components] Furthermore, the composition for forming a protective film may contain, if necessary, a radical polymerization initiator (such as a photoinitiator), 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 polyfunctional acrylic), an adhesion improver, an adhesion aid (such as a silane coupling agent), a surfactant, an antifoaming agent, a rheology modifier, a pigment, a dye, a storage stabilizer, a dissolution accelerator such as a polyhydric phenol or polycarboxylic acid, a sensitizer, and the like.

[0048] The radical polymerization initiator only needs to be able to release a substance that initiates radical polymerization by light irradiation and / or heating. For example, examples of the photo radical polymerization initiator include benzophenone derivatives, imidazole derivatives, bisimidazole derivatives, N-aryl glycine derivatives, organic azide compounds, titanocene compounds, aluminates complexes, organic peroxides, N-alkoxypyridinium salts, thioxanthone derivatives, and the like. More specifically, benzophenone, 1,3-di(tert-butyldioxycarbonyl)benzophenone, 3,3’,4,4’-tetrakis(tert-butyldioxycarbonyl)benzophenone, 3-phenyl-5-isoxazolone, 2-mercaptobenzimidazole, bis(2,4,5-triphenyl)imidazole, 2,2-dimethoxy-1,2-diphenylethane-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 can be mentioned, but are not limited thereto.

[0049] As the above-mentioned photoinitiator, commercially available products can also be used. For example, IRGACURE (registered trademark) 651, 184, 369, 784, etc. manufactured by BASF Japan Ltd. can be mentioned. 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 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. can be mentioned.

[0050] In addition, as the thermal radical polymerization initiator, for example, 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, tert-butyl peroxy-2-ethylhexanoate; azo compounds such as 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), (1-phenylethyl)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, 2,2'-azobis(2-methylpropane); persulfates such as ammonium persulfate, sodium persulfate, potassium persulfate, etc. can be mentioned, but are not limited thereto.

[0051] Examples of commercially available thermal radical polymerization initiators include, for example, Peroyl (registered trademark) IB, NPP, IPP, SBP, TCP, OPP, SA, 355, L, Perbutyl (registered trademark) ND, NHP, MA, PV, 355, A, C, D, E, L, I, O, P, Z manufactured by NOF Corporation; Perhexyl (registered trademark) ND, PV, D, I, O, Z; Perocta (registered trademark) ND; Naiper (registered trademark) PMB, BMT, BW; Pertera (registered trademark) A; Perhexa (registered trademark) MC, TMH, HC, 250, 25B, C, 25Z, 22, V; Perocta (registered trademark) O; Parkmill (registered trademark) ND, D; Permenta (registered trademark) H; Nofmer (registered trademark) BC manufactured by Wako Pure Chemical Industries, Ltd.; V-70, V-65, V-59, V-40, V-30, VA-044, VA-046B, VA-061, V-50, VA-057, VA-086, VF-096, VAm-110, V-601, V-501 manufactured by Wako Pure Chemical Industries, Ltd.; IRGACURE (registered trademark) 184, 369, 651, 500, 819, 907, 784, 2959, CGI1700, CGI1750, CGI1850, CG24-61, DAROCUR (registered trademark) 1116, 1173, 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, etc. manufactured by Lamberti, but are not limited thereto.

[0052] Only one type of radical polymerization initiator may be used, or two or more types may be used in combination. 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, 50 parts by mass or less, 20 parts by mass or less, 10 parts by mass or less with respect to 100 parts by mass of the polymer or compound having a crosslinkable group.

[0053] As the coincidence 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'-butylidenebis(3-methyl-6-t-butylphenol), triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 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'-methylenebis(4-methyl-6-t-butylphenol), 2,2'-methylenebis(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-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 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-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-5-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, etc. can be mentioned., 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. Commercially available products may be used as the above polymerization inhibitor, and specific examples include Irganox-3114 (manufactured by BASF Japan Ltd.).

[0054] Only one kind of polymerization inhibitor may be used, or two or more kinds may be used in combination. 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 the surfactant include polyoxyethylene alkyl ether compounds such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; polyoxyethylene alkylaryl ether compounds such as polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether; polyoxyethylene·polyoxypropylene block copolymer compounds; sorbitan fatty acid ester compounds such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan trioleate, and sorbitan tristearate; polyoxyethylene sorbitan fatty acid ester compounds such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, and polyoxyethylene sorbitan tristearate. Further, fluorine-based surfactants such as the trade names F-top EF301, EF303, EF352 (manufactured by Tochem Products Co., Ltd.), the trade names Megafac F171, F173, R-08, R-30 (manufactured by Dainippon Ink and Chemicals, Inc.), Fluorad FC430, FC431 (manufactured by Sumitomo 3M Limited), the trade names Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd.), etc., and organosiloxane polymer - KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), etc. can be mentioned.

[0056] Only one kind of surfactant may be used, or two or more kinds may be used in combination. The content of the surfactant is preferably 0.1 part by mass or more, 0.5 part by mass or more, 5 parts by mass or less, and 2 parts by mass or less with respect to 100 parts by mass of the polymer or compound having a crosslinkable group.

[0057] As the acid catalyst, acidic compounds, basic compounds, or various compounds that generate acids or bases by 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 amine compounds include tertiary amines such as triethanolamine, tributanolamine, trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, tri-tert-butylamine, tri-n-octylamine, triisopropanolamine, phenyldiethanolamine, stearyldiethanolamine, and diazabicyclooctane; aromatic amines such as pyridine and 4-dimethylaminopyridine. Primary amines such as benzylamine and n-butylamine, and secondary amines such as diethylamine and di-n-butylamine are also included as amine compounds. Examples of ammonium hydroxide compounds include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, benzyltriethylammonium hydroxide, cetyltrimethylammonium hydroxide, phenyltrimethylammonium hydroxide, and phenyltriethylammonium hydroxide.

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

[0061] Examples of thermal acid generators 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 (p-phenolsulfonic acid pyridinium 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® CXC-1612, CXC-1614, TAG-2172, TAG-2179, TAG-2678, TAG2689 (manufactured by King Industries), and SI-45, SI-60, SI-80, SI-100, SI-110, SI-150 (manufactured by Sanshin Chemical Industry Co., Ltd.).

[0062] Examples of photoacid generators include sulfonium salts, iodonium salts, sulfonyldiazomethanes, N-sulfonyloxyimides, 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. For example, bis(4-tert-butylphenyl)iodonium trifluoromethanesulfonate, triphenylsulfonium trifluoromethanesulfonate, phenyl-bis(trichloromethyl)-s-triazine, benzoin tosylate, and N-hydroxysuccinimide trifluoromethanesulfonate can be mentioned.

[0063] Examples of the thermal base generators 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, phenylsulfonylacetic acid guanidine, and phenylpropiolic acid guanidine; 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; dicyandiamide; etc. Also, U-CAT (registered trademark) SA810, SA831, SA841, SA851 [manufactured by San-Apro Ltd.] etc., which are salts of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), can be mentioned.

[0064] Examples of the photo-base generator include alkylamine photo-base generators such as 9-anthrylmethyl = N,N-diethylcarbamate; cycloalkylamine photo-base 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, (E)-N-cyclohexyl-3-(2-hydroxyphenyl)acrylamide; piperidine photo-base generators such as 9-anthrylmethyl = piperidine-1-carboxylate, (E)-1-piperidino-3-(2-hydroxyphenyl)-2-propen-1-one, (2-nitrophenyl)methyl = 4-hydroxypiperidine-1-carboxylate, (2-nitrophenyl)methyl = 4-(methacryloyloxy)piperidine-1-carboxylate; guanidine photo-base generators such as guanidinium = 2-(3-benzoylphenyl)propionate, 1,2-diisopropyl-3-(bis(dimethylamino)methylene)guanidinium = 2-(3-benzoylphenyl)propionate, 1,2-dicyclohexyl-4,4,5,5-tetramethylbiguanidinium = n-butyltriphenylborate, 1,5,7-triazabicyclo[4.4.0]dec-5-enium = 2-(9-oxoxanthene-2-yl)propionate; imidazole photo-base generators such as 1-(9,10-anthraquinone-2-yl)ethyl = imidazole-1-carboxylate, and the like.

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

[0066] The method for preparing the composition for forming the protective film is not particularly limited. That is, a polymer or compound having a crosslinkable group, a solvent, and other components may be mixed at an arbitrary ratio in an arbitrary order to form a uniform solution. The composition for forming the protective film in the solution state thus prepared is preferably used after being filtered using a filter having a pore size of about 0.2 μm or the like.

[0067] As described later, in order to produce a protective film having a film thickness of about 300 nm by the 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 the measured value at 25°C using an E-type viscometer.

[0068] Also, the composition for forming the protective film is preferably photosensitive. For example, it may be a negative-type solvent development type. In the case of a photosensitive composition for forming a protective film, after applying the photosensitive protective film-forming composition (negative type) to the surface end portion, the bevel portion, and optionally the back surface end portion of the substrate, exposure and development are performed on the portion where film curing is desired, so that the bevel portion can be accurately covered with the protective film. By being photosensitive, film thickness control at the wafer edge of the protective film becomes easy, inner hams can be removed, the edge shape can be improved, and advantages such as correcting the deviation of the center position during spin coating can be obtained.

[0069] The composition for forming the 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) described in WO2018 / 190380. The compound (E) is a polymer or compound having a crosslinkable group.

[0070]

Chemical formula

[0071] The entire disclosure of WO2018 / 190380 is incorporated herein by reference in its entirety.

[0072] The composition for forming a protective film may contain polysiloxane. The polysiloxane may be a modified polysiloxane in which a part of the silanol groups is modified, for example, a modified product of polysiloxane in which a part of the silanol groups is modified with alcohol or acetal-protected. Further, the polysiloxane may be, for example, a hydrolysis condensate of a hydrolyzable silane, or a modified product in which at least a part of the silanol groups of the hydrolysis condensate is modified with alcohol or acetal-protected (hereinafter, may be referred to as "modified product of hydrolysis condensate"). The hydrolyzable silane related to the hydrolysis condensate may contain one or more kinds of hydrolyzable silanes. The polysiloxane can be assumed to have a structure having any of a cage type, a ladder type, a linear type, and a branched type main chain. Further, commercially available polysiloxane can be used.

[0073] In the present invention, the "hydrolysis condensate" of the hydrolyzable silane, that is, the product of hydrolysis condensation, includes not only a polyorganosiloxane polymer which is a condensate in which condensation is completely completed, but also a polyorganosiloxane polymer which is a partial hydrolysis condensate in which condensation is not completely completed. Such a partial hydrolysis condensate is also a polymer obtained by hydrolysis and condensation of a hydrolyzable silane, similar to a condensate in which condensation is completely completed, but is stopped by hydrolysis partially and not condensed, and therefore, a Si-OH group remains. Examples of the polysiloxane of the present invention include a hydrolysis condensate of a hydrolyzable silane containing at least one kind of hydrolyzable silane represented by the following formula (1) or a modified product thereof.

[0074] <<Formula (1)>>

Chemical formula

[0075] In formula (1), R 1is a group bonded to a silicon atom, and independently of one another, represents 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 represents 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 is a group or atom bonded to a silicon atom, and independently of one another, represents an alkoxy group, an aralkyloxy group, an acyloxy group, or a halogen atom. a represents an integer from 0 to 3.

[0076] For the specific examples of each group and atom in formula (1), and their preferred carbon numbers, the groups and carbon numbers described above for R in formulas (A-1) and (A-2) can be cited. 1 For the specific examples of each group and atom in formula (1), and their preferred carbon numbers, the groups, atoms and carbon numbers described above for X in formulas (A-1) and (A-2) can be cited. 3 For the specific examples of each group and atom in formula (1), and their preferred carbon numbers, the groups, atoms and carbon numbers described above for X in formulas (A-1) and (A-2) can be cited. 2

[0077] <<<Specific examples of the hydrolyzable silane represented by formula (1)>>> ​​Specific examples of the hydrolyzable silane represented by formula (1) include tetramethoxysilane, tetrachlorosilane, tetraacetoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane, methyltrimethoxysilane, methyltrichlorosilane, methyltriacetoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, methyltriamyloxysilane, methyltriphenoxysilane, methyltribenzyloxysilane, methyltriphenethyloxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, α-glycidoxyethyltrimethoxysilane, α-glycidoxyethyltriethoxysilane, β-glycidoxyethyltrimethoxysilane, β-glycidoxyethyltriethoxysilane, α-glycidoxypropyltrimethoxysilane, α-glycidoxypropyltriethoxysilane, β-glycidoxypropyltrimethoxysilane, β-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltripropoxysilane, γ-glycidoxypropyltributoxysilane, γ-glycidoxypropyltriphenoxysilane, α-glycidoxybutyltrimethoxysilane, α-glycidoxybutyltriethoxysilane, β-glycidoxybutyltriethoxysilane, γ-glycidoxybutyltrimethoxysilane, γ-glycidoxybutyltriethoxysilane, δ-glycidoxybutyltrimethoxysilane, δ-glycidoxybutyltriethoxysilane, (3,4-epoxycyclohexyl)methyltrimethoxysilane, (3,4-epoxycyclohexyl)methyltriethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltriethoxysilane, β-(3,4-epoxycyclohexyl)ethyltripropoxysilane, β-(3,4-epoxycyclohexyl)ethyltributoxysilane, β-(3,4-epoxycyclohexyl)ethyltriphenoxysilane, γ-(3,4-epoxycyclohexyl)propyltrimethoxysilane,γ-(3,4-Epoxycyclohexyl)propyltriethoxysilane, δ-(3,4-epoxycyclohexyl)butyltrimethoxysilane, δ-(3,4-epoxycyclohexyl)butyltriethoxysilane, glycidoxymethyldimethoxysilane, glycidoxymethyldiethoxysilane, α-glycidoxyethylmethyldimethoxysilane, α-glycidoxyethylmethyldiethoxysilane, β-glycidoxyethylmethyldimethoxysilane, β-glycidoxyethylethyldimethoxysilane, α-glycidoxypropylmethyldimethoxysilane, α-glycidoxypropylmethyldiethoxysilane, β-glycidoxypropylmethyldimethoxysilane, β-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldipropoxysilane, γ-glycidoxypropylmethyldibutoxysilane, γ-glycidoxypropylmethyldiphenoxysilane, γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylethyldiethoxysilane, γ-glycidoxypropylvinyldimethoxysilane, γ-glycidoxypropylvinyldiethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltriacetoxysilane, methylvinyldimethoxysilane, methylvinyldiethoxysilane, methylvinyldichlorosilane, methylvinyldiacetoxysilane, dimethylvinylmethoxysilane, dimethylvinylethoxysilane, dimethylvinylchlorosilane, dimethylvinylacetoxysilane, divinyldimethoxysilane, divinyldiethoxysilane, divinyldichlorosilane, divinyldiacetoxysilane, γ-glycidoxypropylvinyldimethoxysilane, γ-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-phenylaminopropyltrimethoxysilane, 3-phenylaminopropyltriethoxysilane, dimethoxymethyl-3-(3-phenoxypropylthiopropyl)silane, triethoxy((2-methoxy-4-(methoxymethyl)phenoxy)methyl)silane, benzyltrimethoxysilane, benzyltriethoxysilane, benzylmethyldimethoxysilane, benzylmethyldiethoxysilane, benzyldimethylmethoxysilane, benzyldimethylethoxysilane, benzyldimethylchlorosilane, phenethyltrimethoxysilane, phenethyltriethoxysilane, 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-propoxyphenyltriethoxysilane, i-propoxyphenyltriacetoxysilane, i-propoxyphenyltrichlorosilane, i-propoxybenzyltrimethoxysilane, i-propoxybenzyltriethoxysilane, i-propoxybenzyltriacetoxysilane, i-propoxybenzyltrichlorosilane, t-butoxyphenyltrimethoxysilane, t-butoxyphenyltriethoxysilane, t-butoxyphenyltriacetoxysilane, t-butoxyphenyltrichlorosilane, t-butoxybenzyltrimethoxysilane, t-butoxybenzyltriethoxysilane, t-butoxybenzyltriacetoxysilane, t-butoxysibenzyltrichlorosilane, methoxynaphthyltrimethoxysilane, methoxynaphthyltriethoxysilane, methoxynaphthyltriacetoxysilane, methoxynaphthyltrichlorosilane, ethoxynaphthyltrimethoxysilane, ethoxynaphthyltriethoxysilane, ethoxynaphthyltriacetoxysilane, ethoxynaphthyltrichlorosilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, γ-chloropropyltriacetoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, β-cyanoethyltriethoxysilane, thiocyanatepropyltriethoxysilane, chloromethyltrimethoxysilane, chloromethyltriethoxysilane, triethoxysilylpropyldiallylisocyanurate, bicyclo[2,2,1]heptenyltriethoxysilane, benzenesulfonylpropyltriethoxysilaneExamples 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 may be the one described in JP-A-2016-003160, (A) a polyfunctional epoxy (meth) acrylate compound, (B) a polyfunctional thiol compound, and (C) 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, it may contain (D) a polymerization inhibitor. The viscosity at 25°C may be 2,000 to 100,000 mPa·s.

[0080] The entire disclosure of JP-A-2016-003160 is incorporated herein by reference.

[0081] The composition for forming a protective film may be a film-forming composition containing a photopolymerizable substance and a photopolymerization initiator, as described in WO2009 / 104643. The photopolymerizable substance is a polymer or compound having a crosslinkable group. The photopolymerizable substance is a compound having at least one cation-polymerizable reactive group, and the cationic polymerization initiator may be a photo cationic polymerization initiator. The photopolymerizable substance is a compound having at least one radical-polymerizable reactive group, and the photopolymerization initiator may be a photo radical 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]

Chemical formula

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

[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 has the formula (2) or formula (3):

[0086]

Chemical formula

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

[0088] The entire disclosure of WO2009 / 104643 is incorporated herein by reference.

[0089] (Protective film) The protective film of the present invention is a cured product of a coating film composed of the composition for forming a protective film of the present invention. Examples of the method for forming the protective film include step (X) in the method for manufacturing a semiconductor device described below.

[0090] The protective film is, for example, a protective film for preventing metal contamination at the edge and bevel portion 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, 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, 300 nm.

[0092] The protective film is, for example, a protective film cured by irradiating light having a wavelength of 170 to 800 nm (for example, 254 nm).

[0093] As characteristics of the protective film that covers the surface edge and bevel portion of a substrate (wafer) for semiconductor manufacturing, 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 property for a stepped substrate, low sublimation amount, affinity for a hydrophobic substrate, no remaining crater foreign substances or the like on the wafer side surface (bevel portion), good edge shape, a function of suppressing inner hump (a phenomenon in which the film-forming composition remains in a tumor shape directly below the injection hole of the nozzle), etc. are preferably satisfied.

[0094] (Method for manufacturing a semiconductor device) The method for manufacturing a semiconductor device according to the present invention is (A) A step of forming a resist film on a semiconductor substrate; (B) A step of forming a resist pattern by irradiating the resist film with light or an electron beam and then developing; (C) A step of processing the semiconductor substrate by etching using the resist pattern as a mask; In the method for manufacturing a semiconductor device including a step (X) of forming a protective film on the surface edge, bevel portion, and optionally the back surface edge of a wafer for semiconductor manufacturing using the composition for forming a protective film of the present invention; is a method for manufacturing a semiconductor device.

[0095] Hereinafter, it will be described in order. <Step (A)> In step (A), a resist film is formed on a semiconductor substrate. The semiconductor substrate is a wafer used for manufacturing a semiconductor element or the like, and in addition to commonly used silicon wafers and germanium wafers, for example, compound semiconductor wafers formed by bonding 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 the size is, for example, 4, 6, 8, 12 inches, etc. Commercially available products may be used.

[0096] When using a semiconductor substrate with an inorganic film formed on its surface, the inorganic film is formed, for example, by ALD (Atomic Layer Deposition), CVD (Chemical Vapor Deposition), reactive sputtering, ion plating, vacuum evaporation, or spin coating (spin-on glass: SOG). Examples of the inorganic film include a polysilicon film, a silicon oxide film, a silicon nitride film, a BPSG (Boro-Phospho Silicate Glass) film, a titanium nitride film, a titanium oxynitride film, a tungsten film, a gallium nitride film, and a gallium arsenide film.

[0097] On such a semiconductor substrate, a resist underlayer film, a resist film, etc. with a predetermined thickness are formed by an appropriate coating method such as spraying, a spinner, or a coater. Generally, in the case of the spin coating method, each of the resist underlayer film forming composition, the resist film forming composition, etc. is supplied through a nozzle or the like from above the center of the rotating disk-shaped substrate. Usually, these films are baked using a heating means such as a hot plate.

[0098] The photoresist used for forming the resist film is not particularly limited as long as it is sensitive to the light used for exposure. In this specification, electron beam resists are also included in the photoresists. Either negative photoresists or positive photoresists can be used. There are positive photoresists composed of novolak resin and 1,2-naphthoquinone diazide sulfonic acid ester, chemically amplified photoresists composed of a binder having a group that decomposes by an acid to increase the alkali dissolution rate and a photoacid generator, chemically amplified photoresists composed of a low molecular compound that decomposes by an acid to increase the alkali dissolution rate of the photoresist, an alkali-soluble binder, and a photoacid generator, and chemically amplified photoresists composed of a binder having a group that decomposes by an acid to increase the alkali dissolution rate, a low molecular compound that decomposes by an acid to increase the alkali dissolution rate of the photoresist, and a photoacid generator, resists containing metal elements, etc. For example, product names V146G manufactured by JSR Corporation, APEX-E manufactured by Shipley Company, PAR710 manufactured by Sumitomo Chemical Co., Ltd., and product names AR2772, SEPR430 manufactured by Shin-Etsu Chemical Co., Ltd. etc. can be mentioned. Also, for example, fluorine atom-containing polymer-based 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) can be mentioned. Preferably, it is a negative photoresist.

[0099] In the resist film forming composition used for forming the resist film, one or more metals can be included. As the form of the metal, in addition to the metal alone, metal salts, metal complexes, and other metal-containing compounds can be mentioned. The metal species is not particularly limited, and for example, tin, indium, antimony, bismuth, gallium, germanium, aluminum, zirconium, hafnium, cerium, lanthanum, cesium, etc. can be mentioned.

[0100] Also, the resist film forming composition used for forming the resist film may be a metal-containing resist. A metal-containing resist, also called a metal oxide resist (MOR), typically includes a tin oxide-based resist. Examples of metal oxide resist materials include coating compositions containing a metal oxo-hydroxone network having an organic ligand by a metal-carbon bond and / or a metal carboxylate bond, as described in JP-A-2019-113855. An example of a metal-containing resist uses a peroxo ligand as a radiation-sensitive stabilizing ligand. The details of peroxo-based metal oxo-hydroxo compounds are described in the patent documents described in paragraph

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

[0101] As the baking conditions for the resist film, the baking temperature is appropriately selected from 70°C to 400°C, and the baking time is appropriately selected from 0.3 minutes to 60 minutes. Preferably, the baking temperature is 80°C to 350°C, and the baking time is 0.5 minutes to 30 minutes. More preferably, the baking temperature is 90°C to 300°C, and the baking time is 0.8 minutes 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, 2,000 nm, preferably 1,000 nm, more preferably 200 nm, and even more preferably 50 nm.

[0103] <Step (X) of forming a protective film> Step (X) of forming a protective film from the composition for forming a protective film of the present invention is performed at an arbitrary time on the surface edge of the wafer for semiconductor manufacturing, the bevel portion, and optionally the back surface edge. In step (X), preferably, the composition for forming a protective film is applied and exposed and developed in a predetermined region. Step (X) may be performed before step (A), may be performed between step (A) and step (B), or may be performed 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 referred to as the front surface, and the opposite surface is referred to as the back surface. The surface edge refers to a region having a width of usually 1 to 10 mm from the edge of the device portion provided on the substrate to the bevel portion. The bevel portion refers to a bent region (wafer side surface) connecting the surface edge and the back surface edge, and the back surface edge refers to a region corresponding to the surface edge of the back surface of the substrate.

[0105] First, the composition for forming a protective film is applied to the semiconductor substrate. The method of applying the composition for forming a protective film is not particularly limited, and for example, known means such as a spin coating method or a spray method can be adopted. For example, when the spin coating method is adopted, while rotating the semiconductor substrate at a predetermined rotation speed, the composition for forming a protective film is supplied through a nozzle from above or in the vicinity of the surface edge of the rotating disk-shaped substrate. Preferably, the bevel portion and / or the back surface edge of the substrate are also supplied through nozzles from their respective vicinities.

[0106] The conditions for spin coating can be appropriately selected and are not limited in any way. Exemplary typical conditions are as follows. · Viscosity of the composition for forming a protective film: about 100 cps or less · Rotation speed of the wafer: ·· During supply of the composition for forming a protective film: 50 to 500 rpm ·· During drying and spin-off: 700 to 2,000 rpm · Thickness of the protective film: 300 nm

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

[0108] Next, the composition for forming a protective film after exposure is developed. The development can be performed by removing the exposed portion of the composition for forming a protective film after exposure with a developer, and the development temperature and time are appropriately selected from 5°C to 50°C and 10 seconds to 300 seconds, respectively.

[0109] Examples of the organic solvent contained in the developer include alcohol solvents, ether solvents, ketone solvents, amide solvents, ester solvents, hydrocarbon solvents, and the like. The organic solvent of the above developer preferably contains an ester solvent, a ketone solvent, or a combination thereof. The above developer may contain one kind of organic solvent alone or two or more kinds of 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 the ether solvent 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, trimethylnonanone, etc.; cyclic ketone solvents such as cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, methylcyclohexanone, etc.; 2,4 - pentanedione, acetonylacetone, acetophenone, etc. Examples of amide solvents include cyclic amide solvents such as N,N’ - dimethylimidazolidinone, N - methylpyrrolidone, etc.; chain amide solvents such as N - methylformamide, N,N - dimethylformamide, N,N - diethylformamide, acetamide, N - methylacetamide, N,N - dimethylacetamide, N - methylpropionamide, etc. Examples of ester solvents include monocarboxylic acid ester solvents such as n - butyl acetate, ethyl lactate, etc.; polyhydric alcohol carboxylate solvents such as propylene glycol acetate, etc.; polyhydric alcohol partial ether carboxylate solvents such as propylene glycol monomethyl ether acetate, etc.; polycarboxylic acid diester solvents such as diethyl oxalate, etc.; carbonate solvents such as dimethyl carbonate, diethyl carbonate, etc. Examples of hydrocarbon solvents include aliphatic hydrocarbon solvents having 5 to 12 carbon atoms such as n - pentane, n - hexane, etc.; aromatic hydrocarbon solvents having 6 to 16 carbon atoms such as toluene, xylene, etc. 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] As the lower limit of the content of the organic solvent in the developer, 80% by mass is preferable, 90% by mass is more preferable, 99% by mass is further preferable, and 100% by mass is particularly preferable. By setting the content of the organic solvent in the developer within the above range, the dissolution contrast between the exposed portion and the unexposed portion can be improved,

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

[0112] Instead of the above organic solvent-based developer, an aqueous developer may be used. Specifically, it may be an alkaline aqueous solution such as sodium hydroxide, potassium hydroxide, sodium silicate, ammonia, monoethylamine, diethylamine, triethylamine, triethanolamine, tetramethylammonium hydroxide, etc. The base concentration of these aqueous solutions is not particularly limited, but for example, it can be 0.1 to 10% by mass.

[0113] In addition, alcohols and surfactants can also be added to the above developer for use. These can be respectively blended in the range of preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, based on 100 parts by mass of the developer. Examples of the surfactant include ionic and non-ionic fluorine-based surfactants, silicone-based surfactants, etc.

[0114] Examples of the development method include a method of immersing the substrate in a tank filled with the developer for a certain period of time (dip method), a method of developing by raising the developer on the substrate surface by surface tension and allowing it to stand for a certain period of time (paddle method), a method of spraying the developer on the substrate surface (spray method), a method of continuously discharging the developer while scanning a developer discharge nozzle at a constant speed on a substrate rotating at a constant speed (dynamic dispense method), etc.

[0115] Next, baking of the composition for forming a protective film after development is performed. By baking the pattern obtained after development, a desired pattern can be formed. The heating temperature in the heat treatment is usually 150°C or higher and 350°C or lower, preferably in the range of 200 to 300°C. The heat treatment time is the time until the composition for forming a protective film is cured, and preferably 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. 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). And, for example, in step (A), a resist film is formed on at least a part of the protective film. In that case, step (Y) of removing the resist film on the upper part of the protective film is performed. In step (Y), the resist film on the upper part of the protective film can be removed with a remover. At this time, similar to the above step (X), it is preferable to apply the remover to the surface edge portion, the bevel portion, and optionally the back surface edge portion of the semiconductor manufacturing wafer. Examples of the resist remover include a mixed solution composed of propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone, water, butyl acetate, an aqueous solution of tetramethylammonium, or a combination thereof. From the viewpoint of removability of the resist film among these, propylene glycol monomethyl ether acetate and water are preferable.

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

[0118] Steps (X), (Y), and (Z) can be carried out simultaneously with steps (A), (B), and (C), or at any point before or after each of these steps. For example, if step (X) is included before step (A), then between step (A) and step (B), a step (Y) of removing the resist film on the upper portion of the protective film can be carried out, and between step (Y) and step (B), a step (Z) of removing the protective film can be carried out. Also, when step (X) is included between step (A) and step (B) or step (C), a step (Z) of removing the protective film can also be carried out between step (X) and step (B) or step (C).

[0119] <Step (B)> In step (B), a resist pattern is formed by irradiating the resist film with light or an electron beam and then developing it.

[0120] The irradiation of the resist film with light or an electron beam is carried out through a mask (reticle) for forming a predetermined pattern. For example, i-line, KrF excimer laser, ArF excimer laser, EUV (extreme ultraviolet), or EB (electron beam) is used. Note that soft bake (SB) may be carried out before exposure, and post-exposure bake (PEB) may be carried out between exposure and development. 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.

[0121] For development, for example, an alkaline developer is used, 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, inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia, primary amines such as ethylamine and n-propylamine, secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, quaternary ammonium salts such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline, and cyclic amines such as pyrrole and piperidine, etc. An aqueous solution of these alkalis can be used. The base concentration of these aqueous solutions is not particularly limited, but can be, for example, 0.1 to 10% by mass.

[0122] Furthermore, an appropriate amount of alcohols such as isopropyl alcohol and surfactants such as nonionic surfactants can be added to the above aqueous solution of alkalis and used. These can be respectively blended in the range of preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, based on 100 parts by mass of the developer. Among these, preferred developers are quaternary ammonium salts, and more preferably tetramethylammonium hydroxide and choline. Furthermore, surfactants and the like can also be added to these developers.

[0123] Instead of the alkaline developer, a method of developing 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 portion where the alkali dissolution rate of the resist has not improved can also be used.

[0124] The semiconductor substrate that has undergone the above exposure and development is baked. The baking means is not particularly limited, but for example, a proximity bake furnace that secures a gap using a plurality of substrate support pins 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 the exposure and before the development. The means and conditions of baking are as described above, but may be set to 90°C or lower when it is necessary to avoid damage to the resist pattern.

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

[0127] For example, the formed resist pattern is used as a mask to process the semiconductor substrate by etching. Or, for example, the formed resist pattern is used as a mask to etch the resist underlayer film, preferably by dry etching, to form a patterned resist. At that time, when the inorganic film is formed on the surface of the used semiconductor substrate, the surface of the inorganic film is exposed, and when the inorganic film is not formed on the surface of the used semiconductor substrate, the surface of the semiconductor substrate is exposed. Then, 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, in addition to the step of shaping by dry etching using a fluorine-based gas such as carbon tetrafluoride, it also includes a surface treatment step such as removing the 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 for manufacturing a semiconductor manufacturing wafer) The method for manufacturing a semiconductor manufacturing wafer of the present invention includes a step of applying the composition for forming a protective film of the present invention to the end portion of a wafer precursor to manufacture a wafer in which the surface end portion and the bevel portion are protected by the formed protective film. The composition for forming a protective film is applied, for example, to the surface end portion, the bevel portion, and optionally the back surface end portion of the wafer precursor.

[0130] The wafer precursor refers to a semiconductor substrate obtained by subjecting it to at least one step of a semiconductor device manufacturing method. For example, in the semiconductor device manufacturing method as described above, it is a product that has undergone a process of forming an inorganic film, a resist underlayer film, a resist film, etc. on the semiconductor substrate, and for example, it is a raw material before being subjected to a process of forming a resist pattern by irradiating light or an electron beam on the resist film and then developing it.

[0131] In one embodiment, the composition for forming a protective film of the present invention is spin-coated onto the surface end portion, the bevel portion, and optionally the back surface end portion of a wafer precursor obtained through one or more steps of a semiconductor device manufacturing process.

[0132] Thereafter, the semiconductor substrate may be baked. In that case, the baking means is not particularly limited, but for example, a proximity bake furnace that secures a gap using a plurality of substrate support pins 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, and for 1 to 30 minutes. After applying the composition for forming a protective film, known processes in the semiconductor manufacturing process such as edge bead removal and back rinsing may be performed on the end face of the protective film.

[0133] (Semiconductor manufacturing wafer) The semiconductor manufacturing wafer of the present invention is a semiconductor manufacturing wafer in which the wafer end portion is protected, and is a semiconductor manufacturing wafer formed by applying the composition for forming a protective film of the present invention to the wafer end portion.

Examples

[0134] Hereinafter, the present invention will be described more specifically with reference to synthesis examples and examples, but the present invention is not limited only to the following examples.

[0135] In the examples, the apparatuses 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 the molecular weight obtained in terms of polystyrene by GPC analysis. The GPC measurement was carried out using a GPC apparatus (trade name: HLC-8320GPC, manufactured by Tosoh Corporation), GPC columns (TSKgel Super-Multipore HZ-N (2 columns)), a column temperature of 40 °C, a eluent (elution solvent) of tetrahydrofuran, a flow rate (flow velocity) of 0.35 mL / min, and a standard sample of polystyrene (manufactured by Sigma-Aldrich).

[0137] (2) Evaporation rate The evaporation rate used in the present invention is the evaporation rate obtained by ASTM D 3539. However, the numerical value of the evaporation rate used in the present invention is the relative value with respect to the evaporation rate of n-butyl acetate. That is, the numerical value of the evaporation rate 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 (n-butyl acetate = 1) of the solvents used in the following examples 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] Synthesis of polymer <Synthesis Example 1> Product name: EOCN-104S (manufactured by Nippon Kayaku Co., Ltd.) 50.00 g, acrylic acid 16.60 g, tetrabutylphosphonium bromide 2.93 g, and hydroquinone 0.13 g were added to 162.54 g of propylene glycol monomethyl ether acetate (PGMEA), and the mixture was heated and stirred at 100 °C for 18 hours under a nitrogen atmosphere. 70 g of an anion exchange resin (product name: Dowex [registered trademark] 550A, manufactured by Murotachi Techno Co., Ltd.) and 70 g of a cation exchange resin (product name: Amberlite [registered trademark] 15JWET, manufactured by Organo Co., Ltd.) were added to the obtained solution, and ion exchange treatment was carried out at room temperature for 4 hours. After separating the ion exchange resin, a compound solution was obtained. The repeating unit of the obtained compound corresponded to the following formula, and the weight average molecular weight measured by GPC in terms of standard polystyrene was 5100.

Chemical formula

[0139] <Synthesis Example 2> Product name: EOCN-104S (manufactured by Nippon Kayaku Co., Ltd.) 15.00 g, acrylic acid 4.98 g, tetrabutylphosphonium bromide 0.88 g, and hydroquinone 0.04 g were added to 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 an anion exchange resin (product name: Dowex [registered trademark] 550A, manufactured by Murotachi Techno Co., Ltd.) and 20 g of a cation exchange resin (product name: Amberlite [registered trademark] 15JWET, manufactured by Organo Co., Ltd.) were added to the obtained solution, and ion exchange treatment was carried out at room temperature for 4 hours. After separating the ion exchange resin, a compound solution was obtained. The repeating unit of the obtained compound corresponded to the following formula, and the weight average molecular weight measured by GPC in terms of standard polystyrene was 6100.

Chemical formula

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

Chemical formula

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

Chemical formula

[0142] [2] Preparation of Composition for Forming Protective Film <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 PGMEA solution of Megafac R-30 (manufactured by Dainippon Ink and Chemicals, Inc.) as a surfactant, 0.05 g of Irganox 3114 (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 0.2 μm pore size polytetrafluoroethylene microfilter 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, Inc.) as a surfactant, 0.05 g of Irganox 3114 (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 0.2 μm pore size polytetrafluoroethylene microfilter 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, Inc.) as a surfactant, 0.05 g of Irganox 3114 (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 0.2 μm pore size polytetrafluoroethylene microfilter 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 PGMEA solution of Megafac R-30 (manufactured by Dainippon Ink and Chemicals, Inc.) as a surfactant, 0.05 g of Irganox 3114 (manufactured by BASF Japan Ltd.) as an antioxidant, 2.47 g of PGMEA, and 3.25 g of DPM were added and mixed. The solution was filtered using a 0.2 μm pore size polytetrafluoroethylene microfilter 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, Inc.) as a surfactant, 0.05 g of Irganox 3114 (manufactured by BASF Japan Ltd.) as an antioxidant, and 6.36 g of EL were added and mixed. The solution was filtered using a 0.2 μm pore size polytetrafluoroethylene microfilter to obtain a composition for forming a protective film.

[0147] <Preparation Example 6> 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 PGMEA solution of Megafac R-30 (manufactured by Dainippon Ink and Chemicals, Inc.) as a surfactant, 0.05 g of Irganox 3114 (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) were added and mixed. The solution was filtered using a 0.2 μm pore size polytetrafluoroethylene microfilter to obtain a composition for forming a protective film.

[0148] [3] Observation of the side surface (bevel part) of the wafer edge after coating As Comparative Examples 1 to 4 and Examples 1 to 2, the composition for forming a protective film prepared in Preparation Examples 1 to 6 was spin-coated on a silicon substrate to a film thickness of 900 nm to form a protective film. The shape of the protective film on the edge side surface (bevel portion) of this silicon substrate was observed using a scanning electron microscope (S-4800) manufactured by Hitachi High-Technologies Corporation (magnification: 50 times). When no abnormal shape (partial bulge or dent) was observed in the protective film, it was evaluated as "〇", and when an abnormal shape (partial bulge or dent) was observed in the protective film, it was evaluated as "×". The results are shown in Table 2 described later.

[0149] [4] Observation of the wafer edge portion (surface end portion) after coating As Comparative Examples 1 to 4 and Examples 1 to 2, the composition for forming a protective film prepared in Preparation Examples 1 to 6 was spin-coated on a silicon substrate to a film thickness of 900 nm to form a protective film. The film shape of the edge portion (surface end portion) of this silicon substrate was observed using DEKTAK XT-A manufactured by BRUKER, and the coating property of the coated film was evaluated. When the coating property was good, it was designated as "〇", when the coating property was slightly poor, it was designated as "△", and when the coating property was poor, it was designated as "×", and the results are shown in Table 2 described later. Here, good coating property means that the thickness of the protective film at a location 500 μm inside from the outermost end of the wafer surface is 80% or more of the thickness of the protective film at a location 1500 μm inside from the outermost end. Slightly poor coating property means that the thickness of the protective film at a location 500 μm inside from the outermost end of the wafer surface is more than 30% and less than 80% of the thickness of the protective film at a location 1500 μm inside from the outermost end. Poor coating property means that the thickness of the protective film at a location 500 μm inside from the outermost end of the wafer surface is less than 30% of the thickness of the protective film at a location 1500 μm inside from the outermost end.

[0150] [5] Evaluation of curability after exposure As Comparative Examples 1 to 4 and Examples 1 to 2, the composition for forming a protective film prepared in Preparation Examples 1 to 6 was spin-coated on a silicon wafer, and then, using the wafer edge exposure module (WEE) of the coater-developer LithiusPro manufactured by Tokyo Electron Limited, mercury lamp light was irradiated at an exposure dose of 130 mJ / cm 2 (wavelength: 254 nm) to the wafer edge portion. After the exposure, development was carried out for 30 seconds using OK73 thinner (manufactured by Tokyo Ohka Kogyo Co., Ltd.) as a developer to form a pattern on the wafer edge portion. Using an optical interference film thickness measuring device (VM-3210) manufactured by Screen Holdings Co., Ltd., the film thickness after coating and the film thickness of the pattern remaining after development were measured, 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 composition for forming a protective film 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

Claims

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 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. 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 claim 1 .

5. 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.

6. 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.

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

8. 2. The composition for forming a wafer edge protection film for semiconductor manufacturing according to claim 1, 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 claims 1 to 8.

10. The protective film of claim 9 having a thickness of 1 to 10,000 nm.

11. The protective film according to claim 9, which is a protective film for preventing metal contamination of an edge and a bevel portion of a wafer surface.

12. The protective film according to claim 9, which is cured by irradiation with light having a wavelength of 170 to 800 nm.

13. A semiconductor manufacturing wafer having a protected wafer surface edge and bevel portion, the semiconductor manufacturing wafer being formed by applying a composition for forming a semiconductor manufacturing wafer edge protection film according to any one of claims 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 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 8. A method for manufacturing a semiconductor device.

15. The method for manufacturing a semiconductor device according to claim 14 , wherein the step (X) is performed before the step (A).

16. The method for manufacturing a semiconductor device according to claim 14, wherein the step (X) is performed between the step (A) and the step (B).

17. The method for manufacturing a semiconductor device according to claim 14 , wherein the step (X) is performed 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; The method for manufacturing a semiconductor device according to claim 14.

19. The method for manufacturing a semiconductor device according to claim 14, further comprising the step (Z) of removing the protective film.

20. 20. The method for manufacturing a semiconductor device according to claim 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 claim 14 , 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 claim 14, 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.

23. The method for producing a semiconductor device according to claim 14, 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.

24. 20. The method for manufacturing a semiconductor device according to claim 19, 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.

25. 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 8 to an edge of a wafer precursor; A method for manufacturing a wafer for semiconductor manufacturing, comprising:

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