Protective film-forming composition

Abstract

A protective film is provided that exhibits high chemical resistance, good optical parameters, and a desirable dry etching selectivity in a lithography process for semiconductor manufacturing. (A) A compound that does not have a repeating structural unit, comprising a terminal group (A1), a multi-group (A2), and a linker (A3), wherein the terminal group (A1) is coupled only to the linker (A3), the multi-group (A2) is coupled only to the linker (A3), the linker (A3) is coupled to the terminal group (A1) at one end and to the multi-group (A2) at the other end, and may optionally be coupled to another linker (A3), and the terminal group (A1) is any one of the structures of the following formula (I). [In formula (I), * indicates a bonding site with a linker (A3). X represents an ether bond, an ester bond, or a nitrogen atom, and when X is an ether bond or an ester bond, n=1, and when X is a nitrogen atom, n=2.] The polyvalent group (A2) is a 2 to 4-valent group selected from the group consisting of -O-, an aliphatic hydrocarbon group, a combination of an aromatic hydrocarbon group with fewer than 10 carbon atoms and an aliphatic hydrocarbon group, and a combination of an aromatic hydrocarbon group with 10 or more carbon atoms and -O-, and the linker (A3) represents an aromatic hydrocarbon group. The composition is a protective film-forming composition for a wet etching solution for semiconductors comprising (B) a thermal acid generating agent (B-1) and / or a curing agent (B-2), and (C) a solvent.

Description

Technology Field

[0001] The present invention relates to a composition for forming a protective film having excellent resistance to a wet etching solution for semiconductors, particularly an aqueous solution of basic hydrogen peroxide, in a lithography process in semiconductor manufacturing. Furthermore, the invention relates to a protective film obtained from the composition, a method for manufacturing a substrate with the protective film attached, a resist underlayer film to which the composition is applied, a method for manufacturing a substrate with a resist pattern attached, and a method for manufacturing a semiconductor device. Background Technology

[0002] As the thinning of the gate insulating film leads to current leakage between the gate electrode and the substrate, causing a problem of increased power consumption, high-dielectric constant films (high-k materials) with a higher relative dielectric constant than SiO2 are used as gate insulating films, and metal gates are used as gate electrodes combined with high-k materials. In the manufacturing process of high-k metal gates, a protective film is prepared on a substrate having a TiN film, a photoresist is applied, and after patterning, the TiN is removed by wet etching. The protective film used here requires resistance to chemicals, particularly resistance to an ammonia hydrogen peroxide solution (SC-1).

[0003] Patent Document 1 discloses a protective film-forming composition for a wet etching solution for semiconductors, comprising a compound or polymer thereof containing at least one set of two adjacent hydroxyl groups within a molecule and a solvent. Prior art literature

[0004] International Patent Application Publication No. 2019 / 124474 The problem to be solved

[0005] There is a demand for the development of a technology that provides a protective film with higher chemical resistance, particularly resistance to ammonia hydrogen peroxide solution (SC-1). means of solving the problem

[0006] The present invention includes the following.

[0007] [1]

[0008] (A) A compound that does not have repeating structural units,

[0009] It includes a terminal device (A1), a multi-device (A2), and a connector (A3),

[0010] The terminal device (A1) is coupled only with the connector (A3), and

[0011] The multi-unit (A2) is coupled only with the connector (A3), and

[0012] The connector (A3) is coupled with the terminal device (A1) at one end and with the multi-device (A2) at the other end, and may optionally be coupled with another connector (A3).

[0013] The terminal organ (A1) is any one of the structures of the following formula (I), and

[0014] [Chemical Formula 1]

[0015]

[0016] [In equation (I), * indicates the connection point with the connector (A3).

[0017] X represents an ether bond, an ester bond, or a nitrogen atom; n=1 when X is an ether bond or an ester bond, and n=2 when X is a nitrogen atom.

[0018] Dagagi (A2) is,

[0019] -O-,

[0020] Aliphatic hydrocarbon group,

[0021] A combination of aromatic hydrocarbon groups and aliphatic hydrocarbon groups having fewer than 10 carbon atoms, and

[0022] A combination of aromatic hydrocarbon groups with 10 or more carbon atoms and -O-

[0023] It is a group consisting of 2 to 4 valent elements selected from the group, and

[0024] The connector (A3) represents an aromatic hydrocarbon group,

[0025] compound,

[0026] (B) a heat-generating agent (B-1) and / or a curing agent (B-2), and

[0027] (C) Solvent

[0028] including,

[0029] A protective film-forming composition for a wet etching solution for semiconductors.

[0030] [2]

[0031] A protective film-forming composition described in [1], wherein the above compound (A) is a compound represented by the following formula (II).

[0032] [Chemical Formula 2]

[0033]

[0034] [Among Equation (II),

[0035] Z 1 , Z 2 Each independently

[0036] [Chemical Formula 3]

[0037]

[0038] [In equation (I), * is Y 1 , or Y 2 It indicates the connection site with.

[0039] X represents an ether bond, an ester bond, or a nitrogen atom; n=1 when X is an ether bond or an ester bond, and n=2 when X is a nitrogen atom.

[0040] Indicates one of the following,

[0041] Y 1 , Y 2 Each independently represents an aromatic hydrocarbon group, and

[0042] X 1 , X 2 -Y each independently 1 -Z 1 or -Y 2 -Z 2 Represents,

[0043] n1 and n2 each independently represent integers from 0 to 4, provided that at least one is 1 or greater, and

[0044] m1 and m2 each independently represent 0 or 1, and

[0045] Q represents a 2 to 4-valent group selected from the group consisting of -O-, an aliphatic hydrocarbon group, a combination of an aromatic hydrocarbon group with fewer than 10 carbon atoms and an aliphatic hydrocarbon group, and a combination of an aromatic hydrocarbon group with 10 or more carbon atoms and -O-.

[0046] [3]

[0047] The above compound (A) is, the following formula (III):

[0048] [Chemical Formula 4]

[0049]

[0050] [In Equation (III), Ar represents a benzene ring, a naphthalene ring, or an anthracene ring. X represents an ether bond, an ester bond, or a nitrogen atom, and n=1 when X is an ether bond or an ester bond, and n=2 when X is a nitrogen atom.]

[0051] A protective film-forming composition described in [1] comprising a substructure represented by

[0052] [4]

[0053] A protective film-forming composition described in any one of [1] to [3], wherein the above compound (A) has a weight-average molecular weight of 300 or more and 1,500 or less.

[0054] [5]

[0055] A protective film-forming composition that does not contain novolak resin, as described in any one of [1] to [4].

[0056] [6]

[0057] A protective film-forming composition as described in any one of [1] to [5], wherein each of the above compound (A), component (B), and solvent (C) does not include a material comprising one or more aromatic groups comprising two or more substituents including a hydroxyl, thiol, and / or amine portion.

[0058] [7]

[0059] A protective film-forming composition described in any one of [1] to [6], wherein the above compound (A) has two or more of the above linkers (A3).

[0060] [8]

[0061] A protective film-forming composition described in any one of [1] to [7], wherein the above component (B) comprises a curing agent (B-2) selected from the group consisting of phenolic curing agents, amide curing agents, amine curing agents, imidazoles, acid anhydride curing agents, and organic phosphines.

[0062] [9]

[0063] A protective film-forming composition described in any one of [1] to [8], comprising (D) a compound having one phenolic hydroxyl group, or a polymer having a unit structure having one phenolic hydroxyl group.

[0064]

[10]

[0065] A protective film characterized by being a sintered coating film made of a protective film-forming composition as described in any one of [1] to [9].

[0066]

[11]

[0067] (A) A compound that does not have repeating structural units,

[0068] It includes a terminal device (A1), a multi-device (A2), and a connector (A3),

[0069] The terminal device (A1) is coupled only with the connector (A3), and

[0070] The multi-unit (A2) is coupled only with the connector (A3), and

[0071] The connector (A3) is coupled with the terminal device (A1) at one end and with the multi-device (A2) at the other end, and may optionally be coupled with another connector (A3).

[0072] The terminal organ (A1) is any one of the structures of the following formula (I), and

[0073] [Chemical Formula 5]

[0074]

[0075] [In equation (I), * indicates the connection point with the connector (A3).

[0076] X represents an ether bond, an ester bond, or a nitrogen atom; n=1 when X is an ether bond or an ester bond, and n=2 when X is a nitrogen atom.

[0077] Dagagi (A2) is,

[0078] -O-,

[0079] Aliphatic hydrocarbon group,

[0080] A combination of aromatic hydrocarbon groups and aliphatic hydrocarbon groups having fewer than 10 carbon atoms, and

[0081] A combination of aromatic hydrocarbon groups with 10 or more carbon atoms and -O-

[0082] It is a group consisting of 2 to 4 valent elements selected from the group, and

[0083] The connector (A3) represents an aromatic hydrocarbon group,

[0084] compound,

[0085] (B) a heat-generating agent (B-1) and / or a curing agent (B-2), and

[0086] (C) Solvent

[0087] including,

[0088] Resist underlayer forming composition.

[0089]

[12]

[0090] A resist underlayer forming composition described in

[11] , wherein the above compound (A) is a compound represented by the following formula (II).

[0091] [Chemical Formula 6]

[0092]

[0093] [Among Equation (II),

[0094] Z 1 , Z 2 Each independently

[0095] [Chemical Formula 7]

[0096]

[0097] [In equation (I), * is Y 1 , or Y 2 It indicates the connection site with.

[0098] X represents an ether bond, an ester bond, or a nitrogen atom; n=1 when X is an ether bond or an ester bond, and n=2 when X is a nitrogen atom.

[0099] Indicates one of the following,

[0100] Y 1 , Y 2 Each independently represents an aromatic hydrocarbon group, and

[0101] X 1 , X 2 -Y each independently 1 -Z 1 or -Y 2 -Z 2 Represents,

[0102] n1 and n2 each independently represent integers from 0 to 4, provided that at least one is 1 or greater, and

[0103] m1 and m2 each independently represent 0 or 1, and

[0104] Q represents a 2 to 4-valent group selected from the group consisting of -O-, an aliphatic hydrocarbon group, a combination of an aromatic hydrocarbon group with fewer than 10 carbon atoms and an aliphatic hydrocarbon group, and a combination of an aromatic hydrocarbon group with 10 or more carbon atoms and -O-.

[0105]

[13]

[0106] The above compound (A) is, the following formula (III):

[0107] [Chemical Formula 8]

[0108]

[0109] [In Equation (III), Ar represents a benzene ring, a naphthalene ring, or an anthracene ring. X represents an ether bond, an ester bond, or a nitrogen atom, and n=1 when X is an ether bond or an ester bond, and n=2 when X is a nitrogen atom.]

[0110] A resist underlayer forming composition described in

[11] , comprising a substructure indicated by

[0111]

[14]

[0112] A resist underlayer forming composition described in any one of

[11] to

[13] , wherein the above compound (A) has a weight-average molecular weight of 300 or more and 1,500 or less.

[0113]

[15]

[0114] A resist underlayer forming composition that does not contain novolak resin, as described in any one of

[11] to

[14] .

[0115]

[16]

[0116] A resist underlayer forming composition as described in any one of

[11] to

[15] , wherein each of the above compound (A), component (B), and solvent (C) does not include a material comprising one or more aromatic groups comprising two or more substituents including a hydroxyl, thiol, and / or amine portion.

[0117]

[17]

[0118] A resist underlayer forming composition described in any one of

[11] to

[16] , wherein the above compound (A) has two or more of the above linkers (A3).

[0119]

[18]

[0120] A resist underlayer forming composition described in any one of

[11] to

[17] , wherein the above component (B) comprises a curing agent (B-2) selected from the group consisting of phenolic curing agents, amide curing agents, amine curing agents, imidazoles, acid anhydride curing agents, and organophosphines.

[0121]

[19]

[0122] A resist underlayer forming composition described in any one of

[11] to

[18] , comprising (D) a compound having one phenolic hydroxyl group, or a polymer having a unit structure having one phenolic hydroxyl group.

[0123]

[20]

[0124]

[11] to

[19] A resist underlayer film characterized by being a sintered product of a coating film formed from a resist underlayer film-forming composition described in any one of

[11] to

[19] .

[0125]

[21]

[0126] A method for manufacturing a protective film-attached substrate characterized by using a protective film-forming composition described in any one of [1] to [9] on a semiconductor substrate having a step and firing to form a protective film.

[0127]

[22]

[0128] A method for manufacturing a substrate with a resist pattern attached, characterized by comprising the steps of: applying a protective film-forming composition described in any one of [1] to [9] or a resist underlayer-forming composition described in any one of

[11] to

[19] onto a semiconductor substrate and firing to form a protective film as a resist underlayer; forming a resist film on the protective film, and then exposing and developing to form a resist pattern, and using the method for manufacturing a semiconductor.

[0129]

[23]

[0130] A method for manufacturing a semiconductor device comprising the steps of: forming a protective film on a semiconductor substrate on which an inorganic film may be formed on the surface using a protective film forming composition described in any one of [1] to [9]; forming a resist pattern on the protective film; dry-etching the protective film using the resist pattern as a mask; exposing the surface of the inorganic film or the semiconductor substrate; and wet-etching and cleaning the inorganic film or the semiconductor substrate using a wet-etching solution for semiconductors using the protective film after dry-etching as a mask.

[0131]

[24]

[0132] A method for manufacturing a semiconductor device comprising the steps of: forming a resist sublayer using a resist sublayer forming composition described in any one of

[11] to

[19] on a semiconductor substrate on which an inorganic film may be formed on the surface; forming a resist pattern on the resist sublayer; dry-etching the resist sublayer using the resist pattern as a mask; exposing the surface of the inorganic film or the semiconductor substrate; and etching the inorganic film or the semiconductor substrate using the resist sublayer after dry-etching as a mask. Effects of the invention

[0133] According to the protective film-forming composition of the present invention, a protective film can be formed in a lithography process in semiconductor manufacturing that exhibits high chemical resistance, good optical parameters, and a desirable dry etching selectivity ratio. Specific details for implementing the invention

[0134] <Composition>

[0135] The protective film-forming composition for a wet etching solution for semiconductors according to the present invention is,

[0136] (A) A compound that does not have repeating structural units,

[0137] It includes a terminal device (A1), a multi-device (A2), and a connector (A3),

[0138] The terminal device (A1) is coupled only with the connector (A3), and

[0139] The multi-unit (A2) is coupled only with the connector (A3), and

[0140] The connector (A3) is coupled with the terminal device (A1) at one end and with the multi-device (A2) at the other end, and may optionally be coupled with another connector (A3).

[0141] The terminal organ (A1) is any one of the structures of the following formula (I), and

[0142] [Chemical Formula 9]

[0143]

[0144] [In equation (I), * indicates the connection point with the connector (A3).

[0145] X represents an ether bond, an ester bond, or a nitrogen atom; n=1 when X is an ether bond or an ester bond, and n=2 when X is a nitrogen atom.

[0146] Dagagi (A2) is,

[0147] -O-,

[0148] Aliphatic hydrocarbon group,

[0149] A combination of aromatic hydrocarbon groups and aliphatic hydrocarbon groups having fewer than 10 carbon atoms, and

[0150] A combination of aromatic hydrocarbon groups with 10 or more carbon atoms and -O-

[0151] It is a group consisting of 2 to 4 valent elements selected from the group, and

[0152] The connector (A3) represents an aromatic hydrocarbon group,

[0153] compound,

[0154] (B) a heat-generating agent (B-1) and / or a curing agent (B-2), and

[0155] (C) Solvent

[0156] Includes

[0157] The protective film-forming composition for a wet etching solution for semiconductors according to the present invention may also be applied as a resist underlayer-forming composition, as described below.

[0158] <Compound (A)>

[0159] "Not having repeating structural units" means to exclude so-called polymers having repeating structural units, such as polyolefins, polyesters, polyamides, and poly(meth)acrylates. Preferably, the weight-average molecular weight of compound (A) is 300 or more and 1,500 or less.

[0160] The “bond” between the terminal group (A1), the multi-group (A2), and the linker (A3) refers to a chemical bond, which usually refers to a covalent bond, but an ionic bond is also acceptable.

[0161] Da-ga-gi (A2) is a 2 to 4-ga-gi.

[0162] Therefore, the aliphatic hydrocarbon group in the definition of the multivalent group (A2) is a 2 to 4-valent aliphatic hydrocarbon group.

[0163] As a non-limiting example, divalent aliphatic hydrocarbon groups include: methylene group, ethylene group, n-propylene group, isopropylene 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 group, 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, 2,2,3-trimethyl-cyclopropylene group, 1-ethyl-2-methyl-cyclopropylene group, 2-ethyl-1-methyl-cyclopropylene group,Examples include alkylene groups of 2-ethyl-2-methyl-cyclopropylene, 2-ethyl-3-methyl-cyclopropylene, n-heptylene, n-octylene, n-nonylene, or n-decanylene.

[0164] Hydrogen at any part of these groups is removed and changed into bound water, thereby inducing trivalent and tetravalent groups.

[0165] Examples of aromatic hydrocarbon groups with fewer than 10 carbon atoms in the definition of multi-group (A2) include benzene, toluene, xylene, mesitylene, cumene, styrene, indene, etc.

[0166] As for aliphatic hydrocarbon groups combined with aromatic hydrocarbon groups having less than 10 carbon atoms, in addition to the above alkylene group, 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,Examples include alkyl groups such as decyl groups.

[0167] In the definition of the multi-group (A2), the aromatic hydrocarbon group and the aliphatic hydrocarbon group having fewer than 10 carbon atoms may be combined with the linker (A3).

[0168] Examples of aromatic hydrocarbon groups with 10 or more carbon atoms in the definition of a multi-group (A2) include naphthalene, azulene, anthracene, phenanthrene, naphthacene, triphenylene, pyrene, chrysene, etc.

[0169] In the definition of the multi-group (A2), it is preferable that the aromatic hydrocarbon group having 10 or more carbon atoms is bonded to the linker (A3) via -O-.

[0170] Examples of aromatic hydrocarbon groups in the definition of the linker (A3) include aromatic hydrocarbon groups with fewer than 10 carbon atoms and aromatic hydrocarbon groups with 10 or more carbon atoms.

[0171] Preferably, the compound (A) has two or more linkers (A3).

[0172] Preferably, compound (A) is represented by the following formula (II).

[0173] [Chemical Formula 10]

[0174]

[0175] [Among Equation (II),

[0176] Z 1 , Z 2 Each independently

[0177] [Chemical Formula 11]

[0178]

[0179] [In equation (I), * is Y 1 , or Y 2 It indicates the connection site with.

[0180] X represents an ether bond, an ester bond, or a nitrogen atom; n=1 when X is an ether bond or an ester bond, and n=2 when X is a nitrogen atom.

[0181] Indicates one of the following,

[0182] Y 1 , Y 2 Each independently represents an aromatic hydrocarbon group, and

[0183] X 1 , X 2 -Y each independently 1 -Z 1 or -Y 2 -Z 2 Represents,

[0184] n1 and n2 each independently represent integers from 0 to 4, provided that at least one is 1 or greater, and

[0185] m1 and m2 each independently represent 0 or 1, and

[0186] Q represents a 2 to 4-valent group selected from the group consisting of -O-, an aliphatic hydrocarbon group, a combination of an aromatic hydrocarbon group with fewer than 10 carbon atoms and an aliphatic hydrocarbon group, and a combination of an aromatic hydrocarbon group with 10 or more carbon atoms and -O-.

[0187] In Equation (II), Z 1 , Z 2 is the terminal device (A1), Q is the multi-device (A2), Y 1 , Y 2 Each corresponds to the above connector (A3), and descriptions, examples, etc. regarding them are used here.

[0188] Preferably, compound (A) is of the following formula (III)

[0189] [Chemical Formula 12]

[0190]

[0191] [In Equation (III), Ar represents a benzene ring, a naphthalene ring, or an anthracene ring. X represents an ether bond, an ester bond, or a nitrogen atom, and n=1 when X is an ether bond or an ester bond, and n=2 when X is a nitrogen atom]

[0192] Includes a substructure indicated by .

[0193] <(B) Heat generating agent (B-1) and / or curing agent (B-2)>

[0194] The protective film-forming composition of the present invention further comprises (B) a thermal acid generating agent (B-1) and / or a curing agent (B-2).

[0195] <Heat generator (B-1)>

[0196] Examples of thermal acid generating agents include, for instance, pyridinium-p-toluenesulfonate, pyridinium-trifluoromethanesulfonate, pyridinium-p-phenolsulfonate, K-PURE [registered trademark] CXC-1612, CXC-1614, TAG-2172, TAG-2179, TAG-2678, and TAG-2689 (all manufactured by King Industries), and SI-45, SI-60, SI-80, SI-100, SI-110, and SI-150 (all manufactured by Sanshin Chemical Industry Co., Ltd.).

[0197] These heat-generating agents can be used in combination of one or more types.

[0198] When the protective film-forming composition of the present invention includes a thermal acid generating agent, the lower limit of the content is typically 0.0001 mass%, preferably 0.01 mass%, more preferably 0.1 mass% with respect to the total solid content of the protective film-forming composition, and the upper limit of the content is typically 20 mass%, preferably 15 mass%, more preferably 10 mass% with respect to the total solid content of the protective film-forming composition.

[0199] <Hardening Agent (B-2)>

[0200] There are no particular limitations on the curing agent used in the protective film-forming composition of the present invention, and any curing agent generally known as such can be used. Preferably, the curing agent is selected from the group consisting of phenolic curing agents, amide curing agents, amine curing agents, imidazoles, acid anhydride curing agents, and organophosphines.

[0201] [Phenol-based curing agent]

[0202] Phenolic curing agents include bisphenol A, bisphenol F, 4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxydiphenyl ether, 1,4-bis(4-hydroxyphenoxy)benzene, 1,3-bis(4-hydroxyphenoxy)benzene, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl ketone, 4,4'-dihydroxydiphenylsulfone, 4,4'-dihydroxybiphenyl, 2,2'-dihydroxybiphenyl, 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, phenol novolac, bisphenol A novolac, o-cresol novolac, m-cresol novolac, p-cresol novolac, Xylenol novolac, poly-p-hydroxystyrene, hydroquinone, resorcinol, catechol, t-butylcatechol, t-butylhydroquinone, fluoroglycinol, pyrogallol, t-butylpyrogallol, allylated pyrogallol, polyallylated pyrogallol, 1,2,4-benzenetriol, 2,3,4-trihydroxybenzophenone, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,4-dihydroxynaphthalene, Examples include 2,5-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,8-dihydroxynaphthalene, allylated or polyallylated products of the above dihydroxynaphthalene, allylated bisphenol A, allylated bisphenol F, allylated phenol novolac, allylated pyrrogallol, etc.

[0203] [Amid-based curing agent]

[0204] Examples of amide-based curing agents include dicyandiamide and its derivatives, polyamide resins, etc.

[0205] [Amine-based curing agent]

[0206] Examples of amine-based curing agents include aliphatic amines, polyetheramines, alicyclic amines, aromatic amines, etc.

[0207] Examples of aliphatic amines include ethylenediamine, 1,3-diaminopropane, 1,4-diaminopropane, hexamethylenediamine, 2,5-dimethylhexamethylenediamine, trimethylhexamethylenediamine, diethylenetriamine, iminobispropylamine, bis(hexamethylene)triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, N-hydroxyethylethylenediamine, tetra(hydroxyethyl)ethylenediamine, etc.

[0208] Examples of polyetheramines include triethylene glycoldiamine, tetraethylene glycoldiamine, diethylene glycolbis(propylamine), polyoxypropylenediamine, and polyoxypropylenediamine.

[0209] Examples of cycloaliphatic amines include isophoronediamine, metacendiamine, N-aminoethylpiperazine, bis(4-amino-3-methyldicyclohexyl)methane, bis(aminomethyl)cyclohexane, 3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro(5,5)undecane, norbornendiamine, etc.

[0210] Aromatic amines include tetrachloro-p-xylenediamine, m-xylenediamine, p-xylenediamine, m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, 2,4-diaminoanisole, 2,4-toluenediamine, 2,4-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 4,4'-diamino-1,2-diphenylethane, 2,4-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, m-aminophenol, m-aminobenzylamine, benzyldimethylamine, 2-(dimethylaminomethyl)phenol, triethanolamine, methylbenzylamine, α-(m-aminophenyl)ethylamine, α-(p-aminophenyl)ethylamine, diaminodiethyldimethyldiphenylmethane, α,α'-bis(4-aminophenyl)-p-diisopropylbenzene, etc. It is possible.

[0211] [Imidazoles]

[0212] Imidazoles include 2-phenylimidazole, 2-ethyl-4(5)-methylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyano-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine, Examples include 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, and epoxy resins and adducts of the imidazoles.

[0213] [Acid Anhydride Curing Agent]

[0214] Examples of acid anhydride-based curing agents include acid anhydrides and modified acid anhydrides.

[0215] Acid anhydrides include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, dodecenylsuccinic anhydride, polyadipic anhydride, polyazellatic anhydride, polysebacic anhydride, poly(ethyl octadecane dihydride) anhydride, poly(phenylhexadecane dihydride) anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, methylhymic anhydride, tetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, methylcyclohexene dicarboxylic anhydride, methylcyclohexene tetracarboxylic anhydride, ethylene glycol bistrimellitate dianhydride, hetic anhydride, and nadic anhydride. Examples include methylnadic acid anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexane-1,2-dicarboxylic acid anhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic acid dianhydride, and 1-methyl-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic acid dianhydride.

[0216] Examples of modified acid anhydrides include the acid anhydride modified with glycol. Here, examples of glycols that can be used for modification include alkylene glycols such as ethylene glycol, propylene glycol, and neopentyl glycol; and polyether glycols such as polyethylene glycol, polypropylene glycol, and polytetramethylene ether glycol. Furthermore, a copolymer polyether glycol of two or more of these glycols and / or polyether glycols may be used. Meanwhile, regarding the modified acid anhydride, it is preferable to modify it with 0.4 moles of glycol or less per 1 mole of acid anhydride.

[0217] [Organic phosphines]

[0218] Examples of organic phosphines include tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine, and phenylphosphine.

[0219] Phosphonium salts include tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium ethyltriphenylborate, tetrabutylphosphonium tetrabutylborate, etc.

[0220] Examples of tetraphenylboron salts include 2-ethyl-4-methylimidazole tetraphenylborate and N-methylmorpholine tetraphenylborate.

[0221] [Other Hardeners]

[0222] Other curing agents include mercaptan-based curing agents, tertiary amines, phosphonium salts, tetraphenylboron salts, organic acid dihydrazides, borohalide complexes, isocyanate-based curing agents, and block isocyanate-based curing agents.

[0223] These curing agents can be used in combination of one or more types.

[0224] When the protective film-forming composition of the present invention includes a curing agent, the lower limit of the content is typically 0.0001 mass%, preferably 0.01 mass%, more preferably 0.1 mass% with respect to the total solid content of the protective film-forming composition, and the upper limit of the content is typically 50 mass%, preferably 40 mass%, more preferably 30 mass% with respect to the total solid content of the protective film-forming composition.

[0225] <Solvent(C)>

[0226] The protective film-forming composition of the present invention can be prepared by dissolving each of the above components in a solvent, preferably an organic solvent, and is used in a uniform solution state.

[0227] As for the organic solvent of the protective film-forming composition according to the present invention, any organic solvent capable of dissolving the above-mentioned component (A), component (B), and other optionally selected solid components may be used without particular limitation. In particular, since the protective film-forming composition according to the present invention is used in a uniform solution state, considering its coating performance, it is recommended to use an organic solvent generally used in lithography processes.

[0228] The above organic solvents include, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, cycloheptanone, 4-methyl-2-pentanol, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, ethyl ethoxyacetate, 2-hydroxyethyl acetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, Examples include 3-methyl ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyn acetate, butyl acetate, ethyl lactic acid, butyl lactic acid, 2-heptanone, methoxycyclopentane, anisole, γ-butyrolactone, N-methylpyrrolidone, N,N-dimethylformamide, and N,N-dimethylacetamide. These solvents may be used alone or in combination of two or more.

[0229] Among these solvents, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactic acid, butyl lactic acid, and cyclohexanone are preferred. In particular, propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate are preferred.

[0230] The solid content of the protective film-forming composition according to the present invention is typically 0.1 to 70 mass%, preferably 0.1 to 60 mass%. The solid content is the ratio of the total components excluding the solvent in the protective film-forming composition. The proportion of compound (A) in the solid content is preferably in the order of 1 to 100 mass%, 1 to 99.9 mass%, 50 to 99.9 mass%, 50 to 95 mass%, and 50 to 90 mass%.

[0231] <Ingredient (D)>

[0232] The protective film-forming composition according to the present invention may further include (D) a compound having one phenolic hydroxyl group, or a polymer having a unit structure having one phenolic hydroxyl group.

[0233] Since it is a “compound having one phenolic hydroxyl group or a polymer having a unit structure having one phenolic hydroxyl group,” compounds or polymers having a phenolic hydroxyl group, such as catechol, are excluded.

[0234] A compound having one phenolic hydroxyl group, or a polymer having a unit structure having one phenolic hydroxyl group, is not particularly limited as long as it is a compound or polymer that does not impair the effects of the present invention.

[0235] The weight-average molecular weight of a compound having one phenolic hydroxyl group, or a polymer having a unit structure having one phenolic hydroxyl group, is also not particularly limited, for example, 300 to 50,000, or 1,000 to 50,000.

[0236] It is preferable that a polymer having a unit structure having one phenolic hydroxyl group comprises a unit structure represented by the following formula (3-1):

[0237] [Chemical Formula 13]

[0238]

[0239] (during food, T 4 represents an alkyl group having 1 to 10 carbon atoms that may be substituted with a hydrogen atom or a halogen group. R 4 represents a halogen group, a carboxyl group, a nitro group, a cyano group, a methylenedioxy group, an acetoxy group, a methylthio group, an alkoxy group having 1 to 9 carbon atoms, an amino group that may be substituted with an alkyl group having 1 to 3 carbon atoms, a hydroxyl group, or an alkyl group having 1 to 10 carbon atoms that may be substituted with a halogen group. r4 represents an integer from 0 to 3. n7 represents an integer from 0 to 2. a is 1.)

[0240] Examples of halogen groups include fluorine, chlorine, bromine, and iodine.

[0241] Alkyl groups 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, Examples include 1-ethyl-2-methyl-cyclopropyl groups, 2-ethyl-1-methyl-cyclopropyl groups, 2-ethyl-2-methyl-cyclopropyl groups, 2-ethyl-3-methyl-cyclopropyl groups, decyl groups, etc.

[0242] Examples of alkoxy groups having 1 to 9 carbon atoms include methoxy groups, ethoxy groups, n-propoxy groups, isopropoxy groups, n-butoxy groups, isobutoxy groups, tert-butoxy groups, sec-butoxy groups, n-pentoxy groups, neopentoxy groups, n-hexyloxy groups, isohexyloxy groups, 3-methylpentoxy groups, etc.

[0243] A polymer having a unit structure having one phenolic hydroxyl group preferably has at least three repeating unit structures.

[0244] A polymer having a unit structure having one phenolic hydroxyl group may be a polymer containing one type of unit structure represented by formula (3-1), or a copolymer containing two or more types.

[0245] Specific examples of a polymer having a unit structure having one phenolic hydroxyl group include a polymer comprising the unit structure described below.

[0246] [Chemical Formula 14]

[0247]

[0248] It is preferable that the protective film-forming composition for a wet etching solution for semiconductors according to the present invention does not include novolak resin. In addition, it is preferable that each of the compound (A), component (B), and solvent (C) does not include a material comprising one or more aromatic groups including two or more substituents comprising a hydroxyl, thiol, and / or amine portion.

[0249] <Protective film, resist underlayer, and method of manufacturing protective film-attached substrate / resist pattern-attached substrate and semiconductor device>

[0250] Hereinafter, a method for manufacturing a substrate with a protective film attached / substrate with a resist pattern attached using a protective film-forming composition / resist underlayer-forming composition according to the present invention, and a method for manufacturing a semiconductor device will be described.

[0251] A protective film-attached substrate / resist pattern-attached substrate according to the present invention can be manufactured by applying the above-described protective film-forming composition / resist underlayer-forming composition onto a semiconductor substrate and firing it.

[0252] Examples of semiconductor substrates to which the protective film-forming composition / resist underlayer-forming composition of the present invention is applied include, for instance, silicon wafers, germanium wafers, and semiconductor wafers such as gallium arsenide, indium phosphide, titanium nitride, gallium nitride, indium nitride, aluminum nitride, and aluminum oxide.

[0253] When using a semiconductor substrate having an inorganic film formed on its surface, the inorganic film is formed by, for example, ALD (Atomic Layer Deposition), CVD (Chemical Vapor Deposition), reactive sputtering, ion plating, vacuum deposition, or spin coating (Spin-on-Glass: SOG). Examples of the inorganic film include low-temperature oxide films, polysilicon films, silicon oxide films, silicon nitride films, silicon oxynitride films, BPSG (Boro-Phospho Silicate Glass) films, titanium nitride films, titanium oxynitride films, tungsten nitride films, gallium nitride films, aluminum oxide, hafnium oxide, tantalum, tantalum nitride, and gallium arsenide films. The semiconductor substrate may be a stepped substrate having so-called vias (holes), trenches (grooves), etc. formed therein. For example, vias have a roughly circular shape when viewed from the top surface, with a diameter of approximately 2 nm to 20 nm and a depth of 50 nm to 500 nm, and trenches have a groove (concave part of the substrate) with a width of 1 nm to 20 nm and a depth of 50 nm to 500 nm. Since the protective film forming composition / resist underlayer forming composition of the present invention has a small weight-average molecular weight and average particle size of the compounds included in the composition, this composition can be embedded in a stepped substrate as described above without defects such as voids. For the next process of semiconductor manufacturing (wet etching / dry etching of the semiconductor substrate, resist pattern formation), the absence of defects such as voids is an important characteristic.

[0254] On such a semiconductor substrate, the protective film-forming composition / resist underlayer-forming composition of the present invention is applied by a suitable application method such as a spinner or a coater. Afterward, a protective film / resist underlayer is formed by baking using a heating means such as a hot plate. The baking conditions are appropriately selected from a baking temperature of 100°C to 400°C and a baking time of 0.3 minutes to 60 minutes. Preferably, the baking temperature is 120°C to 350°C and the baking time is 0.5 minutes to 30 minutes, and more preferably, the baking temperature is 150°C to 300°C and the baking time is 0.8 minutes to 10 minutes. The thickness of the formed protective film / resist underlayer is, for example, 0.001μm to 10μm, preferably 0.002μm to 1μm, and more preferably 0.005μm to 0.5μm. If the baking temperature is lower than the above range, crosslinking becomes insufficient, and it may be difficult to obtain resistance to resist solvents or basic hydrogen peroxide aqueous solutions of the formed protective film / resist sublayer. On the other hand, if the baking temperature is higher than the above range, the protective film / resist sublayer may decompose due to heat.

[0255] Exposure is performed through a mask (reticle) to form a predetermined pattern, and, for example, i-ray, KrF excimer laser, ArF excimer laser, EUV (extreme ultraviolet), or EB (electron beam) is used. An alkaline developer is used for development, and the development temperature is appropriately selected from 5°C to 50°C and the development time from 10 seconds to 300 seconds. As an alkaline developer, for example, an aqueous solution of an alkali such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia water, etc., an aqueous solution of an alkali such as a primary amine such as ethylamine, n-propylamine, etc., a secondary amine such as diethylamine, di-n-butylamine, a tertiary amine such as triethylamine, methyldiethylamine, etc., an alcohol amine such as dimethylethanolamine, triethanolamine, etc., a quaternary ammonium salt such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, etc., or a cyclic amine such as pyrrole, piperidine, etc., may be used. Furthermore, an appropriate amount of an alcohol such as isopropyl alcohol, or a nonionic surfactant, may be added to the above aqueous solution of alkali. Among these, a preferred developer is a quaternary ammonium salt, more preferably tetramethylammonium hydroxide and choline. Furthermore, a surfactant, etc., may be added to these developers. Instead of an alkaline developer, a method may be used to develop using an organic solvent such as butyl acetate, and to develop areas where the alkaline dissolution rate of the photoresist is not enhanced.

[0256] Next, the protective film / resist lower layer is dry-etched using the formed resist pattern as a mask. At that time, if the inorganic film is formed on the surface of the semiconductor substrate used, the surface of the inorganic film is exposed, and if the inorganic film is not formed on the surface of the semiconductor substrate used, the surface of the semiconductor substrate is exposed.

[0257] The protective film / resist underlayer of the present invention can also be applied to a lithography process in which the upper layer is a combination of the resist and other materials (for example, a combination of the resist and a silicon oxide film underneath).

[0258] Furthermore, a desired pattern is formed by using a protective film / resist sublayer after dry etching (and, if a resist pattern remains on the protective film / resist sublayer, the resist pattern as well) as a mask and performing wet etching using a semiconductor wet etching solution.

[0259] As a wet etching solution for semiconductors, a general chemical solution for etching semiconductor wafers can be used, and for example, any substance exhibiting acidity or a substance exhibiting basicity can be used.

[0260] Examples of substances exhibiting acidity include hydrogen peroxide, hydrofluoric acid, ammonium fluoride, acidic ammonium fluoride, ammonium hydrofluoric acid, buffered hydrofluoric acid, hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, or mixtures thereof.

[0261] Examples of substances exhibiting basicity include basic hydrogen peroxide, which is produced by mixing hydrogen peroxide with organic amines such as ammonia, sodium hydroxide, potassium hydroxide, sodium cyanide, potassium cyanide, and triethanolamine to make the pH basic. A specific example is SC-1 (ammonia-hydrogen peroxide solution). In addition, substances capable of making the pH basic, such as mixing urea with hydrogen peroxide and generating ammonia by causing the thermal decomposition of urea by heating to finally make the pH basic, can also be used as a chemical solution for wet etching.

[0262] Among these, it is preferable that it be an acidic hydrogen peroxide or a basic hydrogen peroxide.

[0263] These drug solutions may contain additives such as surfactants.

[0264] The operating temperature of the wet etching solution for semiconductors is preferably 25°C to 90°C, and more preferably 40°C to 80°C. The wet etching time is preferably 0.5 minutes to 30 minutes, and more preferably 1 minute to 20 minutes.

[0265] Examples

[0266] Next, the contents of the present invention will be specifically explained with reference to examples, but the present invention is not limited to these.

[0267] The weight-average molecular weight of the compounds shown in Examples 1 to 4 and Synthesis Example 1 of this specification is the result of measurement by gel permeation chromatography (hereinafter abbreviated as GPC). A GPC device manufactured by Tosho Inc. was used for the measurement, and the measurement conditions, etc. are as follows.

[0268] GPC Column: TSKgel guardcolum SuperMP(HZ)-N, TSKgel SuperMultiporeHZ-N(P009), TSKgel SuperMultiporeHZ-N(P0010)(Manufactured by Tosoh Co., Ltd.)

[0269] Column temperature: 40℃

[0270] Solvent: Tetrahydrofuran (THF)

[0271] Flow rate: 0.35 ml / min

[0272] Standard sample: Polystyrene (manufactured by Toso Co., Ltd.)

[0273] <Example 1>

[0274] To 3.56 g of tetraphenylol ethane tetraglycidyl ether (manufactured by Nippon Kagaku Co., Ltd., product name 1031S) (weight-average molecular weight: 1,033), 0.036 g of K-PURE [trademark registered] TAG-2689 (product of King Industries) as a thermal acid generating agent, 77.12 g of propylene glycol monomethyl ether acetate, and 19.28 g of propylene glycol monomethyl ether were added and prepared as a solution. A protective film-forming composition was prepared by filtering the solution using a polyethylene microfilter with a pore diameter of 0.02 μm.

[0275] [Chemical Formula 15]

[0276]

[0277] <Example 2>

[0278] To 1.78 g of 2-[4-(2,3-epoxypropoxy)phenyl]-2-(4-[1,1-bis[4-([2,3-epoxypropoxy]phenyl)ethyl]phenyl]propane (Mitsubishi Chemical Corporation, product name NC-6000) (weight-average molecular weight: 548), 0.018 g of K-PURE [Trademark Registered] TAG-2689 (product of King Industries) as a thermal acid generating agent, 33.56 g of propylene glycol monomethyl ether acetate, and 9.64 g of propylene glycol monomethyl ether were added to form a solution. A protective film-forming composition was prepared by filtering the solution using a polyethylene microfilter with a pore diameter of 0.02 μm.

[0279] [Chemical Formula 16]

[0280]

[0281] <Example 3>

[0282] To 2.85 g of commercially available epoxy resin (manufactured by DIC Co., Ltd., product name EPICLON HP-6000) (weight-average molecular weight: 361, containing a compound of the structural formula below), 0.029 g of K-PURE [Trademark Registered] TAG-2689 (product of King Industries Co., Ltd.) as a thermal acid generating agent, 61.70 g of propylene glycol monomethyl ether acetate, and 15.42 g of propylene glycol monomethyl ether were added and prepared as a solution. A protective film-forming composition was prepared by filtering the solution using a polyethylene microfilter with a pore diameter of 0.02 μm.

[0283] [Chemical Formula 17]

[0284]

[0285] <Example 4>

[0286] 0.83 g of 2-[4-(2,3-epoxypropoxy)phenyl]-2-(4-[1,1-bis[4-([2,3-epoxypropoxy]phenyl)ethyl]phenyl]propane (Mitsubishi Chemical Corporation, Product Name NC-6000) (weight-average molecular weight: 548), 0.28 g of VP-2500 (product of Nippon Soda Co., Ltd., equivalent to Formula (A), weight-average molecular weight: 3,687) (30 mass% PGMEA solution), to which as thermal acid generating agents: 0.083 g of K-PURE [Trademark Registered] TAG-2689 (product of King Industries), 0.083 g of R-40-LM (DIC Corporation) (1 mass% PGMEA solution), 15.18 g of propylene glycol monomethyl ether acetate, and propylene glycol monomethyl ether 6.62g was added and made into a solution. A protective film-forming composition was prepared by filtering the solution using a polyethylene microfilter with a pore diameter of 0.02μm.

[0287] [Chemical Formula 18]

[0288]

[0289] <Synthesized Example 1>

[0290] A solution of 5.50 g of glycerin monomethacrylate (product name: Blemmer GLM, manufactured by Nichiyu Co., Ltd.), 5.09 g of 5-vinylbenzo[d][1,3]dioxol (manufactured by Cool Pharm LTD.), 0.66 g of 2,2'-azobis(isobutyronitrile) (manufactured by Tokyo Kasei Kogyo Co., Ltd.), and 35.99 g of propylene glycol monomethyl ether was added to a dropping funnel, and then added dropwise to a reaction flask containing 9.00 g of propylene glycol monomethyl ether under a nitrogen atmosphere at 100°C and heated and stirred for 17 hours. 11 g of cation exchange resin (product name: Dow-X [Trademark] 550A, Muromachi Technos Co., Ltd.) and 11 g of anion exchange resin (product name: Amberlite [Trademark] 15JWET, Organo Co., Ltd.) were added to the obtained solution, and ion exchange treatment was performed at room temperature for 4 hours. By separating the ion exchange resin, a resin solution corresponding to formula (B) was obtained, and the weight-average molecular weight (Mw) measured by polystyrene conversion by GPC was 10,800.

[0291] [Chemical Formula 19]

[0292]

[0293] <Comparative Example 1>

[0294] To 6.6 g of the resin solution (solid content 17.4 wt%) obtained in Synthesis Example 1, 0.06 g of pyridinium trifluoromethanesulfonic acid (manufactured by ADEKA Co., Ltd.) as a crosslinking acid catalyst, 0.001 g of a surfactant (manufactured by DIC Co., Ltd., product name: Megapak [product name] R-40, fluorine-based surfactant), 11.5 g of propylene glycol monomethyl ether, and 1.9 g of propylene glycol monomethyl ether acetate were added to prepare a solution of a protective film-forming composition.

[0295] (Formation of a film)

[0296] A protective film-forming composition prepared in Examples 1 to 4 and a film-forming composition prepared in Comparative Example 1 were applied by spin coating onto a silicon substrate having a titanium nitride film formed on its surface, and baked at 250°C for 60 seconds to produce a film with a thickness of 100 nm.

[0297] (Resistance test to aqueous basic hydrogen peroxide solution)

[0298] A coating film prepared on a silicon substrate having a titanium nitride film formed on its surface using the protective film-forming compositions prepared in Examples 1 to 4 and the film-forming composition prepared in Comparative Example 1 was immersed in an aqueous basic hydrogen peroxide solution with the composition shown in Table 1 below for 4 minutes at the temperature shown in the table, and then the condition of the coating film after rinsing and drying was observed visually. The results are shown in Table 2 below. In Table 2, "○" indicates a condition where no peeling is observed on the coating film even after 4 minutes of treatment, and "×" indicates a condition where peeling is observed on part or all of the coating film after 4 minutes of treatment.

[0299] [Table 1]

[0300]

[0301] [Table 2]

[0302]

[0303] From the results of the table above, it was shown that the coating film prepared using the protective film-forming compositions prepared in Examples 1 to 3 had sufficient resistance to basic aqueous hydrogen peroxide solutions. In other words, it was found that these coating films could serve as a protective film against basic aqueous hydrogen peroxide solutions. On the other hand, it was found that the coating film prepared using the film-forming composition prepared in Comparative Example 1 was insufficient as a protective film against basic aqueous hydrogen peroxide solutions.

[0304] (Testing of optical parameters)

[0305] The protective film-forming compositions prepared in Examples 1 to 4 and Comparative Example 1 were each applied onto a silicon wafer using a spinner. The wafers were baked on a hot plate at 250°C for 1 minute to form a resist underlayer (film thickness 50 nm). Then, the n-value (refractive index) and k-value (attenuation coefficient or absorption coefficient) of these protective film-forming compositions at wavelengths of 193 nm and 193 nm were measured using a spectroscopic ellipsometer (JA Woollam, VUV-VASE VU-302). The results are shown in Table 3.

[0306] (Measurement of dry etching rate)

[0307] The protective film-forming compositions prepared in Examples 1 to 4 and Comparative Example 1 were each applied onto a silicon wafer by a spin coater. A resist underlayer was formed by baking on a hot plate at 250°C for 1 minute. Then, a dry etching rate (amount of film thickness reduction per unit time) was measured using a dry etching apparatus (RIE-10NR) manufactured by Samco Co., Ltd. under conditions using N2 (200 sccm), O2 (10 sccm), and RF (60W) as dry etching gases.

[0308] A comparison was made between the dry etching speed of the protective film-forming compositions prepared in Examples 1 to 4 and the dry etching speed of the protective film-forming composition prepared in Comparative Example 1. In Table 3, the dry etching speed of the protective film-forming composition of each example is shown as a "selectivity ratio" when the dry etching speed of Comparative Example 1 is set to 1.00.

[0309] [Table 3]

[0310]

[0311] From the above results, the dry etching rate of the protective film-forming composition prepared in Examples 1 to 4 according to the present invention is smaller compared to the dry etching rate of the protective film-forming composition prepared in Comparative Example 1, and under the dry etching conditions, it can be said that the protective film of the present invention has etching resistance.

[0312] Industrial applicability

[0313] According to the protective film-forming composition of the present invention, a protective film can be formed in a lithography process in semiconductor manufacturing that exhibits high chemical resistance, good optical parameters, and a desirable dry etching selectivity ratio.

Claims

Claim 1 (A) A compound that does not have repeating structural units, represented by the following formula (II): [Equation (II), Z 1 , Z 2 Each independently [In equation (I), * is Y 1 , or Y 2 Indicates the bonding site with. X represents an ether bond, and n=1.] represents, and Y 1 , Y 2 Each independently represents a benzene ring or a naphthalene ring, and X 1 , X 2 -Y each independently 1 -Z 1 or -Y 2 -Z 2 [representing, where n1 and n2 each independently represent an integer from 1 to 4, provided that when Q represents an aliphatic hydrocarbon group, n1 and n2 each independently represent an integer from 2 to 4, m1 and m2 each independently represent 0 or 1, and Q represents a 2 to 4-valent group selected from the group consisting of an aliphatic hydrocarbon group, a combination of an aromatic hydrocarbon group with fewer than 10 carbon atoms and an aliphatic hydrocarbon group, and a combination of an aromatic hydrocarbon group with 10 or more carbon atoms and -O-,], (B) a thermal acid generating agent (B-1) and / or a curing agent (B-2), and (C) a solvent, a protective film-forming composition for a wet etching solution for a semiconductor. Claim 2 delete Claim 3 delete Claim 4 A protective film-forming composition according to claim 1, wherein the compound (A) has a weight-average molecular weight of 300 or more and 1,500 or less. Claim 5 A protective film-forming composition according to claim 1, which does not contain novolak resin. Claim 6 A protective film-forming composition according to claim 1, wherein each of the compound (A), component (B), and solvent (C) does not comprise a material comprising one or more aromatic groups comprising two or more substituents including a hydroxyl, thiol, and / or amine portion. Claim 7 delete Claim 8 A protective film-forming composition according to claim 1, wherein the component (B) comprises a curing agent (B-2) selected from the group consisting of phenolic curing agents, amide curing agents, amine curing agents, imidazoles, acid anhydride curing agents, and organic phosphines. Claim 9 A protective film-forming composition according to claim 1, further comprising (D) a compound having one phenolic hydroxyl group or a polymer having a unit structure having one phenolic hydroxyl group. Claim 10 A protective film characterized by being a sintered product of a coating film formed from a protective film-forming composition described in any one of claims 1, 4 to 6, 8, and 9. Claim 11 (A) A compound that does not have repeating structural units, represented by the following formula (II): [Equation (II), Z 1 , Z 2 Each independently [In equation (I), * is Y 1 , or Y 2 Indicates the bonding site with. X represents an ether bond, and n=1.] represents, and Y 1 , Y 2 Each independently represents a benzene ring or a naphthalene ring, and X 1 , X 2 -Y each independently 1 -Z 1 or -Y 2 -Z 2 [representing, where n1 and n2 each independently represent an integer from 1 to 4, provided that when Q represents an aliphatic hydrocarbon group, n1 and n2 each independently represent an integer from 2 to 4, m1 and m2 each independently represent 0 or 1, and Q represents a 2 to 4-valent group selected from the group consisting of an aliphatic hydrocarbon group, a combination of an aromatic hydrocarbon group with fewer than 10 carbon atoms and an aliphatic hydrocarbon group, and a combination of an aromatic hydrocarbon group with 10 or more carbon atoms and -O-.], (B) a thermal acid generating agent (B-1) and / or a curing agent (B-2), and (C) a solvent, comprising a resist underlayer forming composition. Claim 12 delete Claim 13 delete Claim 14 A resist underlayer forming composition according to claim 11, wherein the compound (A) has a weight-average molecular weight of 300 or more and 1,500 or less. Claim 15 A resist underlayer forming composition that does not contain novolak resin in claim 11. Claim 16 A resist underlayer forming composition according to claim 11, wherein each of the compound (A), component (B), and solvent (C) does not comprise a material comprising one or more aromatic groups comprising two or more substituents including a hydroxyl, thiol, and / or amine portion. Claim 17 delete Claim 18 A resist underlayer forming composition according to claim 11, wherein the above component (B) comprises a curing agent (B-2) selected from the group consisting of phenolic curing agents, amide curing agents, amine curing agents, imidazoles, acid anhydride curing agents, and organic phosphines. Claim 19 In claim 11, a resist underlayer forming composition further comprising (D) a compound having one phenolic hydroxyl group or a polymer having a unit structure having one phenolic hydroxyl group. Claim 20 A resist underlayer characterized by being a sintered product of a coating film formed from a resist underlayer forming composition described in any one of claims 11, 14 to 16, 18 and 19. Claim 21 A method for manufacturing a protective film-attached substrate, characterized by using a protective film-forming composition described in any one of claims 1, 4 to 6, 8, and 9 in the manufacture of a semiconductor, comprising a process of applying the composition onto a semiconductor substrate having a step and firing it to form a protective film. Claim 22 A method for manufacturing a substrate with a resist pattern attached, characterized by comprising: a process of applying a protective film-forming composition described in any one of claims 1, 4 to 6, 8 and 9, or a resist lower layer-forming composition described in any one of claims 11, 14 to 16, 18 and 19 onto a semiconductor substrate and firing to form a protective film as a resist lower layer; a process of forming a resist film on the protective film, followed by exposure and development to form a resist pattern, and using the result for the manufacture of a semiconductor. Claim 23 A method for manufacturing a semiconductor device comprising the steps of: forming a protective film on a semiconductor substrate on which an inorganic film may be formed on the surface, using a protective film-forming composition described in any one of claims 1, 4 to 6, 8 and 9; forming a resist pattern on the protective film; dry-etching the protective film using the resist pattern as a mask; exposing the surface of the inorganic film or the semiconductor substrate; and wet-etching and cleaning the inorganic film or the semiconductor substrate using a wet-etching solution for semiconductors, using the protective film after dry-etching as a mask. Claim 24 A method for manufacturing a semiconductor device comprising the steps of: forming a resist lower layer using a resist lower layer forming composition described in any one of claims 11, 14 to 16, 18 and 19 on a semiconductor substrate on which an inorganic film may be formed on the surface; forming a resist pattern on the resist lower layer; dry-etching the resist lower layer using the resist pattern as a mask; exposing the surface of the inorganic film or the semiconductor substrate; and etching the inorganic film or the semiconductor substrate using the resist lower layer after dry-etching as a mask.

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