Composition for forming resist underlayer film

Abstract

A composition for forming a resist underlayer film, which contains a solvent and a polymer having an alicyclic structure other than the terminal.

Description

Technical Field

[0001] The present invention relates to a resist underlayer film-forming composition, a resist underlayer film, a semiconductor processing substrate, a method for producing a semiconductor element, and a pattern forming method. Background Art

[0002] Microfabrication using photolithography using a photoresist composition has been performed in the manufacture of semiconductor devices. The microfabrication is a method in which a thin film of a photoresist composition is formed on a silicon wafer, active energy rays such as ultraviolet rays are irradiated thereon through a mask pattern on which a pattern of a semiconductor device is drawn, and then the resultant resist pattern is used as a protective film to etch the silicon wafer.

[0003] However, in recent years, with the development of high integration of semiconductor devices, the active energy rays used have also tended to be shorter in wavelength from KrF excimer laser (248nm) to ArF excimer laser (193nm). Along with this, diffuse reflection of active energy rays from the substrate and the influence of standing waves have become a big problem. Therefore, a method of setting an anti-reflective film (Bottom Anti-Reflective Coating: BARC) as a resist bottom layer between the photoresist and the substrate has been widely studied.

[0004] For example, the present applicant has proposed a resist underlayer film-forming composition for lithography containing a polymer having a sulfur atom in its main chain and a solvent (see Patent Document 1).

[0005] Prior art literature

[0006] Patent Literature

[0007] Patent Document 1: Japanese Patent Application Publication No. 2013-033276 Summary of the invention

[0008] Problems to be solved by the invention

[0009] As resist patterns become finer, photolithography defects caused by resist pattern collapse have become a problem.

[0010] Therefore, an object of the present invention is to provide a resist underlayer film-forming composition, a resist underlayer film, a semiconductor processing substrate, a method for producing a semiconductor element, and a pattern forming method, which are capable of suppressing the collapse of a resist pattern.

[0011] Means for solving problems

[0012] The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that the above-mentioned problems can be solved, thereby completing the present invention having the following gist.

[0013] That is, the present invention includes the following contents.

[0014] [1] A resist underlayer film-forming composition comprising a polymer having an alicyclic structure other than at a terminal, and a solvent.

[0015] [2] The resist underlayer film forming composition according to [1], wherein the polymer further has an aromatic hydrocarbon ring.

[0016] [3] The resist underlayer film forming composition according to [1] or [2], wherein the polymer further has a nitrogen-containing ring.

[0017] [4] The resist underlayer film-forming composition according to any one of [1] to [3], wherein the polymer has a structure represented by the following formula (1) as the structure having the alicyclic structure.

[0018]

[0019] (In formula (1), A cy represents a divalent group having an alicyclic structure. n1 and n2 each independently represent 0 or 1. * represents a bond. )

[0020] [5] The resist underlayer film forming composition according to any one of [2] to [4], wherein the polymer has a structure represented by the following formula (2) as the structure having the aromatic hydrocarbon ring.

[0021]

[0022] (In formula (2), Ar 1 represents a divalent organic group having an aromatic hydrocarbon ring. n11 and n12 each independently represent 0 or 1. p1 and p2 each independently represent 0 or 1. A 1 , A 2 , A 3 , A 4 , A 5 and A 6 Each independently represents a hydrogen atom, a methyl group or an ethyl group. * represents a bond. )

[0023] [6] The resist underlayer film forming composition according to any one of [3] to [5], wherein the polymer has a structure represented by the following formula (3) as the structure having the nitrogen-containing ring.

[0024]

[0025] (In formula (3), X 1 It represents a group represented by any one of the following formulas (3-1) to (3-3). 1 and Z2 Each independently represents a single bond or a divalent group represented by the following formula (3-4). 11 , A 12 , A 13 , A 14 , A 15 and A 16 Each independently represents a hydrogen atom, a methyl group or an ethyl group. p3 and p4 each independently represent 0 or 1. * represents a bond. )

[0026]

[0027] (In formulas (3-1) to (3-3), R 1 ~R 5 Each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may be interrupted by an oxygen atom or a sulfur atom, an alkenyl group having 2 to 10 carbon atoms which may be interrupted by an oxygen atom or a sulfur atom, an alkynyl group having 2 to 10 carbon atoms which may be interrupted by an oxygen atom or a sulfur atom, a benzyl group, or a phenyl group, wherein the phenyl group may be substituted with at least one monovalent group selected from an alkyl group having 1 to 6 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a cyano group, and an alkylthio group having 1 to 6 carbon atoms.

[0028] R 1 and R 2 They may be bonded to each other to form a ring having 3 to 6 carbon atoms.

[0029] R 3 and R 4 They may be bonded to each other to form a ring having 3 to 6 carbon atoms.

[0030] * represents a bond. *1 represents a bond to a carbon atom in formula (3). *2 represents a bond to a nitrogen atom in formula (3).

[0031]

[0032] (In formula (3-4), m1 is an integer of 0 to 4, m2 is 0 or 1, m3 is 0 or 1, and m4 is an integer of 0 to 2. When m3 is 1, m1 and m2 are not simultaneously 0. *3 represents a bond to the nitrogen atom in formula (3). *4 represents a bond.)

[0033] [7] The resist underlayer film forming composition according to any one of [1] to [6], further comprising a crosslinking agent.

[0034] [8] The resist underlayer film forming composition according to any one of [1] to [7], further comprising a curing catalyst.

[0035] [9] The resist underlayer film-forming composition according to any one of [1] to [8], which is used for forming an underlayer film of a negative photoresist.

[0036]

[10] The resist underlayer film-forming composition according to any one of [1] to [9], which is used for lithography using ArF excimer laser or EUV.

[0037]

[11] A resist underlayer film which is a cured product of the resist underlayer film-forming composition according to any one of [1] to

[10] .

[0038]

[12] A semiconductor processing substrate comprising a semiconductor substrate and the resist underlayer film according to

[11] .

[0039]

[13] A method for manufacturing a semiconductor device, comprising the following steps:

[0040] A step of forming a resist underlayer film on a semiconductor substrate using the resist underlayer film-forming composition as described in any one of [1] to

[10] ; and

[0041] A step of forming a resist film on the resist underlayer film.

[0042]

[14] A pattern forming method comprising the following steps:

[0043] A step of forming a resist underlayer film on a semiconductor substrate using the resist underlayer film-forming composition according to any one of [1] to

[10] ;

[0044] forming a resist film on the resist underlayer film;

[0045] irradiating the resist film with light or electron beams, and then developing the resist film to obtain a resist pattern; and

[0046] A step of etching the resist underlayer film using the resist pattern as a mask.

[0047] Effects of the Invention

[0048] According to the present invention, a resist underlayer film-forming composition capable of suppressing the collapse of a resist pattern, a resist underlayer film, a semiconductor processing substrate, a method for producing a semiconductor element, and a pattern forming method can be provided. DETAILED DESCRIPTION

[0049] (Resist underlayer film forming composition)

[0050] The resist underlayer film-forming composition of the present invention contains a polymer and a solvent.

[0051] The resist underlayer film-forming composition may contain other components.

[0052] <Polymer>

[0053] The polymer has an alicyclic structure other than the terminal.

[0054] It should be noted that in the present invention, "having an alicyclic structure other than the terminal" does not mean having an alicyclic structure only other than the terminal. Therefore, the polymer may have an alicyclic structure at the terminal.

[0055] In the present invention, the alicyclic structure refers to an alicyclic hydrocarbon structure.

[0056] Examples of the alicyclic structure include alicyclic hydrocarbon structures having 4 to 10 carbon atoms. Examples of the alicyclic hydrocarbon structures having 4 to 10 carbon atoms include a cyclobutane ring structure, a cyclopentane ring structure, a cyclohexane ring structure, a cyclohexene ring structure, a dicyclopentyl ring structure, a dicyclopentenyl ring structure, a norbornane ring structure, a norbornene ring structure, an isobornene ring structure, a bicyclo[2.2.2]oct-2-ene ring structure, and an adamantane ring structure.

[0057] From the perspective of excellent optical properties (n / k), the polymer preferably further has an aromatic hydrocarbon ring. The aromatic hydrocarbon ring may be a monocyclic ring or a polycyclic ring. There are no particular restrictions on the aromatic hydrocarbon ring, and examples thereof include a benzene ring, a naphthalene ring, an anthracene ring, and the like.

[0058] From the viewpoint of excellent optical properties (n / k) and adhesion to a resist, the polymer preferably further has a nitrogen-containing ring.

[0059] The polymer may be a polymer obtained by addition polymerization or a polymer obtained by condensation polymerization.

[0060] <<Formula (1)>>

[0061] From the viewpoint of preferably obtaining the effects of the present invention, the polymer preferably has a structure represented by the following formula (1) as the structure having an alicyclic structure.

[0062]

[0063] (In formula (1), A cy represents a divalent group having an alicyclic structure. n1 and n2 each independently represent 0 or 1. * represents a bond. )

[0064] As A cy The number of carbon atoms in A is not particularly limited, but for example cy , and examples thereof include a divalent group having 4 to 25 carbon atoms and having an alicyclic structure.

[0065] It is preferred that each of the two bonds* in the formula (1) forms a single bond together with one bond* in the formula (2) or (3) described later.

[0066] That is, when the structure represented by formula (1) is represented by X1, the structure represented by formula (2) is represented by X2, and the structure represented by formula (3) is represented by X3, the polymer preferably has at least one of the following structures.

[0067] -X2-X1-X2-

[0068] -X2-X1-X3-

[0069] -X3-X1-X3-

[0070] Examples of the structure represented by formula (1) include the following structures.

[0071]

[0072] In the above formula, Me represents a methyl group and * represents a bond.

[0073] <<Formula (2)>>

[0074] From the viewpoint of excellent optical properties (n / k), the structure having an aromatic hydrocarbon ring in the polymer is preferably a structure represented by the following formula (2).

[0075]

[0076] (In formula (2), Ar 1 represents a divalent organic group having an aromatic hydrocarbon ring. n11 and n12 each independently represent 0 or 1. p1 and p2 each independently represent 0 or 1. A 1 , A 2 , A 3 , A 4 , A 5 and A 6 Each independently represents a hydrogen atom, a methyl group or an ethyl group. * represents a bond. )

[0077] As Ar 1 The number of carbon atoms in the divalent organic group having an aromatic hydrocarbon ring in is not particularly limited, but for example, 1 , and examples thereof include divalent organic groups having 6 to 20 carbon atoms and having an aromatic hydrocarbon ring.

[0078] Ar 1 For example, it represents a divalent organic group represented by any one of the following formulas (2-1) and (2-2).

[0079]

[0080] (In formulas (2-1) to (2-2), R 21 ~R 23 Each independently represents a halogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkenyloxy group having 2 to 6 carbon atoms, an alkynyloxy group having 2 to 6 carbon atoms, an acyl group having 2 to 6 carbon atoms, an aryloxy group having 6 to 12 carbon atoms, an arylcarbonyl group having 7 to 13 carbon atoms, or an aralkyl group having 7 to 13 carbon atoms. * represents a bond.

[0081] In formula (2-1), n13 represents 0 or 1. When n13 is 0, m1 represents an integer of 0 to 4. When n13 is 1, m1 represents an integer of 0 to 6. 21 When there are 2 or more R 21 Can be the same or different.

[0082] In formula (2-2), Z 3 represents a single bond, an oxygen atom, a sulfur atom, a carbonyl group, a sulfonyl group, or an alkylene group having 1 to 6 carbon atoms. n14 and n15 each independently represent 0 or 1. When n14 is 0, m2 represents an integer of 0 to 4. When n14 is 1, m2 represents an integer of 0 to 6. When n15 is 0, m3 represents an integer of 0 to 4. When n15 is 1, m3 represents an integer of 0 to 6. R 22 When there are 2 or more R 22 Can be the same or different. 23 When there are 2 or more R 23 Can be the same or different.)

[0083] In the present specification, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

[0084] In this specification, the alkyl group is not limited to a straight chain, and may be a branched chain or a cyclic chain. Examples of the straight chain or branched chain alkyl group include a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, a n-hexyl group, etc. Examples of the cyclic alkyl group (cycloalkyl group) include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, etc.

[0085] In the present specification, examples of the alkoxy group include a methoxy group, an ethoxy group, an n-pentyloxy group, and an isopropoxy group.

[0086] In the present specification, examples of the alkylthio group include a methylthio group, an ethylthio group, a n-pentylthio group, an isopropylthio group, and the like.

[0087] In the present specification, examples of the alkenyl group include vinyl, 1-propenyl, 2-propenyl, 1-methyl-1-vinyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methyl-1-propenyl, and 2-methyl-2-propenyl.

[0088] In the present specification, examples of the alkynyl group include groups in which the double bonds of the alkenyl groups exemplified in the above-mentioned "alkenyl group" are replaced with triple bonds.

[0089] In the present specification, examples of the alkenyloxy group include a vinyloxy group, a 1-propenyloxy group, a 2-n-propenyloxy group (allyloxy group), a 1-n-butenyloxy group, and an isopentenyloxy group.

[0090] In the present specification, examples of the alkynyloxy group include a 2-propenyloxy group, a 1-methyl-2-propenyloxy group, a 2-methyl-2-propenyloxy group, a 2-butenyloxy group, and a 3-butenyloxy group.

[0091] In the present specification, examples of the acyl group include an acetyl group and a propionyl group.

[0092] In the present specification, examples of the aryloxy group include a phenoxy group and a naphthoxy group.

[0093] In the present specification, examples of the arylcarbonyl group include a phenylcarbonyl group and the like.

[0094] In the present specification, examples of the aralkyl group include a benzyl group and a phenethyl group.

[0095] In the present specification, examples of the alkylene group include a methylene group, an ethylene group, a 1,3-propylene group, a 2,2-propylene group, a 1-methylethylene group, a 1,4-butylene group, a 1-ethylethylene group, a 1-methylpropylene group, a 2-methylpropylene group, a 1,5-pentylene group, a 1-methylbutylene group, a 2-methylbutylene group, a 1,1-dimethylpropylene group, a 1,2-dimethylpropylene group, a 1-ethylpropylene group, a 2-ethylpropylene group, a 1,6-hexylene group, a 1,4-cyclohexylene group, a 1,8-octylene group, a 2-ethyloctylene group, a 1,9-nonylene group, and a 1,10-decylene group.

[0096] Examples of the structure represented by the following formula (2X) in formula (2) include the following structures.

[0097]

[0098] (In formula (2X), Ar 1 , n11 and n12 are each the same as Ar in formula (2) 1 , n11 and n12 have the same meaning. * indicates a bonding bond. )

[0099]

[0100]

[0101] In the above formula, Me represents a methyl group and * represents a bond.

[0102] <<Formula (3)>>

[0103] From the viewpoint of excellent optical properties (n / k) and adhesion to a resist, the polymer has a structure represented by the following formula (3) as a structure having a nitrogen-containing ring.

[0104]

[0105] (In formula (3), X 1 It represents a group represented by any one of the following formulas (3-1) to (3-3). 1 and Z 2 Each independently represents a single bond or a divalent group represented by the following formula (3-4). 11 , A 12 , A 13 , A 14 , A 15 and A 16 Each independently represents a hydrogen atom, a methyl group or an ethyl group. p3 and p4 each independently represent 0 or 1. * represents a bond. )

[0106]

[0107] (In formulas (3-1) to (3-3), R 1 ~R 5 Each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may be interrupted by an oxygen atom or a sulfur atom, an alkenyl group having 2 to 10 carbon atoms which may be interrupted by an oxygen atom or a sulfur atom, an alkynyl group having 2 to 10 carbon atoms which may be interrupted by an oxygen atom or a sulfur atom, a benzyl group, or a phenyl group, wherein the phenyl group may be substituted with at least one monovalent group selected from an alkyl group having 1 to 6 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a cyano group, and an alkylthio group having 1 to 6 carbon atoms.

[0108] R 1 and R 2 They may be bonded to each other to form a ring having 3 to 6 carbon atoms.

[0109] R 3 and R 4 They may be bonded to each other to form a ring having 3 to 6 carbon atoms.

[0110] * represents a bond. *1 represents a bond to a carbon atom in formula (3). *2 represents a bond to a nitrogen atom in formula (3).

[0111]

[0112] (In formula (3-4), m1 is an integer of 0 to 4, m2 is 0 or 1, m3 is 0 or 1, and m4 is an integer of 0 to 2. When m3 is 1, m1 and m2 are not simultaneously 0. *3 represents a bond to the nitrogen atom in formula (3). *4 represents a bond.)

[0113] As R in formulas (3-1) to (3-3) 1 ~R 5 The alkyl group having 1 to 10 carbon atoms which may be interrupted by an oxygen atom or a sulfur atom includes, for example, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkoxyalkyl group having 2 to 10 carbon atoms, an alkoxyalkoxyalkyl group having 3 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, and an alkylthioalkyl group having 2 to 10 carbon atoms.

[0114] Furthermore, the alkyl group having 1 to 10 carbon atoms which may be interrupted by an oxygen atom or a sulfur atom may contain two or more oxygen atoms or sulfur atoms.

[0115] Examples of the structure represented by the following formula (3X) in formula (3) include the following structures.

[0116] However, when the formula (3X) is a hydantoin structure, it is preferred that the polymer structure does not contain two or more different hydantoin structures.

[0117]

[0118] (In formula (3X), X 1 , Z 1 and Z 2 Each of them is related to X in formula (3) 1 , Z 1 and Z 2 The meaning is the same. * indicates a bond. )

[0119]

[0120]

[0121] In the above formula, * represents a bonding bond.

[0122] For example, the polymer is not a reaction product of a hydantoin-containing compound (A) having two epoxy groups and a hydantoin-containing compound (B) different from the hydantoin-containing compound (A).

[0123] Examples of the polymer include polymers having the following structures.

[0124] Polymer Specific Example 1

[0125]

[0126] Polymer Specific Example 2

[0127]

[0128] Polymer Specific Example 3

[0129]

[0130] Polymer Specific Example 4

[0131]

[0132] Polymer Specific Example 5

[0133]

[0134] Polymer Specific Example 6

[0135]

[0136] Polymer Specific Example 7

[0137]

[0138] Polymer Specific Example 8

[0139]

[0140] Polymer Specific Example 9

[0141]

[0142] Polymer Specific Example 10

[0143]

[0144] Polymer Specific Example 11

[0145]

[0146] Polymer Specific Example 12

[0147]

[0148] Polymer Specific Example 13

[0149]

[0150] Polymer Specific Example 14

[0151]

[0152] Polymer Specific Example 15

[0153]

[0154] Polymer Specific Example 16

[0155]

[0156] Polymer Specific Example 17

[0157]

[0158] Polymer Specific Example 18

[0159]

[0160] Polymer Specific Example 19

[0161]

[0162] Polymer Specific Example 20

[0163]

[0164] Polymer Specific Example 21

[0165]

[0166] Polymer Specific Example 22

[0167]

[0168] Polymer Specific Example 23

[0169]

[0170] Polymer Specific Example 24

[0171]

[0172] Polymer Specific Example 25

[0173]

[0174] In the above formula, Me represents a methyl group.

[0175] There is no particular limitation on the molecular weight of the polymer.

[0176] The weight average molecular weight of the polymer is, for example, 1,000 to 100,000, preferably 2,000 to 50,000, more preferably 4,000 to 30,000, particularly preferably 5,000 to 20,000.

[0177] There is no particular limitation on the method for producing the polymer.

[0178] An example of a polymer can be obtained, for example, by the following reaction (I).

[0179] (I): Reaction of a compound represented by the following formula (1A), a compound represented by the following formula (2A), and a compound represented by the following formula (3A).

[0180]

[0181] (In formula (1A), A cy , n1 and n2 are each cy , n1 and n2 have the same meaning. )

[0182]

[0183] (In formula (2A), Ar 1 , A 1 , A 2 , A 3 , A 4 , A 5 , A 6 , n11, n12, p1 and p2 are each the same as Ar in formula (2) 1 , A 1 , A 2 , A 3 , A 4 , A 5 , A 6 , n11, n12, p1 and p2 have the same meaning. )

[0184]

[0185] (In formula (3A), X 1 , Z 1 , Z 2 , A 11 , A 12 , A 13 , A 14 , A 15 and A 16 Each of them is related to X in formula (3) 1 , Z 1 , Z 2 , A 11 , A 12 , A13 , A 14 , A 15 and A 16 Same meaning.)

[0186] In reaction (I), the mass ratio of the compound represented by formula (1A) is not particularly limited, but is preferably 30% to 70% by mass, more preferably 35% to 65% by mass, and particularly preferably 40% to 60% by mass, relative to the total of the compound represented by formula (1A), the compound represented by formula (2A) and the compound represented by formula (3A).

[0187] In reaction (I), the mass ratio of the compound represented by formula (2A) is not particularly limited, but is preferably 5% to 45% by mass, more preferably 10% to 40% by mass, and particularly preferably 15% to 35% by mass, relative to the total of the compound represented by formula (1A), the compound represented by formula (2A) and the compound represented by formula (3A).

[0188] In reaction (I), the mass ratio of the compound represented by formula (3A) is not particularly limited, but is preferably 5% to 45% by mass, more preferably 10% to 40% by mass, and particularly preferably 15% to 35% by mass, relative to the total of the compound represented by formula (1A), the compound represented by formula (2A), and the compound represented by formula (3A).

[0189] Reaction (I) can be carried out in the presence of a catalyst, for example, tetrabutyl bromide Ethyltriphenylphosphine bromide That kind of season The amount of the catalyst used can be selected from a range of 0.1 to 10% by mass relative to the total mass of the polymer raw material used in the reaction. The most suitable conditions for the polymerization reaction can be selected from a range of 80 to 160° C. and a range of 2 to 50 hours, for example.

[0190] The content of the polymer in the resist underlayer film-forming composition is not particularly limited, but is preferably 30 to 95% by mass, more preferably 50 to 90% by mass, and particularly preferably 60 to 85% by mass, based on the film constituent components.

[0191] The film-constituting components are components obtained by removing volatile components (solvent) from the resist underlayer film-forming composition.

[0192] <Cross-linking agent>

[0193] The resist underlayer film-forming composition preferably contains a cross-linking agent.

[0194] The cross-linking agent contained as an optional component in the resist underlayer film-forming composition has, for example, a functional group that can react independently.

[0195] Examples of the crosslinking agent include hexamethoxymethylmelamine, tetramethoxymethylbenzoguanamine, 1,3,4,6-tetrakis(methoxymethyl)glycoluril (tetramethoxymethyl glycoluril) (POWDERLINK [registered trademark] 1174), 1,3,4,6-tetrakis(butoxymethyl)glycoluril, 1,3,4,6-tetrakis(hydroxymethyl)glycoluril, 1,3-bis(hydroxymethyl)urea, 1,1,3,3-tetrakis(butoxymethyl)urea, and 1,1,3,3-tetrakis(methoxymethyl)urea.

[0196] The crosslinking agent may be a nitrogen-containing compound described in International Publication No. 2017 / 187969, which has 2 to 6 substituents represented by the following formula (1d) bonded to a nitrogen atom in one molecule.

[0197]

[0198] (In formula (1d), R 1 represents a methyl group or an ethyl group. * represents a bond to a nitrogen atom. )

[0199] The nitrogen-containing compound having 2 to 6 substituents represented by the formula (1d) in one molecule may be a glycoluril derivative represented by the following formula (1E).

[0200]

[0201] (In formula (1E), the four R 1 Each independently represents a methyl group or an ethyl group, R 2 and R 3 Each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group.)

[0202] Examples of the glycoluril derivative represented by the above formula (1E) include compounds represented by the following formulas (1E-1) to (1E-6).

[0203]

[0204] The nitrogen-containing compound having 2 to 6 substituents represented by formula (1d) in one molecule can be obtained by reacting a nitrogen-containing compound having 2 to 6 substituents represented by the following formula (2d) bonded to a nitrogen atom in one molecule with at least one compound represented by the following formula (3d).

[0205]

[0206] (In formula (2d) and formula (3d), R 1 Represents methyl or ethyl, R 4 represents an alkyl group having 1 to 4 carbon atoms. * represents a bond to a nitrogen atom. )

[0207] The glycoluril derivative represented by the above formula (1E) can be obtained by reacting a glycoluril derivative represented by the following formula (2E) with at least one compound represented by the above formula (3d).

[0208] The nitrogen-containing compound having 2 to 6 substituents represented by the formula (2d) in one molecule is, for example, a glycoluril derivative represented by the following formula (2E).

[0209]

[0210] (In formula (2E), R 2 and R 3 Each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group, and R 4 Each independently represents an alkyl group having 1 to 4 carbon atoms. )

[0211] Examples of the glycoluril derivatives represented by the above formula (2E) include compounds represented by the following formulas (2E-1) to (2E-4). Further examples of the compounds represented by the above formula (3d) include compounds represented by the following formulas (3d-1) and (3d-2).

[0212]

[0213] Regarding the nitrogen-containing compound having 2 to 6 substituents represented by formula (1d) bonded to a nitrogen atom in one molecule, the entire disclosure of WO2017 / 187969 is incorporated herein by reference.

[0214] The crosslinking agent may be a crosslinking compound described in International Publication No. 2014 / 208542 and represented by the following formula (G-1) or formula (G-2).

[0215]

[0216] (Where Q 1 Represents a single bond or m1-valent organic group, R 1 and R 4 Each represents an alkyl group having 2 to 10 carbon atoms, or an alkyl group having 2 to 10 carbon atoms having an alkoxy group having 1 to 10 carbon atoms, and R 2 and R 5 Each represents a hydrogen atom or a methyl group, R 3 and R 6Each represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 40 carbon atoms.

[0217] n1 represents an integer of 1≤n1≤3, n2 represents an integer of 2≤n2≤5, n3 represents an integer of 0≤n3≤3, n4 represents an integer of 0≤n4≤3, and n1, n2, n3, n4 represent integers of 3≤(n1+n2+n3+n4)≤6.

[0218] n5 represents an integer of 1≤n5≤3, n6 represents an integer of 1≤n6≤4, n7 represents an integer of 0≤n7≤3, n8 represents an integer of 0≤n8≤3, and n5, n6, n7, n8 represent integers of 2≤(n5+n6+n7+n8)≤5.

[0219] m1 represents an integer from 2 to 10. )

[0220] The crosslinkable compound represented by the above formula (G-1) or (G-2) may be obtained by reacting a compound represented by the following formula (G-3) or (G-4) with an ether compound containing a hydroxyl group or an alcohol having 2 to 10 carbon atoms.

[0221]

[0222] (Where Q 2 Represents a single bond or an m2-valent organic group. 8 , R 9 , R 11 and R 12 Each represents a hydrogen atom or a methyl group, R 7 and R 10 Each represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 40 carbon atoms.

[0223] n9 represents an integer of 1≤n9≤3, n10 represents an integer of 2≤n10≤5, n11 represents an integer of 0≤n11≤3, n12 represents an integer of 0≤n12≤3, and n9, n10, n11, n12 represent integers of 3≤(n9+n10+n11+n12)≤6.

[0224] n13 represents an integer of 1≤n13≤3, n14 represents an integer of 1≤n14≤4, n15 represents an integer of 0≤n15≤3, n16 represents an integer of 0≤n16≤3, and n13, n14, n15, n16 represent integers of 2≤(n13+n14+n15+n16)≤5.

[0225] m2 represents an integer from 2 to 10. )

[0226] Examples of the compounds represented by the above formula (G-1) and formula (G-2) are shown below.

[0227]

[0228]

[0229]

[0230] Examples of the compounds represented by formula (G-3) and formula (G-4) are shown below.

[0231]

[0232]

[0233] In the formula, Me represents a methyl group.

[0234] The entire disclosure of International Publication No. 2014 / 208542 is incorporated herein by reference.

[0235] When the crosslinking agent is used, the content ratio of the crosslinking agent in the resist underlayer film-forming composition is, for example, 1 mass % to 50 mass %, and preferably 5 mass % to 40 mass % based on the polymer.

[0236] <Curing catalyst>

[0237] As for the curing catalyst contained as an optional component in the resist underlayer film-forming composition, either a thermal acid generator or a photoacid generator may be used, but a thermal acid generator is preferably used.

[0238] Examples of the thermal acid generator include p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridine p-Toluenesulfonate (pyridinium p-toluenesulfonate ), Pyridine phenolsulfonate Pyridine p-Hydroxybenzenesulfonate (Pyridinium phenolsulfonate Salt), pyridinium trifluoromethanesulfonate Sulfonic acid compounds and carboxylic acid compounds such as 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.

[0239] Examples of the photoacid generator include Salt compounds, sulfonimide compounds, and disulfonyldiazomethane compounds, etc.

[0240] As Salt compounds, for example, diphenyl iodide Hexafluorophosphate, diphenyl iodide Trifluoromethanesulfonate, diphenyliodonium Nonafluorobutane sulfonate, diphenyl iodide Perfluorooctane sulfonate, diphenyl iodide Camphorsulfonate, bis(4-tert-butylphenyl)iodide Camphorsulfonate and bis(4-tert-butylphenyl)iodide Iodine triflate and sulfonium salt compounds such as triphenylsulfonium hexafluoroantimonate, triphenylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium camphorsulfonate, and triphenylsulfonium trifluoromethanesulfonate.

[0241] Examples of the sulfonyl imide compound include N-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluoro-n-butanesulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, and N-(trifluoromethanesulfonyloxy)naphthalimide.

[0242] Examples of the disulfonyldiazomethane compound include bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(2,4-dimethylbenzenesulfonyl)diazomethane, and methylsulfonyl-p-toluenesulfonyldiazomethane.

[0243] The curing catalyst may be used alone or in combination of two or more.

[0244] When a curing catalyst is used, the content ratio of the curing catalyst is, for example, 0.1 mass % to 50 mass %, or preferably 1 mass % to 30 mass % based on the cross-linking agent.

[0245] <Solvent>

[0246] As the solvent, an organic solvent that is generally used in a chemical solution for semiconductor photolithography is preferred. Specifically, 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 monoethyl ether, propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, cycloheptanone, 4-methyl-2-pentanol, methyl 2-hydroxyisobutyrate, 2-hydroxyisobutyric acid ethyl ester, ethoxyethyl ester, 2-hydroxyethyl acetate, 3-methoxypropionic acid methyl ester, 3-methoxypropionic acid ethyl ester, 3-ethoxypropionic acid ethyl ester, 3-ethoxypropionic acid methyl ester, methyl pyruvic acid, ethyl pyruvic acid, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, 2-heptanone, methoxycyclopentane, anisole, γ-butyrolactone, N-methylpyrrolidone, N,N-dimethylformamide, and N,N-dimethylacetamide. These solvents can be used alone or in combination of two or more.

[0247] Among these solvents, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, butyl lactate, and cyclohexanone are preferred, and propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate are particularly preferred.

[0248] <Other ingredients>

[0249] A surfactant may be further added to the resist underlayer film-forming composition in order to prevent the generation of pinholes, streaks, and the like and to further improve coating properties to surface unevenness.

[0250] Examples of the surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether, polyoxyethylene alkyl aryl ethers such as polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, and sorbitan tristearate, and sorbitan fatty acid esters such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate. Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as sorbitan tristearate, Eftop EF301, EF303, EF352 (trade names of Tokem Projects), Megaphac F171, F173, R-30 (trade names of DIC Corporation), Fluorolide FC430, FC4 Fluorine-based surfactants such as SC-31 (manufactured by Sumitomo Slide Group, trade name), ASHRAD AG710, S-382, SC101, SC102, SC103, SC104, SC105, and SC106 (manufactured by Asahi Glass Co., Ltd., trade name), and organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0251] The amount of these surfactants blended is not particularly limited, but is usually 2.0 mass % or less, preferably 1.0 mass % or less, based on the total solid content of the resist underlayer film-forming composition.

[0252] These surfactants may be added alone or in combination of two or more.

[0253] The film constituting components contained in the resist underlayer film-forming composition, that is, the components after removing the solvent, are, for example, 0.01% by mass to 10% by mass of the resist underlayer film-forming composition.

[0254] The resist underlayer film-forming composition of the present invention is manufactured, for example, by mixing a polymer and a solvent using a known method. In order to use it as a resist underlayer film-forming composition, it is necessary to be in a uniform solution state. In order to remove metal impurities, foreign matter, etc. present in the composition, the manufactured composition is preferably manufactured by filtering using a filter or the like.

[0255] One of the criteria for evaluating whether the resist underlayer film forming composition is in a uniform solution state is to observe the permeability of a specific microfilter. The resist underlayer film forming composition involved in the present invention preferably passes through microfilters with pore sizes of 0.1μm, 0.05μm, 0.03μm, 0.02μm, and 0.01μm, and presents a uniform solution state.

[0256] The resist underlayer film-forming composition is, for example, a composition for forming an underlayer film of any of a negative photoresist and a positive photoresist, and is preferably a composition for forming an underlayer film of a negative photoresist.

[0257] The composition for forming a resist underlayer film is, for example, a composition for forming a resist underlayer film for lithography using i-rays (365 nm), KrF excimer laser (248 nm), ArF excimer laser (193 nm), EUV (extreme ultraviolet light; 13.5 nm), or EB (electron beam), and is preferably a composition for forming a resist underlayer film for lithography using ArF excimer laser or EUV.

[0258] (Resist Underlayer Film)

[0259] The resist underlayer film of the present invention is a cured product of the resist underlayer film-forming composition described above.

[0260] The resist underlayer film can be produced by, for example, applying the resist underlayer film-forming composition described above on a semiconductor substrate and firing the coating.

[0261] Examples of the semiconductor substrate to which the resist underlayer film-forming composition is applied include a silicon wafer, a germanium wafer, and a compound semiconductor wafer of gallium arsenide, indium phosphide, gallium nitride, indium nitride, aluminum nitride, or the like.

[0262] In the case of using a semiconductor substrate having an inorganic film formed on the surface, the inorganic film is formed, for example, by an ALD (atomic layer deposition) method, a CVD (chemical vapor deposition) method, a reactive sputtering method, an ion plating method, a vacuum evaporation method, or a spin coating method (spin-on glass: SOG). Examples of the above-mentioned inorganic film include polysilicon film, silicon oxide film, silicon nitride film, BPSG (Boro-Phospho Silicate Glass) film, titanium nitride film, titanium oxide nitride film, tungsten film, gallium nitride film, and gallium arsenide film. The inorganic film may be a single layer or a multilayer of more than two layers. In the case of more than one layer, each layer may be an inorganic film of the same type or a different type.

[0263] The thickness of the inorganic film is not particularly limited.

[0264] On such a semiconductor substrate, the resist underlayer film-forming composition of the present invention is applied by a suitable coating method such as a spin coater or a coater. Then, a heating means such as a hot plate is used to bake, thereby forming a resist underlayer film. As baking conditions, it is 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.

[0265] The thickness of the resist underlayer film is, for example, 0.001 μm (1 nm) to 10 μm, 0.002 μm (2 nm) to 1 μm, 0.005 μm (5 nm) to 0.5 μm (500 nm), 0.001 μm (1 nm) to 0.05 μm (50 nm), 0.002 μm (2 nm) to 0.05 μm (50 nm), 0.003 μm (3 nm) to 0.05 μm (50 nm), 0.004 μm (4 nm) to 0.05 μm (50 nm), 0.005 μm (5 nm) to 0.05 μm (500 nm), and 0.006 μm (5 nm) to 0.05 μm (500 nm). 0nm), 0.003μm (3nm) ~ 0.03μm (30nm), 0.003μm (3nm) ~ 0.02μm (20nm), 0.005μm (5nm) ~ 0.02μm (20nm), 0.005μm (5nm) ~ 0.02μm (20nm), 0.003μm (3nm) ~ 0.01μm (10nm), 0.005μm (5nm) ~ 0.01μm (10nm), 0.003μm (3nm) ~ 0.006μm (6nm), or 0.005μm (5nm).

[0266] (Substrates for semiconductor processing)

[0267] A semiconductor processing substrate of the present invention comprises a semiconductor substrate and the resist underlayer film of the present invention.

[0268] As the semiconductor substrate, for example, the above-mentioned semiconductor substrates can be mentioned.

[0269] The resist underlayer film is disposed on, for example, a semiconductor substrate.

[0270] (Semiconductor device manufacturing method, pattern forming method)

[0271] The method for manufacturing a semiconductor device of the present invention includes at least the following steps.

[0272] A step of forming a resist underlayer film on a semiconductor substrate using the resist underlayer film-forming composition of the present invention; and

[0273] A step of forming a resist film on the resist underlayer film.

[0274] The pattern forming method of the present invention includes at least the following steps.

[0275] A step of forming a resist underlayer film on a semiconductor substrate using the resist underlayer film-forming composition of the present invention;

[0276] A step of forming a resist film on the resist underlayer film;

[0277] A step of irradiating the resist film with light or an electron beam and then developing the resist film to obtain a resist pattern; and

[0278] A step of etching the resist underlayer film using the resist pattern as a mask.

[0279] Usually, a resist film is formed on the resist underlayer film.

[0280] The thickness of the resist film is preferably 200 nm or less, more preferably 150 nm or less, further preferably 100 nm or less, and particularly preferably 80 nm or less. In addition, the thickness of the resist film is preferably 10 nm or more, more preferably 20 nm or more, and particularly preferably 30 nm or more.

[0281] The resist film formed on the resist underlayer film by a known method (e.g., coating and firing of the resist) is not particularly limited as long as it is a material that responds to the light or electron beam (EB) used for irradiation. Both negative photoresists and positive photoresists can be used, but negative photoresists are preferably used.

[0282] There is no particular limitation on light or electron beam, and examples thereof include i-rays (365 nm), KrF excimer laser (248 nm), ArF excimer laser (193 nm), EUV (extreme ultraviolet; 13.5 nm), and EB (electron beam), but ArF excimer laser (193 nm) and EUV (extreme ultraviolet; 13.5 nm) are preferred.

[0283] It should be noted that in this specification, a resist that responds to EB is also referred to as a photoresist.

[0284] As photoresists, there are positive photoresists formed of novolac resin and 1,2-naphthoquinone diazosulfonic acid ester, chemically amplified photoresists formed of a binder having a group that increases the alkali dissolution rate by acid decomposition and a photoacid generator, chemically amplified photoresists formed of a low molecular weight compound that increases the alkali dissolution rate of the photoresist by acid decomposition, an alkali-soluble binder, and a photoacid generator, chemically amplified photoresists formed of a binder having a group that increases the alkali dissolution rate by acid decomposition, a low molecular weight compound that increases the alkali dissolution rate of the photoresist by acid decomposition, and a photoacid generator, and resists containing metal elements, etc. For example, JSR Corporation's product name V146G, Shipley's product name APEX-E, Sumitomo Chemical Co., Ltd.'s product name PAR710, Shin-Etsu Chemical Co., Ltd.'s product names AR2772 and SEPR430, etc. can be cited. In addition, for example, fluorine atom-containing polymer photoresists such as those described in Proc. SPIE, Vol. 3999, 330-334 (2000), Proc. SPIE, Vol. 3999, 357-364 (2000), and Proc. SPIE, Vol. 3999, 365-374 (2000) can be cited.

[0285] In addition, WO2019 / 188595, WO2019 / 187881, WO2019 / 187803, WO2019 / 167737, WO2019 / 167725, WO2019 / 187445, WO2019 / 167419, WO2019 / 123842, WO2019 / 054282, WO2019 / 058945, WO2019 / 058890, WO2019 / 039290, WO2019 / 044259, WO2019 / 044231, WO2019 / 026549, WO2018 / 193954, WO2019 / 172054, W O2019 / 021975, WO2018 / 230334, WO2018 / 194123, Japanese Special Opening 2018-180525, WO2018 / 190088, Japanese Special Opening 2018-070596, Japanese Special Opening 2018-028090, Japanese Special Opening 2016-153409, Japanese Special Opening 2016-130240, Japan Special Opening 2016-108325, Japanese Special Opening 2016-047920, Japanese Special Opening 2016-035570, Japan This special issue 2016-035567, Japan’s special issue 2016-035565, Japan’s special issue 2019-101417, Japan’s special issue 2019-117373 , Japanese Special Opening 2019-052294, Japanese Special Opening 2019-008280, Japanese Special Opening 2019-008279, Japanese Special Opening 2019-003176, Japanese Special Opening 2019-003175, Japanese Special Opening 2018-197853, Japanese Special Opening 2019-191298, Japanese Special Opening 2019-0 61217, Japanese Special Opening 2018-045152, Japanese Special Opening 2018-022039, Japanese Special Opening 2016-090441, Japanese Special Opening 2015-10878, Japanese Special Opening 2012-168279, Japanese Special Opening 2012-022261, Japanese Special Opening 2012-022258, Japanese Special Opening 20 11-043749, Japanese Patent Application Laid-Open No. 2010-181857, Japanese Patent Application Laid-Open No. 2010-128369, WO2018 / 031896, Japanese Patent Application Laid-Open No. 2019-113855, WO2017 / 156388, WO2017 / 066319, Japanese Patent Application Laid-Open No. 2018-41099, WO2016 / 065120, WO2015 / 026482, Japanese Patent Application Laid-Open No. 2016-29498, Japanese Patent Application Laid-Open No. 2011-253185, etc., so-called resist compositions, metal-containing resist compositions, etc., but are not limited to these.

[0286] Examples of the resist composition include the following compositions.

[0287] An active light-sensitive or radiation-sensitive resin composition comprising a resin A having a repeating unit having an acid-decomposable group in which a polar group is protected by a protecting group that is detached by the action of an acid, and a compound represented by the following general formula (21).

[0288]

[0289] In the general formula (21), m represents an integer of 1 to 6.

[0290] R 1 and R 2 Each independently represents a fluorine atom or a perfluoroalkyl group.

[0291] L 1 Represents -O-, -S-, -COO-, -SO 2 -or-SO 3 -.

[0292] L 2 represents an alkylene group which may have a substituent or a single bond.

[0293] W 1 It represents a cyclic organic group which may have a substituent.

[0294] M + Represents a cation.

[0295] A metal-containing film-forming composition for extreme ultraviolet or electron beam lithography contains a compound having a metal-oxygen covalent bond and a solvent, wherein the metal element constituting the compound belongs to the third to seventh periods of the third to fifteenth groups of the periodic table.

[0296] A radiation-sensitive resin composition comprising a polymer having a first structural unit represented by the following formula (31) and a second structural unit having an acid-dissociable group represented by the following formula (32), and an acid generator.

[0297]

[0298] (In formula (31), Ar is a group obtained by removing (n+1) hydrogen atoms from an aromatic hydrocarbon having 6 to 20 carbon atoms. R 1 is a hydroxyl group, a thiol group or a monovalent organic group having 1 to 20 carbon atoms. n is an integer of 0 to 11. When n is 2 or more, a plurality of R 1 Same or different. 2 is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group. 3is a monovalent group having 1 to 20 carbon atoms and containing the above-mentioned acid dissociable group. Z is a single bond, an oxygen atom or a sulfur atom. 4 is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group. )

[0299] A resist composition comprising: a resin (A1) containing a structural unit having a cyclic carbonate structure, a structural unit represented by the following formula, and a structural unit having an acid-labile group; and an acid generator.

[0300]

[0301] [Wherein,

[0302] R 2 represents an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, a hydrogen atom or a halogen atom, and X 1 Represents a single bond, -CO-O-* or -CO-NR 4 -*, * represents the bond with -Ar, R 4 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and Ar represents an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have one or more groups selected from a hydroxyl group and a carboxyl group.]

[0303] Examples of the resist film include the following.

[0304] A resist film comprises a base resin comprising a repeating unit represented by the following formula (a1) and / or a repeating unit represented by the following formula (a2), and a repeating unit which generates an acid bonded to a polymer main chain by exposure.

[0305]

[0306] (In formula (a1) and formula (a2), R A Each is independently a hydrogen atom or a methyl group. 1 and R 2 Each R is independently a tertiary alkyl group having 4 to 6 carbon atoms. 3 Each independently represents a fluorine atom or a methyl group. m represents an integer of 0 to 4. 1 X is a single bond, a phenylene group or a naphthylene group, or a linking group having 1 to 12 carbon atoms and containing at least one selected from an ester bond, a lactone ring, a phenylene group and a naphthylene group. 2 is a single bond, an ester bond, or an amide bond. )

[0307] Examples of resist materials include the following.

[0308] A resist material comprising a polymer having a repeating unit represented by the following formula (b1) or (b2).

[0309]

[0310] (In formula (b1) and formula (b2), R A X is a hydrogen atom or a methyl group. 1 is a single bond or an ester group. 2 is a linear, branched or cyclic alkylene group having 1 to 12 carbon atoms or an arylene group having 6 to 10 carbon atoms, and a part of the methylene group constituting the alkylene group may be substituted with an ether group, an ester group or a group containing a lactone ring, and X 2 At least one hydrogen atom contained is replaced by a bromine atom. 3 Rf is a single bond, an ether group, an ester group, or a linear, branched, or cyclic alkylene group having 1 to 12 carbon atoms, and a portion of the methylene groups constituting the alkylene group may be substituted with an ether group or an ester group. 1 ~Rf 4 Each independently represents a hydrogen atom, a fluorine atom or a trifluoromethyl group, but at least one of them is a fluorine atom or a trifluoromethyl group. 1 and Rf 2 They can also be combined to form a carbonyl group. 1 ~R 5 Each is independently a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, a linear, branched or cyclic alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or an aryloxyalkyl group having 7 to 12 carbon atoms, and a part or all of the hydrogen atoms of these groups may be substituted with a hydroxyl group, a carboxyl group, a halogen atom, an oxo group, a cyano group, an amide group, a nitro group, a sultone group, a sulfone group or a sulfonium salt-containing group, and a part of the methylene groups constituting these groups may be substituted with an ether group, an ester group, a carbonyl group, a carbonate group or a sulfonate group. In addition, R 1 and R 2 can combine to form a ring with the sulfur atom to which they are bound.)

[0311] A resist material includes a base resin including a polymer having a repeating unit represented by the following formula (a).

[0312]

[0313] (In formula (a), R A is a hydrogen atom or a methyl group. 1 is a hydrogen atom or an acid-labile group. 2 X is a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, or a halogen atom other than bromine. 1 X is a single bond or a phenylene group, or a linear, branched or cyclic alkylene group having 1 to 12 carbon atoms which may contain an ester group or a lactone ring. 2-O-, -O-CH 2 - or -NH-. m is an integer of 1 to 4. u is an integer of 0 to 3. Wherein, m+u is an integer of 1 to 4. )

[0314] A resist composition that generates acid upon exposure and changes its solubility in a developer by the action of the acid.

[0315] The invention comprises a base component (A) whose solubility in a developer solution changes due to the action of an acid, and a fluorine additive component (F) which is decomposable in an alkaline developer solution.

[0316] The fluorine additive component (F) contains a fluororesin component (F1) having a structural unit (f1) containing an alkali-dissociable group and a structural unit (f2) containing a group represented by the following general formula (f2-r-1).

[0317]

[0318] [In formula (f2-r-1), Rf 21 Each is independently a hydrogen atom, an alkyl group, an alkoxy group, a hydroxyl group, a hydroxyalkyl group or a cyano group. n" is an integer from 0 to 2. * is a bond.]

[0319] The structural unit (f1) includes a structural unit represented by the following general formula (f1-1) or a structural unit represented by the following general formula (f1-2).

[0320]

[0321] [In formula (f1-1) and (f1-2), R is independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms. X is a divalent linking group having no acid dissociable site. A aryl It is a divalent aromatic cyclic group which may have a substituent. 01 is a single bond or a divalent linking group. 2 Each independently is an organic group having a fluorine atom.]

[0322] Examples of the coating material, the coating solution, and the coating composition include the following.

[0323] A coating comprises a metal oxygen-hydroxyl network having organic ligands via metal carbon bonds and / or metal carboxylate bonds.

[0324] Inorganic oxygen / hydroxy based compositions.

[0325] A coating solution comprising: an organic solvent; a first organic metal composition, wherein the first organic metal composition is of formula R z SnO(2-(z / 2)-(x / 2)) (OH) x (Here, 0<z≤2 and 0<(z+x)≤4), formula R' n S X 4-n (where n=1 or 2), or a mixture thereof, wherein R and R' are independently hydrocarbon groups having 1 to 31 carbon atoms, and X is a ligand having a hydrolyzable bond to Sn or a combination thereof; and a hydrolyzable metal compound having the formula MX' v (here, M is a metal selected from Groups 2 to 16 of the periodic table, v is a number from 2 to 6, and X' is a ligand having a hydrolyzable MX bond or a combination thereof).

[0326] A coating solution comprising an organic solvent and a compound of formula RSnO (3 / 2-x / 2) (OH) x The first organometallic compound represented by (wherein 0<x<3), the solution contains about 0.0025M to about 1.5M of tin, R is an alkyl or cycloalkyl group having 3 to 31 carbon atoms, and the alkyl or cycloalkyl group is bonded to tin on a secondary or tertiary carbon atom.

[0327] An aqueous precursor solution for forming an inorganic pattern comprises a mixture of water, metal suboxide cations, polyatomic inorganic anions, and a radiation-sensitive ligand containing a peroxide group.

[0328] Irradiation with light or electron beams is performed, for example, through a mask (photomask) for forming a predetermined pattern.

[0329] There are no particular restrictions on the exposure amount and the irradiation energy of the electron beam.

[0330] Baking (PEB: Post Exposure Bake) may be performed after irradiation with light or electron beams and before development.

[0331] The baking temperature is not particularly limited, but is preferably 60°C to 150°C, more preferably 70°C to 120°C, and particularly preferably 75°C to 110°C.

[0332] The baking time is not particularly limited, but is preferably 1 second to 10 minutes, more preferably 10 seconds to 5 minutes, and particularly preferably 30 seconds to 3 minutes.

[0333] For development, for example, an alkaline developer can be used.

[0334] As development temperature, 5 degreeC - 50 degreeC is mentioned, for example.

[0335] As a development time, 10 seconds - 300 seconds are mentioned, for example.

[0336] As alkaline developer, for example, inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia water, primary amines such as ethylamine, n-propylamine, secondary amines such as diethylamine, di-n-butylamine, tertiary amines such as triethylamine, methyldiethylamine, alcohol amines such as dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, quaternary ammonium salts such as choline, pyrrole, piperidine and other cyclic amines and other alkali aqueous solutions can be used. Further, it is also possible to add an appropriate amount of alcohols such as isopropanol, non-ionic surfactants and the like to the aqueous solution of the above-mentioned alkalis and use them. Among them, the preferred developer is an aqueous solution of a quaternary ammonium salt, and more preferably an aqueous solution of tetramethylammonium hydroxide and an aqueous solution of choline. Further, surfactants and the like can also be added to these developers. It is also possible to use an organic solvent such as butyl acetate instead of an alkaline developer for development, and a method for developing the portion where the alkali dissolution rate of the photoresist is not increased.

[0337] Next, the resist underlayer film is etched using the formed resist pattern as a mask. The etching may be dry etching or wet etching, but dry etching is preferred.

[0338] When the inorganic film is formed on the surface of the semiconductor substrate used, the surface of the inorganic film is exposed, and when the inorganic film is not formed on the surface of the semiconductor substrate used, the surface of the semiconductor substrate is exposed. Then, the semiconductor substrate is processed by a known method (dry etching method, etc.) to manufacture a semiconductor element.

[0339] Example

[0340] Next, the contents of the present invention will be specifically described with reference to Examples, but the present invention is not limited to these.

[0341] <Determination of molecular weight>

[0342] The following are apparatuses and the like used for measuring the weight average molecular weight of the polymers obtained in the following Synthesis Examples and Comparative Synthesis Examples.

[0343] Device: HLC-8420GPC from Higashikata Co., Ltd.

[0344] GPC column: Shodex [registered trademark] Asahipak [registered trademark] (Showa Denko K.K.)

[0345] Column temperature: 40°C

[0346] Flow rate: 0.35mL / min

[0347] Eluent: Tetrahydrofuran (THF)

[0348] Standard sample: Polystyrene (Tosoh Corporation)

[0349] <Synthesis example 1>

[0350] 5.00 g of monomethyl diglycidyl isocyanuric acid (manufactured by Shikoku Chemical Industry Co., Ltd., product name: Me-DGIC, 30 wt% propylene glycol monomethyl ether solution), 1.66 g of 1,6-bis(2,3-epoxypropane-1-yloxy)naphthalene (manufactured by DIC Corporation, product name: HP-4032D), 2.77 g of 1,3-adamantanedicarboxylic acid, and tetrabutyl bromide were added. 0.30 g of propylene glycol monomethyl ether and 21.41 g of propylene glycol monomethyl ether were added to the reaction flask, and heated and stirred at an internal temperature of 105° C. for 24 hours under a nitrogen atmosphere. The obtained reaction product corresponded to formula (1-1), and the weight average molecular weight Mw measured by GPC in terms of polystyrene was 8800.

[0351] Formula (1-1)

[0352]

[0353] <Synthesis example 2>

[0354] 4.00 g of monomethyl diglycidyl isocyanuric acid (manufactured by Shikoku Chemical Industry Co., Ltd., product name: Me-DGIC, 30 wt% propylene glycol monomethyl ether solution), 1.33 g of 1,6-bis(2,3-epoxypropane-1-yloxy)naphthalene (manufactured by DIC Corporation, product name: HP-4032D), 1.96 g of (+)-camphor acid, and tetrabutyl bromide were added. 0.24 g of propylene glycol monomethyl ether and 16.10 g of propylene glycol monomethyl ether were added to the reaction flask, and heated and stirred at an internal temperature of 105° C. for 24 hours under a nitrogen atmosphere. The obtained reaction product corresponded to formula (1-2), and the weight average molecular weight Mw measured by GPC in terms of polystyrene was 9200.

[0355] Formula (1-2)

[0356]

[0357] <Synthesis Example 3>

[0358] 4.00 g of monomethyl diglycidyl isocyanuric acid (manufactured by Shikoku Chemical Industry Co., Ltd., product name: Me-DGIC, 30 wt% propylene glycol monomethyl ether solution), 1.33 g of 1,6-bis(2,3-epoxypropane-1-yloxy)naphthalene (manufactured by DIC Corporation, product name: HP-4032D), 1.70 g of trans-1,4-cyclohexanedicarboxylic acid, and tetrabutyl bromide were added. 0.24 g of propylene glycol monomethyl ether and 15.07 g of propylene glycol monomethyl ether were added to the reaction flask, and heated and stirred at an internal temperature of 105° C. for 24 hours under a nitrogen atmosphere. The obtained reaction product corresponded to formula (1-3), and the weight average molecular weight Mw measured by GPC in terms of polystyrene was 8400.

[0359] Formula (1-3)

[0360]

[0361] <Synthesis example 4>

[0362] 4.00 g of monomethyl diglycidyl isocyanuric acid (manufactured by Shikoku Chemical Industry Co., Ltd., product name: Me-DGIC, 30 wt% propylene glycol monomethyl ether solution), 1.33 g of 1,6-bis(2,3-epoxypropane-1-yloxy)naphthalene (manufactured by DIC Corporation, product name: HP-4032D), 1.80 g of 5-norbornene-2,3-dicarboxylic acid, and tetrabutyl bromide were added. 0.24 g of propylene glycol monomethyl ether and 15.47 g of propylene glycol monomethyl ether were added to the reaction flask, and heated and stirred at an internal temperature of 105° C. for 24 hours under a nitrogen atmosphere. The obtained reaction product corresponded to formula (1-4) and had a weight average molecular weight Mw of 4500 as measured by GPC in terms of polystyrene.

[0363] Formula (1-4)

[0364]

[0365] <Synthesis Example 5>

[0366] 5.00 g of monomethyl diglycidyl isocyanuric acid (manufactured by Shikoku Chemical Industry Co., Ltd., product name: Me-DGIC, 30 wt% propylene glycol monomethyl ether solution), 1.73 g of diglycidyl terephthalate (manufactured by Nagase Chemtex Co., Ltd., product name: Denacol EX-711), 2.77 g of 1,3-adamantanedicarboxylic acid, and tetrabutyl bromide were mixed. 0.30 g of propylene glycol monomethyl ether and 21.67 g of propylene glycol monomethyl ether were added to the reaction flask, and heated and stirred at an internal temperature of 105° C. for 24 hours under a nitrogen atmosphere. The obtained reaction product corresponded to formula (1-5), and the weight average molecular weight Mw measured by GPC in terms of polystyrene was 8400.

[0367] Formula (1-5)

[0368]

[0369] <Synthesis example 6>

[0370] 5.00 g of monomethyl diglycidyl isocyanuric acid (manufactured by Shikoku Chemical Industry Co., Ltd., product name: Me-DGIC, 30% by weight propylene glycol monomethyl ether solution), 2.79 g of resorcinol diglycidyl ether (manufactured by Nagase Chemtex Co., Ltd., product name: Denacol EX-201-IM, 50% by weight propylene glycol monomethyl ether solution), 2.77 g of 1,3-adamantanedicarboxylic acid, and tetrabutyl bromide were mixed. 0.30 g and 18.94 g of propylene glycol monomethyl ether were added to the reaction flask, and heated and stirred at an internal temperature of 105° C. for 24 hours under a nitrogen atmosphere. The obtained reaction product corresponded to formula (1-6), and the weight average molecular weight Mw measured by GPC in terms of polystyrene was 8700.

[0371] Formula (1-6)

[0372]

[0373] <Synthesis Example 7>

[0374] 4.00 g of monomethyl diglycidyl isocyanuric acid (manufactured by Shikoku Chemical Industry Co., Ltd., product name: Me-DGIC, 30 wt% propylene glycol monomethyl ether solution), 1.93 g of naphthalene-type epoxy resin (manufactured by DIC Corporation, product name: HP-4770), 2.53 g of 1,3-adamantanedicarboxylic acid, and tetrabutyl bromide were mixed. 0.24 g of propylene glycol monomethyl ether and 20.79 g of propylene glycol monomethyl ether were added to the reaction flask, and heated and stirred at an internal temperature of 105° C. for 24 hours under a nitrogen atmosphere. The obtained reaction product corresponded to formula (1-7) and had a weight average molecular weight Mw of 9800 as measured by GPC in terms of polystyrene.

[0375] Formula (1-7)

[0376]

[0377] <Synthesis example 8>

[0378] 7.00 g of monomethyl diglycidyl isocyanuric acid (manufactured by Shikoku Chemical Industry Co., Ltd., product name: Me-DGIC, 30 wt% propylene glycol monomethyl ether solution), 1.64 g of 1,3-adamantanedicarboxylic acid, 1.64 g of bis(4-hydroxyphenyl)sulfone, and tetrabutyl bromide were mixed. 0.21 g of propylene glycol monomethyl ether and 12.56 g of propylene glycol monomethyl ether were added to the reaction flask, and heated and stirred at an internal temperature of 105° C. for 24 hours under a nitrogen atmosphere. The obtained reaction product corresponded to formula (1-8), and the weight average molecular weight Mw measured by GPC in terms of polystyrene was 5200.

[0379] Formula (1-8)

[0380]

[0381] <Synthesis Example 9>

[0382] 7.00 g of diglycidyl dimethylhydantoin (manufactured by Shikoku Chemical Industry Co., Ltd., product name: DG-DMH, 30 wt% propylene glycol monomethyl ether solution), 0.81 g of 5-hydroxyisophthalic acid, 1.10 g of 1,3-adamantanedicarboxylic acid, and tetrabutyl bromide were mixed. 0.22 g of propylene glycol monomethyl ether and 12.00 g of propylene glycol monomethyl ether were added to the reaction flask, and heated and stirred at an internal temperature of 105° C. for 24 hours under a nitrogen atmosphere. The obtained reaction product corresponded to formula (1-9) and had a weight average molecular weight Mw of 6300 as measured by GPC in terms of polystyrene.

[0383] Formula (1-9)

[0384]

[0385] <Comparative Synthesis Example 1>

[0386] 5.00 g of monomethyl diglycidyl isocyanuric acid (manufactured by Shikoku Chemical Industry Co., Ltd., product name: Me-DGIC, 30 wt% propylene glycol monomethyl ether solution), 1.66 g of 1,6-bis(2,3-epoxypropane-1-yloxy)naphthalene (manufactured by DIC Corporation, product name: HP-4032D), 2.19 g of 2,2-mercaptoacetic acid, and tetrabutyl bromide were added. 0.30 g of propylene glycol monomethyl ether and 19.10 g of propylene glycol monomethyl ether were added to the reaction flask, and heated and stirred at an internal temperature of 105° C. for 24 hours under a nitrogen atmosphere. The obtained reaction product corresponded to the formula (1-10), and the weight average molecular weight Mw measured by GPC in terms of polystyrene was 1700.

[0387] Formula (1-10)

[0388]

[0389] <Comparative Synthesis Example 2>

[0390] 7.00 g of diglycidyl dimethylhydantoin (manufactured by Shikoku Chemical Industry Co., Ltd., product name: DG-DMH, 30 wt% propylene glycol monomethyl ether solution), 0.81 g of 5-hydroxyisophthalic acid, 0.72 g of L(+)-tartaric acid, and tetrabutyl bromide were mixed. 0.22 g of propylene glycol monomethyl ether and 12.00 g of propylene glycol monomethyl ether were added to the reaction flask, and heated and stirred at an internal temperature of 105° C. for 24 hours under a nitrogen atmosphere. The obtained reaction product corresponded to the formula (1-11), and the weight average molecular weight Mw measured by GPC in terms of polystyrene was 1700.

[0391] Formula (1-11)

[0392]

[0393] <Example 1>

[0394] To 2.707 g of the solution (solid content: 17.4 wt%) of the reaction product of the above formula (1-1) obtained in Synthesis Example 1 were added 0.118 g of tetramethoxymethyl glycoluril (trade name: POWDERLINK [registered trademark] 1174, manufactured by Japan Science Instruments Co., Ltd.) as a crosslinking agent and pyridine as a crosslinking catalyst. - 0.012 g of p-toluenesulfonate, 0.001 g of Megafac R-30N (trade name, manufactured by DIC Corporation), 51.223 g of propylene glycol monomethyl ether, and 5.940 g of propylene glycol monomethyl ether acetate were added to prepare a resist underlayer film-forming composition.

[0395] <Example 2>

[0396] To 2.529 g of the solution (solid content 18.6 wt%) of the reaction product of the above formula (1-2) obtained in Synthesis Example 2 were added 0.118 g of tetramethoxymethyl glycoluril (trade name: POWDERLINK [registered trademark] 1174, manufactured by Japan Science Instruments Co., Ltd.) as a crosslinking agent and pyridine as a crosslinking catalyst. - 0.012 g of p-toluenesulfonate, 0.001 g of Megafac R-30N (trade name, manufactured by DIC Corporation), 51.401 g of propylene glycol monomethyl ether, and 5.940 g of propylene glycol monomethyl ether acetate were added to prepare a resist underlayer film-forming composition.

[0397] <Example 3>

[0398] To 2.588 g of the solution (solid content 18.2 wt%) of the reaction product of the above formula (1-3) obtained in Synthesis Example 3 were added 0.118 g of tetramethoxymethyl glycoluril (trade name: POWDERLINK [registered trademark] 1174, manufactured by Japan Science Instruments Co., Ltd.) as a crosslinking agent and pyridine as a crosslinking catalyst. - 0.012 g of p-toluenesulfonate, 0.001 g of Megafac R-30N (trade name, manufactured by DIC Corporation), 51.342 g of propylene glycol monomethyl ether, and 5.940 g of propylene glycol monomethyl ether acetate were added to prepare a resist underlayer film-forming composition.

[0399] <Example 4>

[0400] To 2.599 g of the solution (solid content 18.1 wt%) of the reaction product of the above formula (1-4) obtained in Synthesis Example 4 were added 0.118 g of tetramethoxymethyl glycoluril (trade name: POWDERLINK [registered trademark] 1174, manufactured by Japan Science Instruments Co., Ltd.) as a crosslinking agent and pyridine as a crosslinking catalyst. - 0.012 g of p-toluenesulfonate, 0.001 g of Megafac R-30N (trade name, manufactured by DIC Corporation), 51.310 g of propylene glycol monomethyl ether, and 5.940 g of propylene glycol monomethyl ether acetate were added to prepare a resist underlayer film-forming composition.

[0401] <Example 5>

[0402] To 2.620 g of the solution (solid content 18.0 wt%) of the reaction product of the above formula (1-5) obtained in Synthesis Example 5 were added 0.118 g of tetramethoxymethyl glycoluril (trade name: POWDERLINK [registered trademark] 1174, manufactured by Japan Science Instruments Co., Ltd.) as a crosslinking agent and pyridine as a crosslinking catalyst. - 0.012 g of p-toluenesulfonate, 0.001 g of Megafac R-30N (trade name, manufactured by DIC Corporation), 51.311 g of propylene glycol monomethyl ether, and 5.940 g of propylene glycol monomethyl ether acetate were added to prepare a resist underlayer film-forming composition.

[0403] <Example 6>

[0404] To 2.542 g of the solution (solid content 18.5 wt%) of the reaction product of the above formula (1-6) obtained in Synthesis Example 6, 0.118 g of tetramethoxymethyl glycoluril (trade name: POWDERLINK [registered trademark] 1174, manufactured by Japan Science Instruments Co., Ltd.) as a crosslinking agent and 0.118 g of pyridine as a crosslinking catalyst were added. - 0.012 g of p-toluenesulfonate, 0.001 g of Megafac R-30N (product name, manufactured by DIC Corporation), 51.389 g of propylene glycol monomethyl ether, and 5.940 g of propylene glycol monomethyl ether acetate were added to prepare a resist underlayer film-forming composition.

[0405] <Example 7>

[0406] To 2.405 g of the solution (solid content 19.6 wt%) of the reaction product of the above formula (1-7) obtained in Synthesis Example 7 were added 0.118 g of tetramethoxymethyl glycoluril (trade name: POWDERLINK [registered trademark] 1174, manufactured by Japan Science Instruments Co., Ltd.) as a crosslinking agent and pyridine as a crosslinking catalyst. - 0.012 g of p-toluenesulfonate, 0.001 g of Megafac R-30N (trade name, manufactured by DIC Corporation), 51.525 g of propylene glycol monomethyl ether, and 5.940 g of propylene glycol monomethyl ether acetate were added to prepare a resist underlayer film-forming composition.

[0407] <Example 8>

[0408] To 2.538 g of the solution (solid content 18.5 wt%) of the reaction product of the above formula (1-8) obtained in Synthesis Example 8 were added 0.118 g of tetramethoxymethyl glycoluril (trade name: POWDERLINK [registered trademark] 1174, manufactured by Japan Science Instruments Co., Ltd.) as a crosslinking agent and pyridine as a crosslinking catalyst. - 0.012 g of p-toluenesulfonate, 0.001 g of Megafac R-30N (trade name, manufactured by DIC Corporation), 51.393 g of propylene glycol monomethyl ether, and 5.940 g of propylene glycol monomethyl ether acetate were added to prepare a resist underlayer film-forming composition.

[0409] <Example 9>

[0410] To 2.458 g of the solution (solid content 19.1 wt%) of the reaction product of the above formula (1-9) obtained in Synthesis Example 9 were added 0.118 g of tetramethoxymethyl glycoluril (trade name: POWDERLINK [registered trademark] 1174, manufactured by Japan Science Instruments Co., Ltd.) as a crosslinking agent and pyridine as a crosslinking catalyst. - 0.012 g of p-toluenesulfonate, 0.001 g of Megafac R-30N (product name, manufactured by DIC Corporation), 51.472 g of propylene glycol monomethyl ether, and 5.940 g of propylene glycol monomethyl ether acetate were added to prepare a resist underlayer film-forming composition.

[0411] <Comparative Example 1>

[0412] To 3.584 g of the solution (solid content 13.1 wt%) of the reaction product of the formula (1-10) obtained in Comparative Synthesis Example 1 were added 0.118 g of tetramethoxymethyl glycoluril (trade name: POWDERLINK [registered trademark] 1174, manufactured by Japan Science Instruments Co., Ltd.) as a crosslinking agent and pyridine as a crosslinking catalyst. - 0.012 g of p-toluenesulfonate, 0.001 g of Megafac R-30N (product name, manufactured by DIC Corporation), 50.346 g of propylene glycol monomethyl ether, and 5.940 g of propylene glycol monomethyl ether acetate were added to prepare a resist underlayer film-forming composition.

[0413] <Comparative Example 2>

[0414] To 2.305 g of the solution (solid content 20.4 wt%) of the reaction product of the formula (1-11) obtained in Comparative Synthesis Example 2 were added 0.118 g of tetramethoxymethyl glycoluril (trade name: POWDERLINK [registered trademark] 1174, manufactured by Japan Science Instruments Co., Ltd.) as a crosslinking agent and pyridine as a crosslinking catalyst. - 0.012 g of p-toluenesulfonate, 0.001 g of Megafac R-30N (trade name, manufactured by DIC Corporation), 51.625 g of propylene glycol monomethyl ether, and 5.940 g of propylene glycol monomethyl ether acetate were added to prepare a resist underlayer film-forming composition.

[0415] [Evaluation of resist solvent resistance]

[0416] The resist underlayer film-forming compositions prepared in Examples 1 to 9 and Comparative Examples 1 to 2 were each applied (spin-coated) on a silicon wafer using a spin coater. The coated silicon wafer was heated on a hot plate at 215°C for 1 minute to form a resist underlayer film with a thickness of 20 nm. Next, in order to confirm the resist solvent resistance of the resist underlayer film, the silicon wafer after the resist underlayer film was formed was immersed in a solvent obtained by mixing propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate in a weight ratio of 7:3 for 1 minute, and then spun dry and baked at 100°C for 30 seconds. The film thickness of the resist underlayer film before and after immersion in the mixed solvent was measured using a film thickness measuring device (product name: RE-3100, manufactured by Dainippon Screen Manufacturing Co., Ltd.).

[0417] Regarding the evaluation of the resist solvent resistance, the film thickness reduction rate (%) of the resist underlayer film removed by solvent immersion was calculated and evaluated by the following calculation formula. The results are shown in Table 1. It should be noted that if the film thickness reduction rate is about 1% or less, it can be said that the resist solvent resistance is sufficient.

[0418] Film thickness reduction rate (%) = (A 0 -A 1 )÷A 0 〕×100

[0419] A 0 : Film thickness before solvent immersion

[0420] A 1 : Film thickness after solvent immersion

[0421] [Table 1]

[0422] Film thickness reduction rate Example 1 -0.50％ Example 2 -0.30％ Example 3 -0.20％ Example 4 0.00％ Example 5 -0.40％ Example 6 -0.20％ Example 7 -0.50％ Example 8 -0.20％ Example 9 0.50％ Comparative Example 1 0.00％ Comparative Example 2 0.30％

[0423] From the above results, it can be seen that the film thickness change of the resist underlayer film forming compositions of Examples 1 to 9 and Comparative Examples 1 to 2 is very small even after being immersed in a resist solvent. Therefore, the resist underlayer film forming compositions of Examples 1 to 9 have sufficient resist solvent resistance to function as a resist underlayer film.

[0424] 〔Evaluation of optical constants〕

[0425] Each of the compositions for forming an underlayer film of the resist prepared in Examples 1 to 9 and Comparative Examples 1 to 2 was applied to a silicon wafer using a spin coater in a film thickness of about 50 nm, and baked (baked) for 60 seconds at 215° C. on a hot plate. The n value (refractive index) and k value (attenuation coefficient) of the obtained underlayer film of the resist were measured using a spectroscopic ellipsometer (VUV-VASE, manufactured by JA Woolam) at a wavelength of 193 nm (ArF excimer laser wavelength). The results are shown in Table 2.

[0426] [Table 2]

[0427] n / k(193nm) Example 1 1.73 / 0.12 Example 2 1.72 / 0.13 Example 3 1.73 / 0.14 Example 4 1.69 / 0.21 Example 5 1.75 / 0.21 Example 6 1.72 / 0.19 Example 7 1.69 / 0.12 Example 8 1.84 / 0.22 Example 9 1.73 / 0.17 Comparative Example 1 1.78 / 0.17 Comparative Example 2 1.72 / 0.17

[0428] As can be seen from the above results, Examples 1 to 9 have appropriate n and k values ​​at 193 nm. Therefore, the coating film obtained from the resist underlayer film-forming composition obtained by Examples 1 to 9 has an anti-reflection function that can suppress reflection (standing wave) from the base substrate, which is a cause of an undesired resist pattern, in a photolithography process using radiation such as an ArF excimer laser. Therefore, it is useful as a resist underlayer film.

[0429] [Formation and evaluation of resist patterns]

[0430] The resist underlayer film-forming compositions prepared in Examples and Comparative Examples were evaluated for lithographic performance by negative tone development (NTD).

[0431] A composition for an anti-reflection layer for controlling reflection was spin-coated on a silicon wafer and heated at 205°C for 1 minute to form an anti-reflection layer (n=1.81, k=0.33, 193 nm). Next, the compositions for forming a resist underlayer film prepared in Examples 1 to 9 and Comparative Examples 1 to 2 were spin-coated and heated at 215°C for 1 minute to form a resist underlayer film. An NTD resist solution was spin-coated on the resist underlayer film, heated at 90°C for 60 seconds, and exposed under specified conditions using an ArF excimer laser exposure device (manufactured by Nikon, NSR-307E). After exposure, the film was heated at 90°C for 60 seconds (PEB), cooled to room temperature on a cooling plate, and developed with n-butyl acetate to form a line / space resist pattern.

[0432] The dimensions of the formed resist pattern were measured using a length-measuring SEM, and the minimum line CD (Min Line CD) obtained by exposure to light of various light intensities is summarized in Table 3 below.

[0433] [Table 3]

[0434]

[0435] From the above results, it can be said that the resist underlayer film-forming compositions of Examples 1 to 9 have improved Min Line CD compared with the resist underlayer film-forming compositions of Comparative Examples 1 to 2. That is, by introducing an alicyclic structure into the resist underlayer film, adhesion with the resist is exhibited, and the undesirable phenomenon of resist pattern collapse can be suppressed.

Claims

1. A resist underlayer film-forming composition comprising a polymer having an alicyclic structure other than at a terminal, and a solvent. 2 . The resist underlayer film forming composition according to claim 1 , wherein the polymer further has an aromatic hydrocarbon ring. 3 . The resist underlayer film-forming composition according to claim 1 , wherein the polymer further has a nitrogen-containing ring.

4. The resist underlayer film-forming composition according to claim 1, wherein the polymer has a structure represented by the following formula (1) as the structure having the alicyclic structure: In formula (1), A cy represents a divalent group having an alicyclic structure; n1 and n2 each independently represent 0 or 1; and * represents a bond.

5. The resist underlayer film forming composition according to claim 2, wherein the polymer has a structure represented by the following formula (2) as the structure having the aromatic hydrocarbon ring: In formula (2), Ar1 represents a divalent organic group having an aromatic hydrocarbon ring; n11 and n12 each independently represent 0 or 1; p1 and p2 each independently represent 0 or 1; A1, A2, A3, A4, A5 and A6 each independently represent a hydrogen atom, a methyl group or an ethyl group; * represents a bond.

6. The resist underlayer film-forming composition according to claim 3, wherein the polymer has a structure represented by the following formula (3) as the structure having the nitrogen-containing ring: In formula (3), X1 represents a group represented by any one of the following formulas (3-1) to (3-3); Z1 and Z2 each independently represent a single bond or a divalent group represented by the following formula (3-4); A 11 , A 12 , A 13 , A 14 , A 15 and A 16 Each independently represents a hydrogen atom, a methyl group or an ethyl group; p3 and p4 each independently represent 0 or 1; * represents a bond, In the formulae (3-1) to (3-3), R1 to R5 each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may be interrupted by an oxygen atom or a sulfur atom, an alkenyl group having 2 to 10 carbon atoms which may be interrupted by an oxygen atom or a sulfur atom, an alkynyl group having 2 to 10 carbon atoms which may be interrupted by an oxygen atom or a sulfur atom, a benzyl group, or a phenyl group, wherein the phenyl group may be substituted with at least one monovalent group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a cyano group, and an alkylthio group having 1 to 6 carbon atoms; R1 and R2 may also be combined with each other to form a ring having 3 to 6 carbon atoms; R3 and R4 may also be combined with each other to form a ring having 3 to 6 carbon atoms; * represents a bond; *1 represents a bond to a carbon atom in formula (3); *2 represents a bond to a nitrogen atom in formula (3); In formula (3-4), m1 is an integer of 0 to 4, m2 is 0 or 1, m3 is 0 or 1, and m4 is an integer of 0 to 2; wherein, When m3 is 1, m1 and m2 are not simultaneously 0; *3 represents a bond to the nitrogen atom in formula (3); and *4 represents a bond. 7 . The resist underlayer film-forming composition according to claim 1 , further comprising a crosslinking agent. 8 . The resist underlayer film forming composition according to claim 1 , further comprising a curing catalyst. 9 . The resist underlayer film-forming composition according to claim 1 , which is used for forming an underlayer film of a negative photoresist. 10 . The resist underlayer film-forming composition according to claim 1 , which is used for lithography using ArF excimer laser or EUV. 11 . A resist underlayer film which is a cured product of the resist underlayer film-forming composition according to claim 1 . 12 . A semiconductor processing substrate comprising a semiconductor substrate and the resist underlayer film according to claim 11 .

13. A method for manufacturing a semiconductor device, comprising the following steps: A step of forming a resist underlayer film on a semiconductor substrate using the resist underlayer film-forming composition according to any one of claims 1 to 10; and A step of forming a resist film on the resist underlayer film.

14. A pattern forming method comprising the following steps: A step of forming a resist underlayer film on a semiconductor substrate using the resist underlayer film-forming composition according to any one of claims 1 to 10; forming a resist film on the resist underlayer film; irradiating the resist film with light or an electron beam, and then developing the resist film to obtain a resist pattern; and A step of etching the resist underlayer film using the resist pattern as a mask.

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