Composition for forming resist underlayer film

Abstract

The present invention provides a composition for forming a resist underlayer film for EB or EUV lithography, the composition comprising a polymer having a structure represented by formula (1) and a solvent. (In formula (1), R1 and R2 each independently represent an alkyl group having 1-6 carbon atoms, which may be substituted by a halogen atom, or a halogen atom. And m1 and m2 each independently represent an integer of 0-4. When there are two or more R1s, the two or more R1s may be the same as or different from each other. When there are two or more R2 groups, the two or more R2 groups may be the same or different. And * represents a bonding position. > # imgabs0 #

Description

Technical Field

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

[0002] All along, in the manufacture of semiconductor devices, micro-machining is performed by using the photolithography of a resist composition. The above-mentioned micro-machining is to form a thin film of a photoresist composition on a semiconductor substrate such as a silicon wafer, irradiate active light such as ultraviolet rays through a mask pattern depicting a device pattern, develop, and use the obtained photoresist pattern as a protective film to etch the substrate, thereby forming a processing method of fine concave-convex corresponding to the above-mentioned photoresist pattern on the substrate surface. In recent years, the high integration of semiconductor devices continues to be carried out. For the active light used, in addition to the i-line (wavelength 365nm), KrF excimer laser (wavelength 248nm), ArF excimer laser (wavelength 193nm) used in the past, the practicality of EUV light (wavelength 13.5nm) or EB (electron beam) in the most advanced micro-machining has also been studied. Accompanied by this, the poor formation of the resist pattern caused by the influence of aspects such as semiconductor substrates has become a big problem. Therefore, in order to solve this problem, a method for arranging a resist lower film between a resist and a semiconductor substrate has been widely studied.

[0003] Patent Document 1 discloses a composition for forming an underlayer film for lithography containing a naphthalene ring having a halogen atom. Patent Document 2 discloses a halogenated antireflective film. Patent Document 3 discloses a composition for forming a resist underlayer film.

[0004] Prior art literature

[0005] Patent Literature

[0006] Patent Document 1: International Publication No. 2006 / 003850

[0007] Patent Document 2: Japanese Patent Application No. 2005-526270

[0008] Patent Document 3: International Publication No. 2020 / 111068 Summary of the invention

[0009] Problems to be solved by the invention

[0010] In semiconductor device processing, in order to improve productivity, as one of the methods for shortening exposure time, high sensitivity of resist is required. In particular, in semiconductor device processing using the most advanced EB (electron beam) or EUV (extreme ultraviolet) lithography technology, EB irradiation time or EUV exposure time affects productivity, so this demand is strong.

[0011] The present invention is completed in view of the above situation, and its purpose is to provide a resist underlayer film forming composition that can form a resist underlayer film that can improve the sensitivity of the resist, as well as a resist underlayer film, a laminate, and a semiconductor element manufacturing method and a pattern forming method using the resist underlayer film forming composition.

[0012] Means of solving the problem

[0013] The present inventors have conducted intensive studies to solve the above problems and, as a result, have found that the above problems can be solved, thereby completing the present invention having the following gist.

[0014] That is, the present invention includes the following aspects.

[0015] [1] A resist underlayer film-forming composition for EB or EUV lithography, comprising a polymer having a structure represented by the following formula (1) and a solvent.

[0016]

[0017] In formula (1), R 1 and R 2 Each independently represents an alkyl group having 1 to 6 carbon atoms which may be substituted by a halogen atom, or a halogen atom;

[0018] m1 and m2 each independently represent an integer from 0 to 4;

[0019] R 1 When there are 2 or more R 1 It can be the same or different;

[0020] R 2 When there are 2 or more R 2 It can be the same or different;

[0021] *Indicates bonding position.

[0022] [2] The resist underlayer film forming composition according to [1], wherein the polymer has a repeating unit represented by the following formula (1-1) as a repeating unit having a structure represented by the above formula (1).

[0023]

[0024] In formula (1-1), R 1 and R 2 Each independently represents an alkyl group having 1 to 6 carbon atoms which may be substituted by a halogen atom, or a halogen atom;

[0025] m1 and m2 each independently represent an integer from 0 to 4;

[0026] R 1 When there are 2 or more R 1 It can be the same or different;

[0027] R 2 When there are 2 or more R 2 It can be the same or different;

[0028] Q 1 represents a divalent organic group having an aromatic hydrocarbon ring;

[0029] n1 and n2 each independently represent 0 or 1.

[0030] [3] The resist underlayer film forming composition according to [2], wherein Q 1 It is represented by the following formula (1-1-1).

[0031]

[0032] In formula (1-1-1), Z 1 represents a single bond, an alkylene group having 1 to 6 carbon atoms which may be substituted by a halogen atom, or a sulfonyl group;

[0033] R 11 and R 12 each independently represents an alkyl group having 1 to 13 carbon atoms which may be substituted by a halogen atom, a hydroxyl group, a methoxy group, a thiol group, an acetyl group, a nitro group, an allyl group, a phenyl group, a naphthyl group, or a halogen atom;

[0034] n11 and n12 each independently represent an integer from 0 to 4;

[0035] R 11 When there are 2 or more R 11 It can be the same or different;

[0036] R 12 When there are 2 or more R 12 It can be the same or different.

[0037] [4] The resist underlayer film forming composition according to any one of [1] to [3], wherein m1 and m2 are 1, R 1 and R 2 It is methyl.

[0038] [5] The resist underlayer film forming composition according to any one of [1] to [4], comprising a crosslinking agent.

[0039] [6] The resist underlayer film forming composition according to [5], wherein the crosslinking agent is a compound having two or more structures represented by the following formula (C).

[0040]

[0041] In formula (C), R 101 represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxyalkyl group having 2 to 6 carbon atoms; * represents a bonding position.

[0042] [7] A resist underlayer film which is a cured product of the resist underlayer film-forming composition according to any one of [1] to [6].

[0043] [8] A laminate comprising a semiconductor substrate and the resist underlayer film according to [7].

[0044] [9] A method for manufacturing a semiconductor device, comprising:

[0045] 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 [6]; and

[0046] A step of forming a resist film on the resist underlayer film.

[0047]

[10] A pattern forming method comprising:

[0048] 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 [6];

[0049] forming a resist film on the resist underlayer film;

[0050] irradiating the resist film with EB or EUV, and then developing the resist film to obtain a resist pattern; and

[0051] A step of etching the resist underlayer film using the resist pattern as a mask.

[0052] Effects of the Invention

[0053] According to the present invention, there can be provided a resist underlayer film-forming composition capable of forming a resist underlayer film capable of improving the sensitivity of a resist, and a resist underlayer film, a laminate, a method for producing a semiconductor element, and a pattern forming method using the resist underlayer film-forming composition. DETAILED DESCRIPTION

[0054] (Resist underlayer film forming composition)

[0055] The resist underlayer film-forming composition of the present invention is a resist underlayer film-forming composition for EB (electron beam) or EUV (extreme ultraviolet) lithography. The resist underlayer film-forming composition contains a polymer (A) and a solvent.

[0056] <Polymer (A)>

[0057] The polymer (A) has a structure represented by the following formula (1).

[0058]

[0059] In formula (1), R 1 and R 2 Each independently represents an alkyl group having 1 to 6 carbon atoms which may be substituted by a halogen atom, or a halogen atom;

[0060] m1 and m2 each independently represent an integer from 0 to 4;

[0061] R 1 When there are 2 or more R 1 It can be the same or different;

[0062] R 2 When there are 2 or more R 2 It can be the same or different;

[0063] *Indicates bonding position.

[0064] As R 1 and R 2 The alkyl group having 1 to 6 carbon atoms which may be substituted with a halogen atom includes, for example, an alkyl group having 1 to 6 carbon atoms.

[0065] Examples of the alkyl group having 1 to 6 carbon atoms include methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, 1-methylcyclopropyl, 2-methylcyclopropyl, n-pentyl, 1-methyl n-butyl, 2-methyl n-butyl, 3-methyl n-butyl, 1,1-dimethyl n-propyl, 1,2-dimethyl n-propyl, 2,2-dimethyl n-propyl, 1-ethyl n-propyl, cyclopentyl, 1-methylcyclobutyl, 2-methylcyclopropyl, n-pentyl, 1-methyl n-butyl, 2-methyl n-butyl, 3-methyl n-butyl, 1,1-dimethyl n-propyl, 1,2-dimethyl n-propyl, 2,2-dimethyl n-propyl, 1-ethyl n-propyl, cyclopentyl, 1-methylcyclobutyl, 2 -methylcyclobutyl, 3-methylcyclobutyl, 1,2-dimethylcyclopropyl, 2,3-dimethylcyclopropyl, 1-ethylcyclopropyl, 2-ethylcyclopropyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n-pentyl, 4-methyl-n-pentyl, 1,1-dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1,3-dimethyl-n-butyl, 2,2-dimethyl-n-butyl, 2,3-dimethyl-n-butyl, 3,3-dimethyl-n-butyl, 1 -ethyl n-butyl, 2-ethyl n-butyl, 1,1,2-trimethyl n-propyl, 1,2,2-trimethyl n-propyl, 1-ethyl-1-methyl n-propyl, 1-ethyl-2-methyl n-propyl, cyclohexyl, 1-methylcyclopentyl, 2-methylcyclopentyl, 3-methylcyclopentyl, 1-ethylcyclobutyl, 2-ethylcyclobutyl, 3-ethylcyclobutyl, 1,2-dimethylcyclobutyl, 1,3-dimethylcyclobutyl, 2,2-dimethylcyclobutyl, 2,3- Dimethylcyclobutyl, 2,4-dimethylcyclobutyl, 3,3-dimethylcyclobutyl, 1-n-propylcyclopropyl, 2-n-propylcyclopropyl, 1-isopropylcyclopropyl, 2-isopropylcyclopropyl, 1,2,2-trimethylcyclopropyl, 1,2,3-trimethylcyclopropyl, 2,2,3-trimethylcyclopropyl, 1-ethyl-2-methylcyclopropyl, 2-ethyl-1-methylcyclopropyl, 2-ethyl-2-methylcyclopropyl, 2-ethyl-3-methylcyclopropyl and the like.

[0066] Among these groups, an alkyl group having 1 to 4 carbon atoms is preferred, a methyl group and an ethyl group are more preferred, and a methyl group is particularly preferred.

[0067] Preferably, m1 and m2 in formula (1-1) are 1, R 1 and R 2 It is methyl.

[0068] Examples of the structure represented by formula (1) include the following structures.

[0069]

[0070] In the formula, * indicates the bonding position.

[0071] The bonding position * in the structure represented by formula (1) is bonded to, for example, a hetero atom. Examples of the hetero atom include an oxygen atom and a nitrogen atom.

[0072] The polymer (A) may have at least one of a repeating structure represented by the following formula (1-1) and a repeating unit represented by the following formula (1-2) as the repeating unit having a structure represented by the formula (1).

[0073] The polymer (A) preferably has a repeating unit represented by the following formula (1-1) as a repeating unit having a structure represented by the formula (1).

[0074]

[0075] In formula (1-1), R 1 and R 2 Each independently represents an alkyl group having 1 to 6 carbon atoms which may be substituted by a halogen atom, or a halogen atom;

[0076] m1 and m2 each independently represent an integer from 0 to 4;

[0077] R 1 When there are 2 or more R 1 It can be the same or different;

[0078] R 2 When there are 2 or more R 2 It can be the same or different;

[0079] Q 1 represents a divalent organic group having an aromatic hydrocarbon ring;

[0080] n1 and n2 each independently represent 0 or 1.

[0081] As Q in formula (1-1) 1 , preferably represented by the following formula (1-1-1).

[0082]

[0083] In formula (1-1-1), Z 1 represents a single bond, an alkylene group having 1 to 6 carbon atoms which may be substituted by a halogen atom, or a sulfonyl group;

[0084] R 11 and R 12 each independently represents an alkyl group having 1 to 13 carbon atoms which may be substituted by a halogen atom, a hydroxyl group, a methoxy group, a thiol group, an acetyl group, a nitro group, an allyl group, a phenyl group, a naphthyl group, or a halogen atom;

[0085] n11 and n12 each independently represent an integer from 0 to 4;

[0086] R 11 When there are 2 or more R 11 It can be the same or different;

[0087] R 12 When there are 2 or more R 12 It can be the same or different.

[0088] As Z in formula (1-1) 1 Preferred are, for example, an alkylene group having 1 to 6 carbon atoms which may be substituted with a halogen atom, and a sulfonyl group.

[0089]

[0090] In formula (1-2), R 1 and R 2 Each independently represents an alkyl group having 1 to 6 carbon atoms which may be substituted by a halogen atom, or a halogen atom;

[0091] m1 and m2 each independently represent an integer from 0 to 4;

[0092] R 1 When there are 2 or more R 1 It can be the same or different;

[0093] R 2 When there are 2 or more R 2 It can be the same or different;

[0094] X 11 represents a divalent group represented by any one of the following formulae (1-2-1) to (1-2-3);

[0095] Z 11 and Z 12 Each independently represents a single bond or a divalent group represented by the following formula (1-2-4).

[0096]

[0097] In formulas (1-2-1) to (1-2-3), 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 by 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;

[0098] R 1 and R 2 They may also be bonded to each other to form a ring with 3 to 6 carbon atoms;

[0099] R 3 and R 4 They may also be bonded to each other to form a ring with 3 to 6 carbon atoms;

[0100] * indicates bonding position;

[0101] *1 represents the bonding position to the carbon atom in formula (1-2);

[0102] *2 represents the bonding position to the nitrogen atom in formula (1-2).

[0103]

[0104] In formula (1-2-4), m1 is an integer from 0 to 4, m2 is 0 or 1, m3 is 0 or 1, and m4 is an integer from 0 to 2; however, when m3 is 1, m1 and m2 are not 0 at the same time; *3 represents the bonding position to the nitrogen atom in formula (1-2); *4 represents the bonding position.

[0105] In the present specification, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0106] In this specification, the alkyl group is not limited to a straight chain, and may be a branched chain or a cyclic group. Examples of the straight chain or branched chain alkyl group include methyl, ethyl, isopropyl, tert-butyl, n-hexyl, etc. Examples of the cyclic alkyl group (cycloalkyl group) include cyclobutyl, cyclopentyl, cyclohexyl, etc.

[0107] In the present specification, examples of the alkoxy group include a methoxy group, an ethoxy group, an n-pentyloxy group, and an isopropoxy group.

[0108] 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.

[0109] 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.

[0110] 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.

[0111] In the present specification, examples of the alkenyloxy group include vinyloxy, 1-propenyloxy, 2-n-propenyloxy (allyloxy), 1-n-butenyloxy, and isopreneoxy.

[0112] In the present specification, examples of the alkynyloxy group include 2-propynyloxy, 1-methyl-2-propynyloxy, 2-methyl-2-propynyloxy, 2-butynyloxy, and 3-butynyloxy.

[0113] In the present specification, examples of the acyl group include an acetyl group and a propionyl group.

[0114] In the present specification, examples of the aryloxy group include a phenoxy group and a naphthoxy group.

[0115] In the present specification, examples of the arylcarbonyl group include a phenylcarbonyl group.

[0116] In the present specification, examples of the aralkyl group include a benzyl group and a phenethyl group.

[0117] In the present specification, examples of the alkylene group include methylene, ethylene, 1,3-propylene, 2,2-propylene, 1-methylethylene, 1,4-butylene, 1-ethylethylene, 1-methylpropylene, 2-methylpropylene, 1,5-pentylene, 1-methylbutylene, 2-methylbutylene, 1,1-dimethylpropylene, 1,2-dimethylpropylene, 1-ethylpropylene, 2-ethylpropylene, 1,6-hexylene, 1,4-cyclohexylene, 1,8-octylene, 2-ethyloctylene, 1,9-nonylene, and 1,10-decylene.

[0118] As R in formulas (1-2-1) to (1-2-3) 1 ~R 5 The alkyl group having 1 to 10 carbon atoms which may be interrupted by an oxygen atom or a sulfur atom may include, 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.

[0119] 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.

[0120] Examples of the structure represented by the following formula in formula (1-1) include the following structures.

[0121]

[0122] *Indicates bonding position.

[0123]

[0124]

[0125] *Indicates bonding position.

[0126] Examples of the structure represented by the following formula in formula (1-2) include the following structures.

[0127]

[0128] *Indicates bonding position.

[0129]

[0130]

[0131]

[0132]

[0133] *Indicates bonding position.

[0134] The polymer (A) may have a structure represented by the following formula (E). The structure represented by formula (E) is, for example, located at a terminal (one terminal or both terminals) of the polymer (A).

[0135]

[0136] In formula (E), Y represents a monovalent group; n11 represents 0 or 1; and * represents a bond.

[0137] Examples of the monovalent group in Y in the formula (E) include monovalent organic groups having 1 to 30 carbon atoms.

[0138] Examples of Y in the formula (E) include a monovalent residue obtained by removing one hydrogen atom from an aliphatic ring which may be substituted with a substituent, and a monovalent aromatic group which may be substituted with a substituent.

[0139] Examples of the substituent include a halogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms.

[0140] Examples of the aromatic group in the monovalent aromatic group which may be substituted with a substituent include aromatic hydrocarbon groups, such as phenyl, naphthyl, and anthracenyl.

[0141] Examples of the compound that imparts the structure represented by the formula (E) to the polymer (A) include compounds represented by the following formula (EA).

[0142]

[0143] In formula (EA), Y and n11 have the same meanings as Y and n11 in formula (E), respectively.

[0144] Examples of the compound represented by formula (EA) include the following compounds.

[0145]

[0146]

[0147]

[0148]

[0149] The polymer (A) may have at the terminal "a non-cyclic aliphatic hydrocarbon group which may be interrupted by a heteroatom-containing group and which may be substituted by a substituent".

[0150] The non-cyclic aliphatic hydrocarbon group refers to a linear or branched alkyl group, a linear or branched alkenyl group, a linear or branched alkynyl group, and any combination thereof. The number of carbon atoms in the non-cyclic aliphatic hydrocarbon group is preferably less than 12, more preferably less than 10.

[0151] Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, 1-methylcyclopropyl, 2-methylcyclopropyl, n-pentyl, 1-methyl n-butyl, 2-methyl n-butyl, 3-methyl n-butyl, 1,1-dimethyl n-propyl, 1,2-dimethyl n-propyl, 2,2-dimethyl n-propyl, 1-ethyl n-propyl, cyclopentyl, 1-methylcyclobutyl, 2-methylcyclobutyl, 3-methylcyclobutyl, 1,2-dimethyl cyclopropyl, 2,3-dimethylcyclopropyl, 1-ethylcyclopropyl, 2-ethylcyclopropyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n-pentyl, 4-methyl-n-pentyl, 1,1-dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1,3-dimethyl-n-butyl, 2,2-dimethyl-n-butyl, 2,3-dimethyl-n-butyl, 3,3-dimethyl-n-butyl, 1-ethyl-n-butyl, 2-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl, 1,2, 2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl, 1-ethyl-2-methyl-n-propyl, cyclohexyl, 1-methylcyclopentyl, 2-methylcyclopentyl, 3-methylcyclopentyl, 1-ethylcyclobutyl, 2-ethylcyclobutyl, 3-ethylcyclobutyl, 1,2-dimethylcyclobutyl, 1,3-dimethylcyclobutyl, 2,2-dimethylcyclobutyl, 2,3-dimethylcyclobutyl, 2,4-dimethylcyclobutyl, 3,3-dimethylcyclobutyl, 1-n-propylcyclopropyl, 2-n-propyl Cyclopropyl, 1-isopropylcyclopropyl, 2-isopropylcyclopropyl, 1,2,2-trimethylcyclopropyl, 1,2,3-trimethylcyclopropyl, 2,2,3-trimethylcyclopropyl, 1-ethyl-2-methylcyclopropyl, 2-ethyl-1-methylcyclopropyl, 2-ethyl-2-methylcyclopropyl, 2-ethyl-3-methylcyclopropyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, and the like.

[0152] Examples of the alkenyl group include 1-propenyl, 2-propenyl, 1-methyl-1-vinyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl, 1-ethylvinyl, 1-methyl-1-propenyl, 1-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-n-propylvinyl, 1-methyl-1-butenyl, 1-methyl-2-butenyl, 1-methyl-3-butenyl, 2-ethyl-2-propenyl, 2-methyl-1-butenyl, 2-methyl-2-butenyl, 2-methyl-3-butenyl, 3-methyl-1- butenyl, 3-methyl-2-butenyl, 3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl, 1-isopropylvinyl, 1,2-dimethyl-1-propenyl, 1,2-dimethyl-2-propenyl, 1-cyclopentenyl, 2-cyclopentenyl, 3-cyclopentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1-pentenyl, 1-methyl-2-pentenyl, 1-methyl-3-pentenyl, 1-methyl-4-pentenyl, 1-n-butylvinyl, 2-methyl-1-pentenyl, 2-methyl-2-pentenyl, 2-methyl-3-pentenyl, 2-methyl- 4-pentenyl, 2-n-propyl-2-propenyl, 3-methyl-1-pentenyl, 3-methyl-2-pentenyl, 3-methyl-3-pentenyl, 3-methyl-4-pentenyl, 3-ethyl-3-butenyl, 4-methyl-1-pentenyl, 4-methyl-2-pentenyl, 4-methyl-3-pentenyl, 4-methyl-4-pentenyl, 1,1-dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl, 1,2-dimethyl-1-butenyl, 1,2-dimethyl-2-butenyl, 1,2-dimethyl-3-butenyl, 1-methyl-2-ethyl-2-propenyl, 1-sec-butylvinyl, 1,3-dimethyl -1-butenyl, 1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl, 1-isobutylvinyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 2-isopropyl-2-propenyl, 3,3-dimethyl-1-butenyl, 1-ethyl-1-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 1-n-propyl-1-propenyl, 1-n-propyl-2-propenyl, 2-ethyl-1-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1,1,2-trimethyl-2-propenyl, 1-tert-butylvinyl, 1-methyl-1-ethyl-2-propenyl, 1-ethyl-2-methyl-1-propenyl, 1-ethyl-2-methyl-2-propenyl, 1-isopropyl-1-propenyl, 1-isopropyl-2-propenyl, 1-methyl-2-cyclopentenyl, 1-methyl-3-cyclopentenyl, 2-methyl-1-cyclopentenyl, 2-methyl-2-cyclopentenyl cyclopentenyl, 2-methyl-3-cyclopentenyl, 2-methyl-4-cyclopentenyl, 2-methyl-5-cyclopentenyl, 2-methylenecyclopentyl, 3-methyl-1-cyclopentenyl, 3-methyl-2-cyclopentenyl, 3-methyl-3-cyclopentenyl, 3-methyl-4-cyclopentenyl, 3-methyl-5-cyclopentenyl, 3-methylenecyclopentyl, 1-cyclohexenyl, 2-cyclohexenyl and 3-cyclohexenyl, etc.

[0153] Examples of the alkynyl group include ethynyl, 1-propynyl, and 2-propynyl.

[0154] The hetero atom is not particularly limited, but is usually an oxygen atom, a sulfur atom or a nitrogen atom.

[0155] Examples of the heteroatom-containing group include an ether group, a thioether group, a carbonyl group, a thiocarbonyl group, an ester group, a thioester group, a thioester group, an amide group, a urea group, and an oxysulfonyl group.

[0156] "Interruptible with heteroatom-containing groups" means that the carbon-carbon bonds of the acyclic aliphatic hydrocarbon group of the present invention may contain one or more ether bonds, thioether bonds, carbonyl bonds, thiocarbonyl bonds, ester bonds, thioester bonds, thioester bonds, amide bonds, urea bonds, oxysulfonyl bonds, etc. In the case of containing two or more bonds, the types of bonds may be one or two or more.

[0157] Specific examples of heteroatom-containing groups interrupting a non-cyclic aliphatic hydrocarbon group are shown in the following formulae: In the formulae, * indicates a bonding position.

[0158]

[0159] "May be substituted by a substituent" means that all or part of the hydrogen atoms of the non-cyclic aliphatic hydrocarbon group of the present invention may be substituted by, for example, a hydroxyl group, a straight-chain or branched-chain alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an acyloxy group having 1 to 10 carbon atoms, and a carboxyl group.

[0160] Regarding the alkyl group, it is as described above.

[0161] Examples of the alkoxy group include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, 1-methyl n-butoxy, 2-methyl n-butoxy, 3-methyl n-butoxy, 1,1-dimethyl n-propoxy, 1,2-dimethyl n-propoxy, 2,2-dimethyl n-propoxy, 1-ethyl n-propoxy, n-hexyloxy, 1-methyl n-pentoxy, 2-methyl n-pentoxy, 3-methyl n-pentoxy, 4-methyl n-pentoxy, 1,1-dimethyl n-butoxy, 1,2 -dimethyl-n-butoxy, 1,3-dimethyl-n-butoxy, 2,2-dimethyl-n-butoxy, 2,3-dimethyl-n-butoxy, 3,3-dimethyl-n-butoxy, 1-ethyl-n-butoxy, 2-ethyl-n-butoxy, 1,1,2-trimethyl-n-propoxy, 1,2,2-trimethyl-n-propoxy, 1-ethyl-1-methyl-n-propoxy, and 1-ethyl-2-methyl-n-propoxy, cyclopentyloxy, cyclohexyloxy, norbornyloxy, adamantyloxy, adamantylmethoxy, adamantylethoxy, tetracyclodecyloxy, tricyclodecyloxy, and the like.

[0162] The acyloxy group refers to an acyloxy group represented by the following formula (20).

[0163] Z-COO-* (20)

[0164] In formula (20), Z represents a hydrogen atom or an alkyl group having 1 to 9 carbon atoms among the above-mentioned alkyl groups, and * represents a bonding portion to the above-mentioned acyclic aliphatic hydrocarbon group.

[0165] An acyclic aliphatic hydrocarbon group having less than 12 carbon atoms and containing a heteroatom is preferred, an acyclic aliphatic hydrocarbon group having less than 12 carbon atoms and containing an oxygen atom is more preferred, an acyclic aliphatic hydrocarbon group having less than 12 carbon atoms interrupted by at least two selected from an ether group, a carbonyl group and an ester group is further preferred, and an acyclic aliphatic hydrocarbon group having less than 12 carbon atoms interrupted by an ether group and an ester group is most preferred.

[0166] The acyclic aliphatic hydrocarbon group preferably has at least one unsaturated bond (eg, double bond or triple bond). The acyclic aliphatic hydrocarbon group preferably has 1 to 3 unsaturated bonds. The unsaturated bond is preferably a double bond.

[0167] The "non-cyclic aliphatic hydrocarbon group which may be interrupted by a group containing a heteroatom and may be substituted by a substituent" can be derived, for example, by reacting a saturated or unsaturated dicarboxylic acid anhydride such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, methylmaleic acid, ethylmaleic acid, dimethylmaleic acid, or citraconic acid with the terminal of the polymer by a method known per se.

[0168] An example of a method for producing the polymer (A) will be described.

[0169] The polymer (A) can be obtained, for example, by the following reaction (I) or (II).

[0170] (I): Reaction of a compound represented by the following formula (1A) with at least one of a compound represented by the following formula (2-1A) and a compound represented by the following formula (2-2A).

[0171] (II): Reaction of a compound represented by the following formula (1A), at least one of a compound represented by the following formula (2-1A) and a compound represented by the following formula (2-2A), and a compound represented by formula (EA).

[0172]

[0173] In formula (1A), R 1 , R 2 , m1 and m2 are respectively related to R in formula (1) 1 , R 2 , m1 and m2 have the same meaning.

[0174]

[0175] In formula (2-1A), Q 1 , n1 and n2 are respectively related to Q in formula (1-1) 1 , n1 and n2 have the same meaning.

[0176] In formula (2-2A), X 11 , Z 11 and Z 12 Respectively with X in formula (1-2) 11 , Z 11 and Z 12 have the same meaning.

[0177] Reactions (I) and (II) can be carried out in the presence of a catalyst, for example. The catalyst is, for example, a quaternary phosphonium salt such as tetrabutylphosphonium bromide, ethyltriphenylphosphonium bromide, or a quaternary ammonium salt such as benzyltriethylammonium chloride. 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 reaction raw materials used in the reaction. For the temperature and time of the reaction, the optimal conditions can be selected, for example, from a range of 80 to 160° C. and 2 to 50 hours.

[0178] The molecular weight of the polymer (A) is not particularly limited. The lower limit of the weight average molecular weight of the polymer (A) is, for example, 500, 1,000, 2,000 or 3,000.

[0179] The upper limit of the weight average molecular weight of the polymer (A) is, for example, 100,000, 50,000 or 30,000.

[0180] The content of the polymer (A) 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, relative to the film constituent components in the resist underlayer film-forming composition.

[0181] The film constituting components refer to components other than the solvent in the resist underlayer film forming composition.

[0182] <Solvent>

[0183] The solvent used in the resist underlayer film-forming composition is not particularly limited as long as it can uniformly dissolve the components contained in the polymer (A), and is preferably an organic solvent generally used in a chemical solution for semiconductor photolithography. 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-hydroxyisobutyrate, methyl ... ethyl isobutyrate, ethyl ethoxylate, 2-hydroxyethyl acetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, 2-heptanone, methoxycyclopentane, anisole, γ-butyrolactone, N-methylpyrrolidone, N,N-dimethylformamide and N,N-dimethylacetamide. These solvents can be used alone or in combination of two or more.

[0184] 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.

[0185] <Crosslinking agent>

[0186] The resist underlayer film-forming composition may contain a cross-linking agent.

[0187] The cross-linking agent is not particularly limited.

[0188] Examples of the cross-linking agent include compounds having two or more structures represented by the following formula (C).

[0189]

[0190] In formula (C), R 101represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxyalkyl group having 2 to 6 carbon atoms. * represents a bonding position.

[0191] The bonding position is, for example, a nitrogen atom, a carbon atom constituting an aromatic hydrocarbon ring, or the like.

[0192] As R 101 , preferably a hydrogen atom, a methyl group, an ethyl group or a group represented by the following structure.

[0193]

[0194] In the structure, R 102 Indicates a hydrogen atom, a methyl group, or an ethyl group. *Indicates a bonding position.

[0195] As the crosslinking agent, melamine compounds, guanamine compounds, glycoluril compounds, urea compounds, and compounds having a phenolic hydroxyl group are preferred, and these may be used alone or in combination of two or more.

[0196] The melamine compound is not particularly limited as long as it has a group reactive with a hydroxyl group.

[0197] Examples of the melamine compound include hexamethylolmelamine, hexamethoxymethylmelamine, a compound in which 1 to 6 hydroxymethyl groups of hexamethylolmelamine are methoxymethylated, or a mixture thereof, hexamethoxyethylmelamine, hexaacyloxymethylmelamine, a compound in which 1 to 6 hydroxymethyl groups of hexamethylolmelamine are acyloxymethylated, or a mixture thereof.

[0198] The guanamine compound is not particularly limited as long as it has a group reactive with a hydroxyl group.

[0199] Examples of the guanamine compound include tetramethylolguanamine, tetramethoxymethylguanamine, a compound in which 1 to 4 hydroxymethyl groups of tetramethylolguanamine are methoxymethylated, or a mixture thereof, tetramethoxyethylguanamine, tetraacyloxyguanamine, a compound in which 1 to 4 hydroxymethyl groups of tetramethylolguanamine are acyloxymethylated, or a mixture thereof.

[0200] The glycoluril compound is not particularly limited as long as it is a glycoluril compound having a group that can react with a hydroxyl group.

[0201] Examples of the glycoluril compound include tetramethylol glycoluril, tetramethoxy glycoluril, tetramethoxymethyl glycoluril, a compound in which 1 to 4 hydroxymethyl groups of tetramethylol glycoluril are methoxymethylated or a mixture thereof, a compound in which 1 to 4 hydroxymethyl groups of tetramethylol glycoluril are acyloxymethylated or a mixture thereof, and the like.

[0202] In addition, the glycoluril compound may be, for example, a glycoluril derivative represented by the following formula (1E).

[0203]

[0204] In formula (1E), four R1s each independently represent a methyl group or an ethyl group, and R2 and R3 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group.

[0205] Examples of the glycoluril derivative represented by the above formula (1E) include compounds represented by the following formulas (1E-1) to (1E-6).

[0206]

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

[0208]

[0209] In formula (2E), R2 and R3 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group, and R4 each independently represents an alkyl group having 1 to 4 carbon atoms.

[0210]

[0211] In formula (3d), R 1 It represents a methyl or ethyl group.

[0212] Examples of the glycoluril derivatives represented by the above formula (2E) include compounds represented by the following formulas (2E-1) to (2E-4). Examples of the compounds represented by the above formula (3d) include compounds represented by the following formulas (3d-1) and (3d-2).

[0213]

[0214] The urea compound is not particularly limited as long as it has a group reactive with a hydroxyl group.

[0215] Examples of the urea compound include tetramethylol urea, tetramethoxymethyl urea, a compound in which 1 to 4 methylol groups of tetramethylol urea are methoxymethylated, or a mixture thereof, and tetramethoxyethyl urea.

[0216] Examples of the compound having a phenolic hydroxyl group include compounds represented by the following formula (111) or formula (112).

[0217]

[0218] In formula (111) and formula (112), Q 2 It represents a single bond or an m2-valent organic group.

[0219] R 8 , R 9 , R 11 and R 12 represent a hydrogen atom or a methyl group, respectively.

[0220] R 7 and R 10 Each of them represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 40 carbon atoms.

[0221] n9 represents an integer of 1≤n9≤3, n 10 It means 2≤n 10 An integer ≤5, n 11 Indicates 0≤n 11 An integer ≤3, n 12 Indicates 0≤n 12 An integer ≤3, and 3≤(n9+n 10 +n 11 +n 12 )≤6.

[0222] n 13 Indicates 1≤n 13 An integer ≤3, n 14 Indicates 1≤n 14 An integer ≤ 4, n 15 Indicates 0≤n 15 An integer ≤3, n 16 Indicates 0≤n 16 An integer ≤3, and 2≤(n 13 +n 14 +n 15 +n 16 )≤5.

[0223] m2 represents an integer from 2 to 10.

[0224] As Q 2 The m2-valent organic group in the formula (a) includes, for example, an m2-valent organic group having 1 to 4 carbon atoms.

[0225] Examples of the compound represented by formula (111) or formula (112) include the following compounds.

[0226]

[0227]

[0228] The above compounds can be obtained as products of Asahi Organic Materials Industries, Ltd. and Honshu Chemical Industries, Ltd. As the product, for example, there is TMOM-BP, a product of Asahi Organic Materials Industries, Ltd.

[0229] Among them, glycoluril compounds are preferred, specifically, tetrakishydroxymethyl glycoluril, tetramethoxy glycoluril, tetramethoxymethyl glycoluril, compounds in which 1 to 4 hydroxymethyl groups of tetrakishydroxymethyl glycoluril are methoxymethylated or mixtures thereof, compounds in which 1 to 4 hydroxymethyl groups of tetrakishydroxymethyl glycoluril are acyloxymethylated or mixtures thereof are preferred, and tetramethoxymethyl glycoluril is preferred.

[0230] The molecular weight of the cross-linking agent is not particularly limited, but is preferably 500 or less.

[0231] The content of the crosslinking agent in the resist underlayer film-forming composition is not particularly limited, but is, for example, 1 mass % to 50 mass %, and preferably 5 mass % to 40 mass % based on the polymer (A).

[0232] <Curing Catalyst>

[0233] As the curing catalyst contained as an optional component in the resist underlayer film-forming composition, any of a thermal acid generator and a photoacid generator can be used, and a thermal acid generator is preferably used.

[0234] Examples of the thermal acid generator include sulfonic acid compounds and carboxylic acid compounds such as p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium p-toluenesulfonate (pyridinium p-toluenesulfonate), pyridinium phenolsulfonate, pyridinium p-hydroxybenzenesulfonate (pyridinium p-phenolsulfonate), pyridinium trifluoromethanesulfonate, salicylic acid, camphorsulfonic acid, 5-sulfosalicylic acid, 4-chlorobenzenesulfonic acid, 4-hydroxybenzenesulfonic acid, benzenedisulfonic acid, 1-naphthalenesulfonic acid, citric acid, benzoic acid, hydroxybenzoic acid, N-methylmorpholine-p-toluenesulfonic acid, N-methylmorpholine-p-hydroxybenzenesulfonic acid, and N-methylmorpholine-5-sulfosalicylic acid.

[0235] Examples of the photoacid generator include onium salt compounds, sulfonyl imide compounds, and disulfonyldiazomethane compounds.

[0236] Examples of the onium salt compound include iodonium salt compounds such as diphenyliodonium hexafluorophosphate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, diphenyliodonium perfluoro-n-octanesulfonate, diphenyliodonium camphorsulfonate, bis(4-tert-butylphenyl)iodonium camphorsulfonate, and bis(4-tert-butylphenyl)iodonium trifluoromethanesulfonate; and sulfonium salt compounds such as triphenylsulfonium hexafluoroantimonate, triphenylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium camphorsulfonate, and triphenylsulfonium trifluoromethanesulfonate.

[0237] Examples of the sulfonyl imide compound include N-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluoro-n-butanesulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, and N-(trifluoromethanesulfonyloxy)naphthalimide.

[0238] 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.

[0239] The curing catalyst may be used alone or in combination of two or more.

[0240] When a curing catalyst is used, the content ratio of the curing catalyst relative to the cross-linking agent is, for example, 0.1 mass % to 50 mass %, or preferably 1 mass % to 30 mass %.

[0241] <Other ingredients>

[0242] 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 against surface unevenness.

[0243] 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), Megapac F171, F173, R-30 (trade names of DIC Corporation), Fluorado FC430, Fluorine-based surfactants such as FC431 (trade name, manufactured by Sumitomo 3M Co., Ltd.), Asahigard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, and SC106 (trade name, manufactured by AGC Co., Ltd.), and organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0244] The amount of these surfactants blended 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.

[0245] These surfactants may be added alone or in combination of two or more.

[0246] The solid content contained in the resist underlayer film-forming composition of the present invention, that is, the components other than the above-mentioned solvent, is, for example, 0.01 mass % to 10 mass %.

[0247] (Resist Underlayer Film)

[0248] The resist underlayer of the present invention is a cured product of the above-mentioned resist underlayer film-forming composition.

[0249] The resist underlayer film can be produced, for example, by applying the resist underlayer film-forming composition described above on a semiconductor substrate and firing the coating.

[0250] Examples of the semiconductor substrate to which the resist underlayer film-forming composition is applied include silicon wafers, germanium wafers, and compound semiconductor wafers such as gallium arsenide, indium phosphide, gallium nitride, indium nitride, and aluminum nitride.

[0251] When a semiconductor substrate having an inorganic film formed on the surface is used, the inorganic film is formed by, for example, ALD (atomic layer deposition) method, CVD (chemical vapor deposition) method, reactive sputtering method, ion plating method, vacuum evaporation method, spin coating method (spin-on glass: SOG). Examples of the inorganic film include polycrystalline silicon film, silicon oxide film, silicon nitride film, borophosphosilicate glass (BPSG) film, titanium nitride film, titanium oxynitride film, tungsten film, gallium nitride film, and gallium arsenide film.

[0252] On such a semiconductor substrate, the resist lower 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 lower 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.

[0253] Examples of the thickness of the resist underlayer film include 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), and 0.005 μm (5 nm) to 0.05 μm. (50nm), 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).

[0254] The method for measuring the film thickness of the resist underlayer film in this specification is as follows.

[0255] ·Measurement device name: Ellipsometry film thickness measurement device RE-3100 (SCREEN Corporation)

[0256] SWE (Single Wavelength Ellipsometer) Mode

[0257] 8-point arithmetic average (for example, 8 points are measured at 1 cm intervals in the X direction of the wafer)

[0258] (Laminate)

[0259] The laminated body of the present invention comprises a semiconductor substrate and the resist underlayer film of the present invention.

[0260] As the semiconductor substrate, for example, the above-mentioned semiconductor substrates can be cited.

[0261] The resist underlayer film is disposed on, for example, a semiconductor substrate.

[0262] (Semiconductor device manufacturing method, pattern forming method)

[0263] The method for manufacturing a semiconductor device of the present invention includes at least the following steps.

[0264] A step of forming a resist underlayer film on a semiconductor substrate using the resist underlayer film-forming composition of the present invention;

[0265] A step of forming a resist film on the resist underlayer film.

[0266] The pattern forming method of the present invention includes at least the following steps.

[0267] A step of forming a resist underlayer film on a semiconductor substrate using the resist underlayer film-forming composition of the present invention;

[0268] ・Step of forming a resist film on the resist underlayer film

[0269] A process of irradiating a resist film with EB or EUV and then developing the resist film to obtain a resist pattern;

[0270] A step of etching the resist underlayer film using the resist pattern as a mask.

[0271] Usually, a resist film is formed on the resist underlayer film.

[0272] 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.

[0273] The resist film formed on the resist underlayer film by a known method (eg, coating, firing) is not particularly limited as long as it is a resist film that responds to EB or EUV used in irradiation. Both negative photoresists and positive photoresists can be used.

[0274] It should be noted that, in this specification, a resist responsive to EB is also referred to as a photoresist.

[0275] As photoresists, there are positive photoresists containing novolac resin and 1,2-naphthoquinone diazosulfonic acid ester, chemically amplified photoresists containing a binder having a group that increases the alkali dissolution rate by acid decomposition and a photoacid generator, chemically amplified photoresists containing a low molecular compound that increases the alkali dissolution rate of the photoresist by acid decomposition, an alkali-soluble binder, and a photoacid generator, and chemically amplified photoresists containing a binder having a group that increases the alkali dissolution rate by acid decomposition, a low molecular 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 (trade name V146G), Shipley Co., Ltd. trade name APEX-E, Sumitomo Chemical (trade name PAR710), Shin-Etsu Chemical Co., Ltd. trade name AR2772, 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.

[0276] 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, W O2018 / 193954, WO2019 / 172054, WO2019 / 021975, WO2018 / 230334, WO2018 / 194123, Japanese Special Opening 2018-180525, WO2018 / 190088, Japanese Special Opening 2018-0 70596, Japanese Special Opening 2018-028090, Japanese Special Opening 2016-153409, Japanese Special Opening 2016-130240, Japanese Special Opening 2016-108325, Japanese Special Opening 2016-047920, Japanese Special Opening 2016-035570, Japanese Special Opening 2016 -035567, Japan’s special opening 2016-035565, Japan’s special opening 2019-101417, Japan’s special opening 2019-117373, Japan’s special opening 2019-052294, Japan’s special opening 2019 -008280, Japan’s special opening 2019-008279, Japan’s special opening 2019-003176, Japan’s special opening 2019-003175, Japan’s special opening 2018-197853, Japan’s special opening 2019 -191298, Japan’s special opening 2019-061217, Japan’s special opening 2018-045152, Japan’s special opening 2018-022039, Japan’s special opening 2016-090441, Japan’s special opening 2015 -10878, Japan’s special opening 2012-168279, Japan’s special opening 2012-022261, Japan’s special opening 2012-022258, Japan’s special opening 2011-043749, Japan’s special opening 2010-181857, Japanese Patent Application No. 2010-128369, WO2018 / 031896, Japanese Patent Application Patent Application No. 2019-113855, WO2017 / 156388, WO20 17 / 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 thereto.

[0277] Examples of the resist composition include the following compositions.

[0278] An active light-sensitive or radiation-sensitive resin composition comprising a resin A and a compound represented by the general formula (121), wherein the resin A comprises 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.

[0279]

[0280] In the general formula (121), m represents an integer of 1-6.

[0281] R1 and R2 each independently represent a fluorine atom or a perfluoroalkyl group.

[0282] L1 represents -O-, -S-, -COO-, -SO2- or -SO3-.

[0283] L2 represents an alkylene group which may have a substituent or a single bond.

[0284] W1 represents a cyclic organic group which may have a substituent.

[0285] M + Represents a cation.

[0286] A composition for forming a metal-containing film 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 period to the seventh period of the third group to the fifteenth group of the periodic table.

[0287] A radiation-sensitive resin composition comprises a polymer and an acid generator, wherein the polymer has a first structural unit represented by the following formula (31) and a second structural unit including an acid-dissociable group represented by the following formula (32).

[0288]

[0289] In formula (31), Ar is a group obtained by removing (n+1) hydrogen atoms from an aromatic hydrocarbon having 6 to 20 carbon atoms. 1 is a hydroxyl group, a sulfanyl 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, multiple R 1 Same or different. 2 is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group. 3 It is a monovalent group containing the above-mentioned acid dissociable group and having 1 to 20 carbon atoms. 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.

[0290] A resist composition comprising a resin (A1) and an acid generator, wherein the resin (A1) comprises 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,

[0291]

[0292] In the formula, R2 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 is a single bond, -CO-O-* or -CO-NR 4 -*, * indicates the bonding position 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 and which may have one or more groups selected from a hydroxyl group and a carboxyl group.

[0293] Examples of the resist film include the following films.

[0294] A resist film comprising a base resin, wherein the base resin comprises a repeating unit represented by the following formula (a1) and / or a repeating unit represented by the following formula (a2), and a repeating unit that generates an acid bonded to a polymer main chain by exposure,

[0295]

[0296] 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 from 0 to 4. 1 is a single bond, a phenylene group or a naphthylene group, or a linking group having 1 to 12 carbon atoms and including at least one selected from an ester bond, a lactone ring, a phenylene group and a naphthylene group. 2 It is a single bond, an ester bond or an amide bond.

[0297] Examples of resist materials include the following.

[0298] A resist material comprising a polymer having a repeating unit represented by the following formula (b1) or (b2).

[0299]

[0300] 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. 2is 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 combine 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 They may also form a ring together with the sulfur atom to which they are bonded.

[0301] A resist material comprising a base resin comprising a polymer containing a repeating unit represented by the following formula (a):

[0302]

[0303] In formula (a), R A is a hydrogen atom or a methyl group. 1 is a hydrogen atom or an acid-labile group. 2 It 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 is -O-, -O-CH2- or -NH-. m is an integer of 1 to 4. u is an integer of 0 to 3. However, m+u is an integer of 1 to 4.

[0304] A resist composition which generates an acid upon exposure and whose solubility in a developer changes under the action of the acid.

[0305] It contains a base material component (A) whose solubility in a developer changes under the action of an acid and a fluorine additive component (F) which shows decomposability with respect to an alkali developer.

[0306] The fluorine additive component (F) contains a fluororesin component (F1), and the fluororesin component (F1) has 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).

[0307]

[0308] In the formula (f2-r-1), Rf 21 are each independently a hydrogen atom, an alkyl group, an alkoxy group, a hydroxyl group, a hydroxyalkyl group or a cyano group. n” is an integer of 0 to 2. * is the bonding position.

[0309] The above structural unit (f1) contains a structural unit represented by the following general formula (f1-1) or a structural unit represented by the following general formula (f1-2).

[0310]

[0311] In the formulas (f1-1) and (f1-2), R are each 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 moiety. A aryl is a divalent aromatic cyclic group which may have a substituent. X 01 is a single bond or a divalent linking group. R 2 are each independently an organic group having a fluorine atom.

[0312] Examples of the coating, coating solution and coating composition are as follows.

[0313] A coating containing a metal oxy-hydroxide network having an organic ligand through a metal-carbon bond and / or a metal carboxylate bond.

[0314] A composition based on inorganic oxygen / hydroxide.

[0315] A coating solution which contains an organic solvent, a first organometallic composition and a hydrolyzable metal compound, and the first organometallic composition has the formula R z SnO (2-(z / 2)-(x / 2)) (OH) x (wherein, 0 < z ≤ 2 and 0 < (z + x) ≤ 4), the formula R’ n SnX 4-n(wherein n=1 or 2), or a mixture thereof, wherein R and R' are independently a hydrocarbon group having 1 to 31 carbon atoms, and X is a ligand having a hydrolyzable bond to Sn or a combination thereof; the hydrolyzable metal compound is represented by the formula MX' v (wherein, M is a metal selected from Groups 2 to 16 of the periodic table, v=a number from 2 to 6, and X' is a ligand having a hydrolyzable MX bond or a combination thereof).

[0316] A coating solution comprising an organic solvent, a RSnO (3 / 2-x / 2) (OH) x (wherein 0<x<3) represents a first organometallic compound. The solution contains about 0.0025M to about 1.5M of tin, and R is an alkyl or cycloalkyl group having 3 to 31 carbon atoms, and the alkyl or cycloalkyl group is bonded to the tin on a secondary or tertiary carbon atom.

[0317] An inorganic pattern forming precursor aqueous solution comprises a mixture of water, metal subvalent oxide cations, polyatomic inorganic anions and a radiation sensitive ligand containing a peroxide group.

[0318] EB or EUV irradiation is performed, for example, through a mask (photomask) for forming a predetermined pattern. The resist underlayer film-forming composition of the present invention is preferably used for EUV (extreme ultraviolet) exposure. There are no particular restrictions on the irradiation energy of the electron beam and the exposure amount of EUV.

[0319] Baking (PEB: Post Exposure Bake) may also be performed after EB or EUV irradiation and before development.

[0320] The baking temperature is not particularly limited, but is preferably 60 to 150° C., more preferably 70 to 120° C., and particularly preferably 75 to 110° C. 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.

[0321] For development, for example, an alkali developer is used.

[0322] As an image development temperature, 5 degreeC - 50 degreeC is mentioned, for example.

[0323] The development time may be, for example, 10 seconds to 300 seconds.

[0324] As the alkaline developer, for example, inorganic alkalis 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, cyclic amines such as pyrrole and piperidine can be used. In addition, it is also possible to add an appropriate amount of surfactants such as alcohols such as isopropanol and nonionics to the aqueous solution of the above-mentioned alkalis for use. Among them, the preferred developer is an aqueous solution of a quaternary ammonium salt, and is further preferably an aqueous solution of tetramethylammonium hydroxide and an aqueous solution of choline. In addition, surfactants etc. can also be added to these developers. As an alternative to the alkaline developer, it is also possible to develop with organic solvents such as butyl acetate, and develop the part where the alkali dissolution rate of the photoresist is not improved.

[0325] 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.

[0326] 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. After that, the semiconductor substrate is processed by a known method (dry etching method, etc.) to manufacture a semiconductor element.

[0327] Example

[0328] Next, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples.

[0329] The weight average molecular weights of the polymers shown in Synthesis Examples 1 to 3 and Comparative Synthesis Examples 1 and 2 in this specification are the results of measurements based on gel permeation chromatography (hereinafter referred to as GPC). A GPC apparatus manufactured by Tosoh Corporation was used for the measurements, and the measurement conditions and the like were as follows.

[0330] GPC columns: Shodex GF-310HQ, Shodex GF-510HQ, Shodex GF-710HQ (registered trademark) (Showa Denko KK)

[0331] Column temperature: 40°C

[0332] Solvent: N,N-dimethylformamide (DMF)

[0333] Flow rate: 0.6ml / min

[0334] Standard sample: Polystyrene (manufactured by Tosoh Corporation)

[0335] <Synthesis example 1>

[0336] 4.00 g of 3,3',5,5'-tetramethylbiphenyl diglycidyl ether (Mitsubishi Chemical Co., Ltd.), 3.48 g of bis(3,5-dimethyl-4-hydroxyphenyl) sulfone (Tokyo Chemical Industry Co., Ltd.), and 0.28 g of tetrabutylphosphonium bromide (Hokuko Chemical Industry Co., Ltd.) were added to 31.01 g of propylene glycol monomethyl ether and dissolved. After nitrogen replacement of the reaction container, the reaction was carried out at 120°C for 24 hours to obtain a polymer solution. GPC analysis was performed, and the weight average molecular weight of the obtained polymer 1 converted by standard polystyrene was 22,600, and the dispersity was 3.4. The structure present in polymer 1 is shown in the following formula.

[0337]

[0338] <Synthesis example 2>

[0339] 4.00 g of 3,3',5,5'-tetramethylbiphenyl diglycidyl ether (Mitsubishi Chemical Co., Ltd.), 3.81 g of 2,2-bis(4-hydroxyphenyl)hexafluoropropane (Tokyo Chemical Industry Co., Ltd.), and 0.28 g of tetrabutylphosphonium bromide (Hokuko Chemical Industry Co., Ltd.) were added to 12.13 g of propylene glycol monomethyl ether and dissolved. After nitrogen substitution in the reaction vessel, the reaction was carried out at 120°C for 24 hours to obtain a polymer solution. GPC analysis was performed, and the weight average molecular weight of the obtained polymer 2 converted by standard polystyrene was 22,000, and the dispersion degree was 2.8. The structure present in polymer 2 is shown in the following formula.

[0340]

[0341] <Synthesis example 3>

[0342] 7.00 g of 3,3',5,5'-tetramethylbiphenyl diglycidyl ether (Mitsubishi Chemical Corporation), 2.96 g of diethylbarbital (Yashiro Pharmaceutical Co., Ltd.), 2.21 g of 3,5-diiodosalicylic acid (Tokyo Chemical Industry Co., Ltd.) and 0.48 g of tetrabutylphosphonium bromide (Hokko Chemical Industry Co., Ltd.) were added to 29.53 g of propylene glycol monomethyl ether and dissolved. After nitrogen replacement of the reaction container, the reaction was carried out at 120°C for 24 hours to obtain a polymer solution. GPC analysis was performed, and the weight average molecular weight of the obtained polymer 3 converted by standard polystyrene was 5600, and the dispersion degree was 2.3. The structure present in polymer 3 is shown in the following formula.

[0343]

[0344] <Comparative Synthesis Example 1>

[0345] 5.00 g of monoallyl diglycidyl isocyanuric acid (manufactured by Shikoku Chemical Industry Co., Ltd.), 5.75 g of bis(3,5-dimethyl-4-hydroxyphenyl) sulfone (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.16 g of 2,6-di-tert-butyl-p-cresol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 0.46 g of tetrabutylphosphonium bromide (manufactured by Hokuko Chemical Industry Co., Ltd.) were added to 45.45 g of cyclohexanone and dissolved. After nitrogen substitution in the reaction vessel, the reaction was carried out at 120° C. for 24 hours to obtain a polymer solution. GPC analysis was performed, and the weight average molecular weight of the obtained polymer 4 converted by standard polystyrene was 16200, and the dispersion degree was 2.9. The structure present in polymer 4 is shown in the following formula.

[0346]

[0347] <Comparative Synthesis Example 2>

[0348] 9.00 g of monoallyl diglycidyl isocyanuric acid (manufactured by Shikoku Chemical Industry Co., Ltd.), 11.36 g of 2,2-bis(4-hydroxyphenyl)hexafluoropropane (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.28 g of 2,6-di-tert-butyl-p-cresol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 1.09 g of tetrabutylphosphonium bromide (manufactured by Hokuko Chemical Industry Co., Ltd.) were added to 26.56 g of propylene glycol monomethyl ether and dissolved. After nitrogen substitution in the reaction vessel, the reaction was carried out at 120° C. for 24 hours to obtain a polymer solution. GPC analysis was performed, and the weight average molecular weight of the obtained polymer 5 converted by standard polystyrene was 17,500, and the dispersity was 2.4. The structure present in polymer 5 is shown in the following formula.

[0349]

[0350] (Preparation of Resist Underlayer Film-Forming Composition)

[0351] The polymers, crosslinking agents, curing catalysts, surfactants and solvents obtained in the above-mentioned Synthesis Examples 1 to 2 and Comparative Synthesis Examples 1 to 2 were mixed in the proportions shown in Tables 1-1 and 1-2, and filtered with a 0.1 μm fluororesin filter to prepare compositions for forming resist underlayer films.

[0352] The meanings of the abbreviations in Table 1-1 and Table 1-2 are as follows.

[0353] PGME-PL: imidazo[4,5-d]imidazole-2,5(1H,3H)dione, tetrahydro-1,3,4,6-tetrakis[(2-methoxy-1-methylethoxy)methyl]-

[0354] ·PyPSA: pyridinium p-hydroxybenzenesulfonic acid

[0355] ·PGMEA: Propylene glycol monomethyl ether acetate

[0356] PGME: Propylene glycol monomethyl ether

[0357] Cy:cyclohexanone

[0358] Each added amount is expressed in parts by mass.

[0359] It should be noted that the addition ratio of the polymer in Table 1-1 and Table 1-2 does not refer to the addition amount of the polymer solution but indicates the addition amount of the polymer itself.

[0360] Table 1-1

[0361]

[0362] Table 1-2

[0363]

[0364] (Dissolution test in photoresist solvent)

[0365] The resist underlayer film-forming compositions of Examples 1 to 2 and Comparative Examples 1 to 2 were coated on silicon wafers using a spin coater. The silicon wafers were baked on a hot plate at 205°C for 60 seconds to obtain resist underlayer films with a thickness of 5 nm. The resist underlayer films were immersed in a mixed solution of propylene glycol monomethyl ether / propylene glycol monomethyl ether acetate = 70 / 30 (volume ratio) as a solvent used for photoresists, and the film thickness was changed to It is considered "good" when it is less than The results are shown in Table 2.

[0366] (Film-forming property test)

[0367] The resist underlayer film-forming compositions of Examples 1 to 2 and Comparative Examples 1 to 2 were applied to silicon wafers using a spin coater. The silicon wafers were baked on a hot plate at 205°C for 60 seconds to obtain resist underlayer films with a thickness of 5 nm. The surface roughness (Sa) of these resist underlayer films was measured using an atomic force microscope (AFM). It is considered "good" when it is less than The results are shown in Table 2.

[0368] Table 2

[0369] Dissolution test Film forming properties Example 1 good good Example 2 good good Comparative Example 1 good good Comparative Example 2 good good

[0370] (Resist Patterning Evaluation)

[0371] (Test of forming a resist pattern using EUV exposure equipment)

[0372] The compositions for forming the resist underlayer film of Examples 1 to 2 and Comparative Examples 1 to 2 were respectively coated on a silicon wafer using a spin coater. The silicon wafer was baked on a hot plate at 205°C for 60 seconds to obtain a resist underlayer film with a film thickness of 5 nm. A positive resist solution for EUV was spin-coated on the resist underlayer film and heated at 130°C for 60 seconds to form an EUV resist film. The resist film was exposed under specified conditions using an EUV exposure device (NXE3400B). After exposure, it was baked at 100°C for 60 seconds (PEB), cooled to room temperature on a cooling plate, and developed by spin immersion for 30 seconds using a 2.38% tetramethylammonium hydroxide aqueous solution (NMD-3) as a photoresist developer. A resist pattern with a hole size of 17nm to 20nm was formed. The length of the resist pattern was measured using a scanning electron microscope (manufactured by Hitachi High-Tech Novel Devices, CG6300).

[0373] The photoresist pattern thus obtained was evaluated to see whether a 20 nm contact hole (C / H) could be formed. In all cases of Examples 1 to 2 and Comparative Examples 1 to 2, it was confirmed that a 20 nm C / H pattern was formed. In addition, the EUV irradiation amount that formed a 20 nm hole was designated as the optimal irradiation energy, and the irradiation energy (mJ / cm 2 ) are shown in Table 3. It was confirmed that Examples 1 and 2 had improved sensitivity compared with Comparative Examples 1 and 2.

[0374] Table 3

[0375]

Claims

1. A resist underlayer film-forming composition, which is a resist underlayer film-forming composition for EB or EUV lithography, and comprises a polymer having a structure represented by the following formula (1), and a solvent; In formula (1), R 1 and R 2 Each independently represents an alkyl group having 1 to 6 carbon atoms which may be substituted by a halogen atom, or a halogen atom; m1 and m2 each independently represent an integer from 0 to 4; R 1 When there are 2 or more R 1 It can be the same or different; R 2 When there are 2 or more R 2 It can be the same or different; *Indicates bonding position.

2. The resist underlayer film-forming composition according to claim 1, wherein the polymer has a repeating unit represented by the following formula (1-1) as a repeating unit having a structure represented by the above formula (1); In formula (1-1), R 1 and R 2 Each independently represents an alkyl group having 1 to 6 carbon atoms which may be substituted by a halogen atom, or a halogen atom; m1 and m2 each independently represent an integer from 0 to 4; R 1 When there are 2 or more R 1 It can be the same or different; R 2 When there are 2 or more R 2 It can be the same or different; Q 1 represents a divalent organic group having an aromatic hydrocarbon ring; n1 and n2 each independently represent 0 or 1.

3. The resist underlayer film-forming composition according to claim 2, wherein Q 1 It is shown in the following formula (1-1-1); In formula (1-1-1), Z 1 represents a single bond, an alkylene group having 1 to 6 carbon atoms which may be substituted by a halogen atom, or a sulfonyl group; R 11 and R 12 Each independently represents an alkyl group having 1 to 13 carbon atoms which may be substituted by a halogen atom, a hydroxyl group, a methoxy group, a thiol group, an acetyl group, a nitro group, an allyl group, a phenyl group, a naphthyl group, or a halogen atom; n11 and n12 each independently represent an integer from 0 to 4; R 11 When there are 2 or more R 11 It can be the same or different; R 12 When there are 2 or more R 12 It can be the same or different.

4. The resist underlayer film forming composition according to claim 1, wherein m1 and m2 are 1, R 1 and R 2 It is methyl. The resist underlayer film-forming composition according to claim 1 , comprising a cross-linking agent.

6. The resist underlayer film-forming composition according to claim 5, wherein the crosslinking agent is a compound having two or more structures represented by the following formula (C); In formula (C), R 101 represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxyalkyl group having 2 to 6 carbon atoms; * represents a bonding position. 7 . A resist underlayer film which is a cured product of the resist underlayer film-forming composition according to claim 1 . 8 . A laminate comprising a semiconductor substrate and the resist underlayer film according to claim 7 .

9. A method for manufacturing a semiconductor device, comprising: 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 6; and A step of forming a resist film on the resist underlayer film.

10. A pattern forming method comprising 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 6; forming a resist film on the resist underlayer film; irradiating the resist film with EB or EUV, 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.

Images