Composition for forming resist underlayer film

Abstract

Provided is a composition for forming a resist underlayer film or the like, used for forming a resist underlayer film that maintains favorable sensitivity, exhibits an improved etching rate, and allows formation of a fine and favorable resist pattern. The composition for forming a resist underlayer film contains a polymer (A) having a structure represented by the following formula (1), and a solvent. (In formula (1), R101 and R102 each independently represent an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an aralkyl group, a heterocyclic group, or a halogenated, aminated, or nitrated derivative group thereof. * represents a bond).

Description

Composition for forming a resist underlayer film

[0001] The present invention relates to a composition for forming a resist underlayer film, a resist underlayer film, a laminate, a method for manufacturing a semiconductor device, and a method for forming a pattern.

[0002] Conventionally, microfabrication using lithography with resist compositions has been performed in the manufacturing of semiconductor devices. This microfabrication method involves forming a thin film of a photoresist composition on a semiconductor substrate such as a silicon wafer, irradiating it with an active light such as ultraviolet light through a mask pattern on which the device pattern is drawn, developing the film, and then etching the substrate using the resulting photoresist pattern as a protective film, thereby forming fine irregularities on the substrate surface corresponding to the photoresist pattern. In recent years, semiconductor devices have become more highly integrated, and in addition to the conventionally used i-line (wavelength 365 nm), KrF excimer laser (wavelength 248 nm), and ArF excimer laser (wavelength 193 nm), the practical application of EUV light (wavelength 13.5 nm) or EB (electron beam) is being considered for cutting-edge microfabrication. Consequently, poor resist pattern formation has become a major problem. Therefore, in order to solve this problem, methods of providing a resist underlayer film between the resist and the semiconductor substrate are being widely investigated.

[0003] A composition for forming a resist underlayer has been proposed, comprising a polymer (A) containing isocyanuric acid units and a solvent (see Patent Documents 1 and 2).

[0004] International Publication No. 2009 / 096340 Brochure International Publication No. 2013 / 018802 Brochure

[0005] Examples of properties required for a resist underlayer film include that no intermixing with a resist film formed on an upper layer occurs (being insoluble in a resist solvent), and that a favorable resist pattern can be formed by improving the sensitivity and adhesion of the resist pattern. The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a composition for forming a resist underlayer film that can improve the etching rate while maintaining good sensitivity and can form a fine and favorable resist pattern, as well as a resist underlayer film, a laminate, a method for producing a semiconductor device, and a pattern forming method using the composition for forming a resist underlayer film.

[0006] In order to solve the above problems, the inventors of the present invention have conducted intensive studies, found that the above problems can be solved, and completed the present invention having the following gist.

[0007] That is, the present invention includes the following aspects. [1] A composition for forming a resist underlayer film, comprising a polymer (A) having a structure represented by the following formula (1) and a solvent. (In formula (1), R １０１ and R １０２ each independently represent an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an aralkyl group, a heterocyclic group, or a halogenated, aminated or nitrated derivative group thereof. * represents a bond.) [2] The composition for forming a resist underlayer film according to [1], wherein the polymer (A) is a polymer having a structure represented by the following formula (2). (In formula (2), each A independently represents a hydrogen atom, a methyl group, or an ethyl group. R １０１ and R １０２ are R in formula (1) １０１ and R １０２ are the same as defined above. * represents a bond.) [3] The composition for forming a resist underlayer film according to [2], wherein the polymer (A) is a polymer having a structural unit represented by the following formula (3). (In formula (3), A is the same as A in formula (2). R １０１ and R １０２ are R in formula (1) １０１ and R １０２It is the same as above. Q represents a divalent group.) [4] The resist underlayer film forming composition according to [3], wherein Q in formula (3) is represented by the following formula (3-1) or formula (3-2). (In formula (3-1), Q １ represents a divalent organic group. n1 and n2 each independently represent 0 or 1. In formula (3-2), X １ Z represents a group expressed by any of the following formulas (3-2-1) to (3-2-3). １ and Z ２ Each of these independently represents a single bond or a group represented by the following formula (3-2-4). * represents a bond. (In formulas (3-2-1) to (3-2-3), R １ and R ２ Each of these independently represents a hydrogen atom, 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, a benzyl group, or a phenyl group, and each of the alkyl groups having 1 to 6 carbon atoms, the benzyl group, and the phenyl group may independently be substituted with a group or atom selected from the group consisting of alkyl groups having 1 to 6 carbon atoms, halogen atoms, alkoxy groups having 1 to 6 carbon atoms, alkoxyalkyl groups having 2 to 6 carbon atoms, nitro groups, cyano groups, hydroxyl groups, and alkylthio groups having 1 to 6 carbon atoms, and R １ and R ２ These may be bonded to each other to form a ring with 3 to 6 carbon atoms. ３ represents 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, a benzyl group, or a phenyl group. The alkyl group having 1 to 6 carbon atoms, the benzyl group, and the phenyl group may each be independently substituted with a group or atom selected from the group consisting of alkyl groups having 1 to 6 carbon atoms, halogen atoms, alkoxy groups having 1 to 6 carbon atoms, alkoxyalkyl groups having 2 to 6 carbon atoms, nitro groups, cyano groups, hydroxyl groups, and alkylthio groups having 1 to 6 carbon atoms. * represents a bond. *1 represents a bond that bonds to a carbon atom in formula (3-2). *2 represents a bond that bonds to a nitrogen atom in formula (3-2). (In formula (3-2-4), m represents an integer from 1 to 4. n represents an integer from 0 to 4. p1 and p2 each independently represent 0 or 1. *3 represents a bond that connects to the nitrogen atom in formula (3-2). *4 represents a bond.) [5] Q in formula (3-1) １ The divalent organic group is a divalent group containing a sulfur atom, an alkylene group, an alkenylene group, an alkylylene group, and a divalent group containing an aromatic ring, wherein the aromatic ring may be substituted with a group or atom 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, a hydroxyl group, a fluoroalkyl group, and an alkylthio group having 1 to 6 carbon atoms, as described in [4]. [6] Q in formula (3-1) １ A resist underlayer film forming composition according to [5], wherein the divalent group containing a sulfur atom is represented by the following formula (3-1-1). (In formula (3-1-1), R ３１ , R ３２ , and R ３３ Each independently represents a single bond or an alkylene group having 1 to 3 carbon atoms. r represents 0 or 1. * represents a bond.) [7] A resist underlayer film forming composition according to any one of [3] to [6], wherein the polymer has a structure represented by the following formula (E) at its terminal. (In formula (E), E represents a group having 1 to 20 carbon atoms. n represents 0 or 1. * represents a bond.) [8] The resist underlayer film forming composition according to [7], wherein E in formula (E) represents a monovalent group having a ring structure. [9] The resist underlayer film forming composition according to any one of [1] to [8], wherein the solvent comprises at least one selected from the group consisting of alkylene glycol monoalkyl ethers and monocarboxylic acid esters of alkylene glycol monoalkyl ethers.

[10] The resist underlayer film forming composition according to any one of [1] to [9], further comprising a crosslinking agent.

[11] The resist underlayer film forming composition according to

[10] , wherein the crosslinking agent is at least one selected from the group consisting of aminoplast crosslinking agents and phenoplast crosslinking agents.

[12] The resist underlayer film forming composition according to any one of [1] to

[11] , further comprising a curing catalyst.

[13] A resist underlayer formation composition according to any one of [1] to

[12] , used in EUV lithography.

[14] A resist underlayer, which is a cured product of the resist underlayer formation composition according to any one of [1] to

[13] .

[15] A laminate comprising a semiconductor substrate and the resist underlayer according to

[14] .

[16] A method for manufacturing a semiconductor device, comprising the steps of: forming a resist underlayer on a semiconductor substrate using the resist underlayer formation composition according to any one of [1] to

[13] ; and forming a resist film on the resist underlayer.

[17] A pattern formation method, comprising the steps of: forming a resist underlayer on a semiconductor substrate using the resist underlayer formation composition according to any one of [1] to

[13] ; forming a resist film on the resist underlayer; irradiating the resist film with light or an electron beam, then developing the resist film to obtain a resist pattern; and etching the resist underlayer using the resist pattern as a mask.

[0008] According to the present invention, it is possible to provide a resist underlayer film formation composition that can improve etching speed while maintaining good sensitivity and form a fine and good resist pattern, as well as a method for manufacturing a resist underlayer film, a laminate, a semiconductor device, and a pattern formation method using the resist underlayer film formation composition.

[0009] (Composition for forming a resist underlayer film) The resist underlayer film composition of the present invention comprises a polymer (A) and a solvent. Here, polymer (A) is a polymer having a structure represented by the following formula (1).

[0010] In formula (1), R １０１ and R １０２ Each of these independently represents an alkyl group, alkenyl group, alkynyl group, aryl group, aralkyl group, heterocyclic group, or a halogenated, aminated, or nitrated derivative group thereof. * represents a bond.

[0011] The present invention is characterized in that a polymer having a specific structure represented by formula (1), for example, isocyanuric acid having a specific substituent such as a diacetoxypropyl group, is included in the resist underlayer film forming composition. As a result, the resist underlayer film formed from the resist underlayer film forming composition is a film that can improve etching rate and form a fine and good resist pattern while maintaining good sensitivity.

[0012] The resist underlayer film forming composition of the present invention may contain a crosslinking agent, a curing catalyst, and the like.

[0013] The following describes each component contained in the resist underlayer film formation composition.

[0014] <Polymer (A) according to the present invention> As described above, polymer (A) has a structure represented by the following formula (1). The polymer may further have a structure other than the structure represented by the following formula (1).

[0015] <<Structure represented by formula (1)>>

[0016] In formula (1), R １０１ and R １０２Each of these independently represents an alkyl group, alkenyl group, alkynyl group, aryl group, aralkyl group, heterocyclic group, or a halogenated, aminated, or nitrated derivative group thereof. * represents a bond.

[0017] R １０１ and R １０２ In this context, alkyl groups are alkyl groups having 1 to 18 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-heptyl, and cyclohexyl groups. Alkenyl groups are alkenyl groups having 2 to 6 carbon atoms, such as vinyl, 1-propenyl, and 2-propenyl groups. Alkynyl groups are alkynyl groups having 2 to 6 carbon atoms, such as ethynyl and propargyl groups. Aryl groups are aryl groups having 6 to 20 carbon atoms, such as phenyl, tolyl, naphthyl, methylnaphthyl, anthryl, and ethylanthryl groups. Aalkyl groups are aralkyl groups having 7 to 22 carbon atoms, such as benzyl, phenethyl, naphthylmethyl, naphthylethyl, anthryl, and anthrylmethyl groups. Examples of heterocyclic groups include imidazole, pyrazole, pyridazine, pyrimidine, quinoline, benzoxazole, thiophene, dithiol, thiazole, thiadiazole, and benzothiazole groups. These alkyl groups, alkenyl, alkynyl, aryl, aralkyl, and heterocyclic groups can also be used as halogenated (fluorinated, brominated, iodized), aminated, or nitrated derivative groups. Examples include chloromethyl, dichloromethyl, trichloromethyl, trifluoromethyl, aminophenyl, and nitrobenzyl groups. １０１ and R １０２ They may be the same or different.

[0018] The polymer (A) described above preferably has a structure represented by the following formula (2).

[0019] In formula (2), A independently represents a hydrogen atom, a methyl group, or an ethyl group. １０１and R １０２ R in equation (1) １０１ and R １０２ It is the same as above. * represents a coupling.

[0020] <<Structural unit represented by formula (3)>> The polymer (A) above is preferably a polymer having a structural unit represented by the following formula (3).

[0021] In equation (3), A is the same as A in equation (2). １０１ and R １０２ R in equation (1) １０１ and R １０２ It is the same as this. Q represents a divalent group.

[0022] Q in formula (3) is not particularly limited as long as it is a divalent group. The number of carbon atoms in the divalent group may be, for example, 1 to 40, 1 to 20, or 1 to 15.

[0023] In formula (3), Q may or may not have a ring structure. In formula (3), Q may or may not have a heteroatom. Examples of heteroatoms include oxygen, nitrogen, and sulfur atoms. In formula (3), Q may have a halogen atom. In this specification, examples of halogen atoms include fluorine, chlorine, bromine, and iodine atoms.

[0024] In formula (3), Q is preferably represented by the following formula (3-1) or formula (3-2) from the viewpoint of suitably obtaining the effects of the present invention.

[0025] In formula (3-1), Q １ n1 represents a divalent organic group. n1 and n2 each independently represent 0 or 1.

[0026] In formula (3-2), X １ Z represents a group expressed by any of the following formulas (3-2-1) to (3-2-3). １ and Z ２Each of these independently represents a single bond or a group represented by the following formula (3-2-4). * represents a bond.

[0027] In formulas (3-2-1) to (3-2-3), R １ and R ２ Each of these independently represents a hydrogen atom, 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, a benzyl group, or a phenyl group, and each of the alkyl groups having 1 to 6 carbon atoms, the benzyl group, and the phenyl group may independently be substituted with a group or atom selected from the group consisting of alkyl groups having 1 to 6 carbon atoms, halogen atoms, alkoxy groups having 1 to 6 carbon atoms, alkoxyalkyl groups having 2 to 6 carbon atoms, nitro groups, cyano groups, hydroxyl groups, and alkylthio groups having 1 to 6 carbon atoms, and R １ and R ２ These may be bonded to each other to form a ring with 3 to 6 carbon atoms. ３ represents 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, a benzyl group, or a phenyl group, and the alkyl group having 1 to 6 carbon atoms, the benzyl group, and the phenyl group may each be independently substituted with a group or atom selected from the group consisting of alkyl groups having 1 to 6 carbon atoms, halogen atoms, alkoxy groups having 1 to 6 carbon atoms, alkoxyalkyl groups having 2 to 6 carbon atoms, nitro groups, cyano groups, hydroxyl groups, and alkylthio groups having 1 to 6 carbon atoms. * represents a bond. *1 represents a bond that bonds to the carbon atom in formula (3-2). *2 represents a bond that bonds to the nitrogen atom in formula (3-2).

[0028] In formula (3-2-4), m represents an integer from 1 to 4. n represents an integer from 0 to 4. p1 and p2 each independently represent 0 or 1. *3 represents a bond that connects to the nitrogen atom in formula (3-2). *4 represents a bond.

[0029] Q in equation (3-1) １The divalent organic group preferably represents a divalent group containing a sulfur atom, an alkylene group, an alkenylene group, an alkynylene group, or a divalent group containing an aromatic ring. The aromatic ring may be substituted with a group or atom selected from the group consisting of C1-C6 alkyl groups, halogen atoms, C1-C6 alkoxy groups, nitro groups, cyano groups, hydroxyl groups, fluoroalkyl groups, and C1-C6 alkylthio groups. Examples of divalent groups containing an aromatic ring include a phenylene group, a naphthylene group, or an anthrylene group, or a divalent group represented by the following formula (Q1-A). The phenylene group, the naphthylene group, the anthrylene group, and the aromatic ring in formula (Q1-A) may each be independently substituted with a group or atom selected from the group consisting of C1-C6 alkyl groups, halogen atoms, C1-C6 alkoxy groups, nitro groups, cyano groups, hydroxyl groups, fluoroalkyl groups, and C1-C6 alkylthio groups.

[0030]

[0031] In formula (Q1-A), R ａ Each of these independently represents a group or atom selected from the group consisting of alkyl groups having 1 to 6 carbon atoms, halogen atoms, alkoxy groups having 1 to 6 carbon atoms, nitro groups, cyano groups, hydroxyl groups, fluoroalkyl groups, and alkylthio groups having 1 to 6 carbon atoms. W represents a single bond, -CH ２ -, -C(CH ３ ) ２ -, -C (CF ３ ) ２ -, -CR １８ R １９ - represents R １８ and R １９ R is a single bond or an alkyl group, １８ and R １９ These elements may be joined to form a ring. Each n independently represents an integer from 0 to 4. * represents a join.

[0032] Q in the above equation (3-1) １More specifically, examples of divalent organic groups include divalent groups containing sulfur atoms with 2 to 20 carbon atoms, alkylene groups with 1 to 20 carbon atoms, alkenylene groups with 2 to 20 carbon atoms, alkynylene groups with 2 to 20 carbon atoms, and divalent groups containing aromatic rings with 6 to 50 carbon atoms.

[0033] Q in equation (3-1) １ The divalent group containing a sulfur atom is preferably represented by the following formula (3-1-1).

[0034] In formula (3-1-1), R ３１ , R ３２ , and R ３３ Each of these independently represents a single bond or an alkylene group with 1 to 3 carbon atoms. r represents 0 or 1. * represents a bond.

[0035] In particular, Q in equation (3-1) １ It is preferable that the group is a divalent group containing a disulfide bond.

[0036] Q in equation (3-1) １ Examples of groups represented by formula (3-1) when is a divalent group containing a sulfur atom include the following groups: (* indicates a link.)

[0037] Q in equation (3-1) １ The alkylene group in formula (3-1) may have a ring structure. Examples of ring structures include a cyclohexane ring. １ However, examples of groups represented by formula (3-1) when they are alkylene or alkenylene groups include the following:

[0038] Q in equation (3-1) １ However, in the case of a divalent group containing an aromatic ring, more specifically a phenylene group, a naphthylene group, or anthrylene group, or a divalent group represented by the above formula (Q1-A), examples of the group represented by formula (3-1) include the following groups. (* indicates a link.)

[0039] Examples of groups represented by formula (3-2) include the following: (* indicates a link.)

[0040] The polymer may further have a structure represented by the following formula (E) at its ends. The structure represented by formula (E) may be present at one end of the polymer or at both ends. (In formula (E), E represents a group having 1 to 20 carbon atoms. n represents 0 or 1. * represents a bond.)

[0041] The element E in formula (E) is not particularly limited as long as it is a group having 1 to 20 carbon atoms. In formula (E), E represents, for example, a monovalent group having a ring structure. Examples of ring structures include aromatic rings and non-aromatic rings. Examples of aromatic rings include aromatic hydrocarbon rings. Examples of aromatic hydrocarbon rings include benzene rings, naphthalene rings, and anthracene rings. Non-aromatic rings may be monocyclic or polycyclic. Non-aromatic rings may also be hydrocarbon rings or heterocyclic rings. Polycyclic non-aromatic rings may be hydrocarbon rings or fused rings of hydrocarbon rings and heterocyclic rings. The element E in formula (E) may or may not have a heteroatom. Examples of heteroatoms include oxygen atoms, nitrogen atoms, and sulfur atoms. The element E in formula (E) may or may not have a halogen atom.

[0042] Examples of structures represented by formula (E) include those represented by the following formulas (E-1) to (E-10). (In formula (E-1), R Ｅ１ , R Ｅ２ and R Ｅ３each independently represent a hydrogen atom, a linear or branched hydrocarbon group having 1 to 13 carbon atoms, or a hydroxy group, and R Ｅ１ , R Ｅ２ and R Ｅ３ at least one of which is said hydrocarbon group. n represents 0 or 1. * represents a binding site.)

[0043] (In formulas (E-2) to (E-4), R Ｅ４ represents a hydrogen atom or a methyl group, R Ｅ５ and R Ｅ６ each independently represent a hydrogen atom, a linear or branched hydrocarbon group having 1 to 6 carbon atoms, an alicyclic hydrocarbon group, a phenyl group, a benzyl group, a benzyloxy group, a benzylthio group, an imidazole group or an indole group, and the hydrocarbon group, the alicyclic hydrocarbon group, the phenyl group, the benzyl group, the benzyloxy group, the benzylthio group, the imidazole group and the indole group may have at least one hydroxy group or methylthio group as a substituent, R Ｅ７ represents a hydrogen atom or a hydroxy group, Q Ｅ１ represents an arylene group, each n independently represents 0 or 1, y represents an integer of 1 to 4, w represents an integer of 1 to 4, x1 represents 0 or 1, and x2 represents an integer of 1 to 5. * represents a binding site.)

[0044] (In formula (E-5), R Ｅ８ , R Ｅ９ and R Ｅ１０ each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 13 carbon atoms, a halogen atom or a hydroxy group, and R Ｅ８ , R Ｅ９ and R Ｅ１０ at least one of which represents said alkyl group, Ar represents a benzene ring, a naphthalene ring or an anthracene ring, two carbonyl groups each bind to two adjacent carbon atoms of the ring represented by Ar, and X Ｅ１ represents a linear or branched alkyl group having 1 to 6 carbon atoms which may have an alkoxy group having 1 to 3 carbon atoms as a substituent. * represents a binding site.)

[0045] (In formulas (E-6) and (E-7), R Ｅ１１ represents an optionally substituted alkyl group having 1 to 6 carbon atoms, a phenyl group, a pyridyl group, a halogen atom or a hydroxy group, and R Ｅ１２ each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxy group, a halogen atom or an ester group represented by -C(=O)O-X, X represents an optionally substituted alkyl group having 1 to 6 carbon atoms, and R Ｅ１３ each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxy group or a halogen atom, and R Ｅ１４ represents a single bond or a divalent organic group having 1 to 8 carbon atoms, and R Ｅ１５ represents a divalent organic group having 1 to 8 carbon atoms, and A Ｅ１ each independently represents an aromatic ring or an aromatic heterocyclic ring, n each independently represents 0 or 1, u represents 1 or 2. * represents a bonding site.)

[0046] (In formulas (E-8) and (E-9), A Ｅ２ each independently represents an aryl group having 6 to 40 carbon atoms, and R Ｅ１６ represents a halogen atom, an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, and R Ｅ１７ and R Ｅ１８ each independently represent a hydrogen atom, a halogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms or an optionally substituted aryl group having 6 to 40 carbon atoms, n represents 0 or 1, n1 and n3 each independently represent an integer of 1 to 12, n2 represents an integer of 0 to 11. * represents a bonding site.)

[0047] (In formula (E-10), X represents a phenyl group, naphthyl group or anthracenyl group substituted with at least one group selected from the group consisting of a halogen atom, a hydroxy group, and a linear or branched alkoxy group having 1 to 6 carbon atoms, n represents 0 or 1. * represents a bonding site.)

[0048] Specific examples of E in formula (E) include the following groups. (* indicates a link.)

[0049] The resist underlayer film formation composition may contain other polymers or other additives besides the polymer (A) mentioned above as film components.

[0050] The proportion of structural units represented by formula (3) in polymer (A) is not particularly limited, but from the viewpoint of suitably obtaining the effects of the present invention, it is preferably 10 mol% or more, and more preferably 20 mol% or more, relative to the total structural units of polymer (A). The proportion of structural units represented by formula (3) in polymer (A) is preferably 100 mol% or less, and more preferably 80 mol% or less, relative to the total structural units of polymer (A).

[0051] The weight-average molecular weight Mw of polymer (A) is not particularly limited, but is preferably 300 or more, more preferably 500 or more, even more preferably 1,000 or more, even more preferably 1,500 or more, and particularly preferably 2,000 or more. There is also no particular upper limit to the weight-average molecular weight Mw, but it is preferable that the weight-average molecular weight Mw is 50,000 or less. In the present invention, the weight-average molecular weight Mw is a polystyrene equivalent value measured by gel permeation chromatography (GPC).

[0052] The content of polymer (A) of the present invention in the resist underlayer film forming composition is not particularly limited, but is preferably 50% to 99% by mass, more preferably 60% to 97% by mass, and particularly preferably 70% to 95% by mass, relative to the non-volatile content. Non-volatile content refers to components other than the solvent in the resist underlayer film forming composition.

[0053] There are no particular limitations on the method for producing the polymer, but examples include the following methods (i) to (ii): (i): A method of reacting a diepoxy compound represented by the following formula (3A) with a compound represented by the following formula (3-1A) or formula (3-2A). (ii): A method of reacting a diepoxy compound represented by the following formula (3A) with a compound represented by the following formula (3-1A) or formula (3-2A) with a compound represented by the following formula (EA). Note that in (i) to (ii), other compounds may be used in combination. By using the compound represented by formula (EA), the group represented by formula (E) can be introduced to the ends of the polymer.

[0054] (In equation (3A), A is the same as A in equation (3). Also, in equation (3A), R １０１ and R １０２ These are R in equation (3), respectively. １０１ and R １０２ It is the same as this.

[0055] (In equation (3-1A), Q １ n1 and n2 are, respectively, Q in equation (3-1). １ (This is the same as n1 and n2.)

[0056] (In formula (3-2A), X １ Z １ , and Z ２ These are the X in equation (3-2), respectively. １ Z １ , and Z ２ It is the same as Z. １ and Z ２ The hydrogen atom bonded to it is usually an active hydrogen atom.

[0057] (In equation (EA), n and E are the same as n and E in equation (E), respectively.)

[0058] The diepoxy compound represented by formula (3A) above can be obtained, for example, by reacting a monomer represented by formula (T) below with an acid anhydride represented by formula (U) below, as follows. The reaction method can be in accordance with the method for producing isocyanuric acid derivatives described in Japanese Patent Application Publication No. 2-279684.

[0059]

[0060] The acid anhydride (formula (U)) used in this invention is an acid anhydride obtained from two molecules of monocarboxylic acid, and unlike acid anhydrides obtained from dicarboxylic acid used as curing agents for epoxy resins, it does not have the function of a curing agent for epoxy resins. １０１ and R １０２ Acid anhydrides of formula (U) containing include, for example, acetic anhydride, propionic anhydride, n-butyric anhydride, n-valeric anhydride, n-hexanoic anhydride, and trifluoroacetic anhydride. Depending on the type of acid anhydride (formula (U)), R of formula (1) １０１ and R １０２ However, R is determined １０１ and R １０２ A hydrocarbon group having 1 to 5 carbon atoms is preferred.

[0061] <Solvent> The solvent is not particularly limited and may be water or an organic solvent. Examples of organic solvents include alkylene glycol monoalkyl ethers and monocarboxylic acid esters of alkylene glycol monoalkyl ethers.

[0062] Examples of alkylene groups in alkylene glycol monoalkyl ethers include alkylene groups having 2 to 4 carbon atoms. Examples of alkyl groups in alkylene glycol monoalkyl ethers include alkyl groups having 1 to 4 carbon atoms. Examples of the number of carbon atoms in alkylene glycol monoalkyl ethers include 3 to 8. Examples of alkylene glycol monoalkyl ethers include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, and propylene glycol monoethyl ether.

[0063] Examples of alkylene groups in the monocarboxylic acid esters of alkylene glycol monoalkyl ethers include alkylene groups having 2 to 4 carbon atoms. Examples of alkyl groups in the monocarboxylic acid esters of alkylene glycol monoalkyl ethers include alkyl groups having 1 to 4 carbon atoms. Examples of monocarboxylic acids in the monocarboxylic acid esters of alkylene glycol monoalkyl ethers include saturated monocarboxylic acids having 2 to 4 carbon atoms. Examples of saturated monocarboxylic acids having 2 to 4 carbon atoms include acetic acid, propionic acid, and butyric acid. Examples of the number of carbon atoms in the monocarboxylic acid esters of alkylene glycol monoalkyl ethers include 5 to 10. Examples of monocarboxylic acid esters of alkylene glycol monoalkyl ethers include methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, and propylene glycol propyl ether acetate.

[0064] Other organic solvents include, for example, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, cycloheptanone, 4-methyl-2-pentanol, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, ethyl ethoxyacetate, 2-hydroxyethyl acetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, 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.

[0065] Among these solvents, alkylene glycol monoalkyl ethers and monocarboxylic acid esters of alkylene glycol monoalkyl ethers are preferred.

[0066] These solvents can be used individually or in combination of two or more.

[0067] The mass percentage of the organic solvent in the solvent is not particularly limited, but 50% to 100% by mass is preferred.

[0068] The solvent content in the resist underlayer film forming composition is not particularly limited, but is preferably 50% to 99.99% by mass, more preferably 75% to 99.95% by mass, and particularly preferably 90% to 99.9% by mass.

[0069] <Crosslinking agent> The crosslinking agent is not particularly limited. The crosslinking agent has a different structure from polymer (A) of the present invention.

[0070] As crosslinking agents, aminoplast crosslinking agents and phenoplast crosslinking agents are preferred. Aminoplast crosslinking agents are addition condensates of compounds having amino groups, such as melamine and guanamine, with formaldehyde. Phenoplast crosslinking agents are addition condensates of compounds having phenolic hydroxyl groups with formaldehyde.

[0071] Examples of crosslinking agents include compounds having two or more of the following structures. (In the structure, 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 bond. The bond is, for example, attached to a nitrogen atom or a carbon atom constituting an aromatic hydrocarbon ring.

[0072] R １０１ Preferably, the group is a hydrogen atom, a methyl group, an ethyl group, or a group represented by the following structure. (In the structure, R １０２ represents a hydrogen atom, a methyl group, or an ethyl group. * represents a bonding bond.

[0073] Preferred crosslinking agents include melamine compounds, guanamine compounds, glycoluryl compounds, urea compounds, and compounds having a phenolic hydroxyl group. These can be used individually or in combination of two or more.

[0074] Examples of melamine compounds include hexamethylmelamine, hexamethoxymethylmelamine, compounds in which one to six methylol groups of hexamethylmelamine are methoxymethylated or mixtures thereof, hexamethoxyethylmelamine, hexaacyloxymethylmelamine, compounds in which one to six methylol groups of hexamethylmelamine are acyloxymethylated or mixtures thereof.

[0075] Examples of guanamine compounds include tetramethylolguanamine, tetramethoxymethylguanamine, compounds in which one to four methylol groups of tetramethylolguanamine are methoxymethylated or mixtures thereof, tetramethoxyethylguanamine, tetraacyloxyguanamine, compounds in which one to four methylol groups of tetramethylolguanamine are acyloxymethylated or mixtures thereof.

[0076] Examples of glycoluryl compounds include tetramethylol glycoluryl, tetramethoxy glycoluryl, tetramethoxymethyl glycoluryl, compounds in which one to four methylol groups of tetramethylol glycoluryl are methoxymethylated or mixtures thereof, and compounds in which one to four methylol groups of tetramethylol glycoluryl are acyloxymethylated or mixtures thereof.

[0077] Furthermore, the glycoluryl compound may also be, for example, a glycoluryl derivative represented by the following formula (1E). (In equation (1E), four R １ Each of these independently represents either a methyl group or an ethyl group, R ２ and R ３ Each of these independently represents a hydrogen atom, an alkyl group with 1 to 4 carbon atoms, or a phenyl group.

[0078] Examples of glycoluryl derivatives represented by formula (1E) include compounds represented by the following formulas (1E-1) to (1E-6).

[0079] A glycoluryl derivative represented by formula (1E) can be obtained, for example, by reacting a glycoluryl derivative represented by the following formula (2E) with at least one compound represented by the following formula (3d).

[0080] (In formula (2E), R ２ and R ３ Each of these independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group, R ４ Each of these independently represents an alkyl group having 1 to 4 carbon atoms.

[0081] (In formula (3d), R １ (This represents a methyl group or an ethyl group.)

[0082] Examples of glycoluryl derivatives represented by formula (2E) include the compounds represented by formulas (2E-1) to (2E-4) below. Furthermore, examples of compounds represented by formula (3d) include the compounds represented by formulas (3d-1) and (3d-2) below.

[0083] Examples of urea compounds include tetramethylolurea, tetramethoxymethylurea, compounds in which one to four methylol groups of tetramethylolurea are methoxymethylated or mixtures thereof, and tetramethoxyethylurea.

[0084] Examples of compounds having a phenolic hydroxyl group include compounds represented by the following formulas (G-1) or (G-2). (In equations (G-1) and (G-2), Q １ R indicates a single bond or an m1-valent organic group. １ and R ４ Each of these 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. ２ and R ５ Each represents either a hydrogen atom or a methyl group. ３ and R ６Each of these represents an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 40 carbon atoms. １ is 1 ≤ n １ n is an integer ≤ 3. ２ is 2 ≤ n ２ An integer n ≤ 5 ３ is 0 ≤ n ３ n is an integer ≤ 3. ４ is 0 ≤ n ４ integers ≤ 3, 3 ≤ (n １ +n ２ +n ３ +n ４ This shows integers n ≤ 6. ５ is 1 ≤ n ５ n is an integer ≤ 3. ６ is 1 ≤ n ６ An integer n ≤ 4 ７ is 0 ≤ n ７ n is an integer ≤ 3. ８ is 0 ≤ n ８ integers ≤ 3, 2 ≤ (n ５ +n ６ +n ７ +n ８ (This represents an integer between 5 and 2. m1 represents an integer between 2 and 10.)

[0085] Furthermore, examples of compounds having a phenolic hydroxyl group include compounds represented by the following formulas (G-3) or (G-4). Compounds represented by formulas (G-1) or (G-2) may be obtained by reacting a compound represented by the following formula (G-3) or (G-4) with a hydroxyl group-containing ether compound or an alcohol having 2 to 10 carbon atoms. (In equations (G-3) and (G-4), Q ２ R indicates a single bond or an m2 valent organic group. ８ , R ９ , R １１ and R １２ Each represents either a hydrogen atom or a methyl group. ７ and R １０ Each of these represents an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 40 carbon atoms. ９ is 1 ≤ n ９ n is an integer ≤ 3. １０ is 2 ≤ n １０ An integer n ≤ 5１１ is 0 ≤ n １１ n is an integer ≤ 3. １２ is 0 ≤ n １２ integers ≤ 3, 3 ≤ (n ９ +n １０ +n １１ +n １２ This shows integers n ≤ 6. １３ is 1 ≤ n １３ n is an integer ≤ 3. １４ is 1 ≤ n １４ An integer n ≤ 4 １５ is 0 ≤ n １５ n is an integer ≤ 3. １６ is 0 ≤ n １６ integers ≤ 3, 2 ≤ (n １３ +n １４ +n １５ +n １６ ) indicates an integer ≤ 5. m² indicates an integer between 2 and 10. ) Q ２ Examples of m2 valent organic groups in this context include m2 valent organic groups having 1 to 4 carbon atoms.

[0086] Examples of compounds represented by formula (G-1) or formula (G-2) include the following compounds.

[0087] Examples of compounds represented by formula (G-3) or formula (G-4) include the following compounds. The above compound can be obtained as a product of Asahi Organic Chemicals Co., Ltd. and Honshu Chemical Industry Co., Ltd. An example of such a product is TMOM-BP, a product of Asahi Organic Chemicals Co., Ltd.

[0088] Among these, glycoluryl compounds are preferred, specifically tetramethylol glycoluryl, tetramethoxy glycoluryl, tetramethoxymethyl glycoluryl, compounds in which one to four methylol groups of tetramethylol glycoluryl are methoxymethylated or mixtures thereof, compounds in which one to four methylol groups of tetramethylol glycoluryl are acyloxymethylated or mixtures thereof, and tetramethoxymethyl glycoluryl is more preferred.

[0089] The molecular weight of the crosslinking agent is not particularly limited, but it is preferably 500 or less.

[0090] The content of the crosslinking agent in the resist underlayer film forming composition is not particularly limited, but is, for example, 5% to 90% by mass, preferably 10% to 70% by mass, relative to the polymer (A) of the present invention.

[0091] <Curing Catalyst> The curing catalyst included as an optional component in the resist underlayer film formation composition can be either a thermal acid generator or a photoacid generator, but it is preferable to use a thermal acid generator. Examples of thermal acid generating agents include sulfonic acid compounds and carboxylic acid compounds such as p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium-p-toluenesulfonate (pyridinium-p-toluenesulfonic acid), pyridinium phenolsulfonic acid, pyridinium-p-hydroxybenzenesulfonic acid (pyridinium salt of p-phenolsulfonic acid), pyridinium-trifluoromethanesulfonic acid, salicylic acid, camphorsulfonic acid, 5-sulfosalicylic acid, 4-chlorobenzenesulfonic acid, 4-hydroxybenzenesulfonic acid, benzenedisulfonic acid, 1-naphthalenesulfonic acid, citric acid, benzoic acid, hydroxybenzoic acid, N-methylmorpholine-p-toluenesulfonic acid, N-methylmorpholine-p-hydroxybenzenesulfonic acid, and N-methylmorpholine-5-sulfosalicylic acid.

[0092] Examples of photoacid generators include onium salt compounds, sulfonimide compounds, and disulfonyldiazomethane compounds.

[0093] Examples of iodonium salt compounds include iodonium salt compounds such as diphenyliodonium hexafluorophosphate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoron-butanesulfonate, diphenyliodonium perfluoron-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 nonafluoron-butanesulfonate, triphenylsulfonium camphorsulfonate and triphenylsulfonium trifluoromethanesulfonate.

[0094] Examples of sulfonimide compounds include N-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluoron-butanesulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, and N-(trifluoromethanesulfonyloxy)naphthalimide.

[0095] Examples of disulfonyl diazomethane compounds include bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(2,4-dimethylbenzenesulfonyl)diazomethane, and methylsulfonyl-p-toluenesulfonyldiazomethane.

[0096] Only one type of curing catalyst may be used, or two or more types may be used in combination.

[0097] When a curing catalyst is used, the content of the curing catalyst is, for example, 0.1% to 50% by mass relative to the crosslinking agent, preferably 1% to 30% by mass.

[0098] <Other components> The resist underlayer film forming composition does not produce pinholes or striations, and surfactants can be added to further improve the coatability against surface unevenness.

[0099] Examples of surfactants include linear or branched alkylbenzenesulfonic acids (e.g., dodecylbenzenesulfonic acid), polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether, polyoxyethylene alkylaryl ethers such as polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether, polyoxyethylene / polyoxypropylene block copolymers, sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, and sorbitan tristearate, and polyoxyethylene sorbitan monolaurate. Examples include nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters like polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate; fluorinated surfactants such as F-Top EF301, EF303, EF352 (manufactured by Tochem Products Co., Ltd., product name), Megafac F171, F173, R-30 (manufactured by DIC Corporation, product name), Florard FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd., product name), Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGC Inc., product name); and organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.). The amount of these surfactants added is usually 2.0% by mass or less, preferably 1.0% by mass or less, relative to the total solid content of the resist underlayer film forming composition. These surfactants may be added individually or in combination of two or more types.

[0100] The solid content of the resist underlayer film forming composition of the present invention, i.e., the components excluding the solvent, is, for example, 0.01% to 10% by mass.

[0101] The resist underlayer film formation composition is preferably used in EUV lithography.

[0102] (Resist Underlayer Film) The resist underlayer film of the present invention is a cured product of the resist underlayer film forming composition described above. The resist underlayer film can be manufactured, for example, by coating the resist underlayer film forming composition described above onto a semiconductor substrate and firing it.

[0103] Examples of semiconductor substrates to which the resist underlayer film formation 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.

[0104] When a semiconductor substrate with an inorganic film formed on its surface is used, the inorganic film is formed by, for example, ALD (atomic layer deposition), CVD (chemical vapor deposition), reactive sputtering, ion plating, vacuum deposition, or spin coating (spin-on-glass: SOG). Examples of the inorganic film include polysilicon films, silicon oxide films, silicon nitride films, BPSG (Boro-Phosphoric Acid Glass) films, titanium nitride films, titanium oxide nitride films, tungsten films, gallium nitride films, and gallium arsenide films.

[0105] The resist underlayer film forming composition of the present invention is applied to such a semiconductor substrate by an appropriate coating method such as a spinner or coater. Subsequently, the resist underlayer film is formed by baking using a heating means such as a hot plate. The baking conditions are appropriately selected from a bake temperature of 100°C to 400°C and a bake time of 0.3 minutes to 60 minutes. Preferably, the bake temperature is 120°C to 350°C and the bake time is 0.5 minutes to 30 minutes, and more preferably, the bake temperature is 150°C to 300°C and the bake time is 0.8 minutes to 10 minutes.

[0106] The thickness of the resist underlayer film can be, 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 ( The wavelengths are 5 nm to 0.05 μm (50 nm), 0.003 μm (3 nm) to 0.03 μm (30 nm), 0.003 μm (3 nm) to 0.02 μm (20 nm), 0.005 μm (5 nm) to 0.02 μm (20 nm), 0.003 μm (3 nm) to 0.01 μm (10 nm), 0.005 μm (5 nm) to 0.01 μm (10 nm), 0.003 μm (3 nm) to 0.006 μm (6 nm), or 0.005 μm (5 nm).

[0107] The method for measuring the film thickness of the resist underlayer in this specification is as follows: • Measurement device name: Ellipsometer-type film thickness measuring device RE-3100 (SCREEN Corporation) • SWE (single-wavelength ellipsometer) mode • Arithmetic mean of 8 points (for example, 8 points measured at 1 cm intervals in the wafer X direction)

[0108] (Laminate) The laminate of the present invention comprises a semiconductor substrate and a resist underlayer film of the present invention. Examples of the semiconductor substrate include the semiconductor substrate described above. The resist underlayer film is disposed on top of the semiconductor substrate, for example.

[0109] (Method for manufacturing semiconductor devices, method for forming patterns) The method for manufacturing semiconductor devices of the present invention includes at least the following steps: - A step of forming a resist underlayer film on a semiconductor substrate using the resist underlayer film forming composition of the present invention; and - A step of forming a resist film on the resist underlayer film.

[0110] The pattern formation method of the present invention includes at least the following steps: • A step of forming a resist underlayer film on a semiconductor substrate using the resist underlayer film formation composition of the present invention; • A step of forming a resist film on the resist underlayer film; • A step of irradiating the resist film with light or an electron beam, 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.

[0111] Typically, a resist film is formed on top of a resist underlayer. The thickness of the resist film can be, for example, 3,000 nm or less, 2,000 nm or less, 1,800 nm or less, 1,500 nm or less, or 1,000 nm or less. The lower limits are 100 nm, 80 nm, 50 nm, 30 nm, 20 nm, and 10 nm.

[0112] The resist film formed on the resist underlayer by a known method (e.g., coating and firing of a resist composition) is not particularly limited as long as it responds to light or electron beam (EB) used for irradiation. Both negative-type and positive-type photoresists can be used. In this specification, resists that respond to EB are also referred to as photoresists. Examples of photoresists include positive-type photoresists consisting of a novolac resin and 1,2-naphthoquinone diazide sulfonic acid ester, chemically amplified photoresists consisting of a binder having a group that decomposes with acid to increase the alkali dissolution rate and a photoacid generator, chemically amplified photoresists consisting of a low-molecular-weight compound that decomposes with acid to increase the alkali dissolution rate of the photoresist, an alkali-soluble binder and a photoacid generator, and chemically amplified photoresists consisting of a binder having a group that decomposes with acid to increase the alkali dissolution rate and a low-molecular-weight compound that decomposes with acid to increase the alkali dissolution rate of the photoresist and a photoacid generator, and resists containing metal elements. Examples include V146G (manufactured by JSR Corporation), APEX-E (manufactured by Cyprey Corporation), PAR710 (manufactured by Sumitomo Chemical Co., Ltd.), and AR2772 and SEPR430 (manufactured by Shin-Etsu Chemical Co., Ltd.). Additionally, examples include fluorine-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).

[0113] Also, 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, WO201 9 / 172054, WO2019 / 021975, WO2018 / 230334, WO2018 / 194123, JP 2018-180525, WO2018 / 190088, JP 2018-070596, JP 2018-028090, JP 2016-153409, JP 2016-130240, JP 2016-108325, JP 2016-047920, JP 2016-035570, JP 2016-035567, JP 2016-035565, JP 2019-101417, JP 2019-117373, JP 2019-052294, JP 2019-008280, JP 2019-008279, JP 2019-003176, JP 2019-003175, JP 2018-197853, JP 2019-191298, JP 2019-061217, JP 2018-045152, JP 2018-022039, JP 2016-090441, JP 2015-10878, JP 2012-168279, JP 2012-022261, JP 2012-022258, JP 2011-043749, JP 2010-18 While so-called resist compositions and metal-containing resist compositions such as resist compositions, radiation-sensitive resin compositions, and high-resolution patterning compositions based on organometallic solutions described in JP 1857, JP 2010-128369, WO2018 / 031896, JP 2019-113855, WO2017 / 156388, WO2017 / 066319, JP 2018-41099, WO2016 / 065120, WO2015 / 026482, JP 2016-29498, JP 2011-253185, etc., can be used, they are not limited to these.

[0114] Examples of resist compositions include the following compositions.

[0115] A photosensitive or radiation-sensitive resin composition comprising resin A having repeating units with acid-degradable groups whose polar groups are protected by protecting groups that are removed by the action of an acid, and a compound represented by the following general formula (121).

[0116] In general formula (121), m represents an integer from 1 to 6. １ and R ２ Each of these independently represents either a fluorine atom or a perfluoroalkyl group. １ is -O-, -S-, -COO-, -SO ２ -, or -SO ３ Represents -. L ２ W represents an alkylene group or single bond which may have substituents. １ This represents a cyclic organic group which may have substituents. ＋ This represents a cation.

[0117] A metal-containing film-forming composition for extreme ultraviolet or electron beam lithography, comprising a compound having a metal-oxygen covalent bond and a solvent, wherein the metal element constituting the compound belongs to the third to seventh period of groups 3 to 15 of the periodic table.

[0118] A radiation-sensitive resin composition comprising a polymer having a first structural unit represented by the following formula (31) and a second structural unit represented by the following formula (32) that includes an acid-dissociable group, and an acid generator.

[0119] (In formula (31), Ar is a group obtained by removing (n+1) hydrogen atoms from an arene having 6 to 20 carbon atoms. １ R is a hydroxyl group, a sulfanyl group, or a monovalent organic group having 1 to 20 carbon atoms. n is an integer from 0 to 11. If n is 2 or greater, multiple R １ They are the same or different. R ２ R is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. In formula (32), ３ R is 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(These are a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.)

[0120] A resist composition containing a resin (A1) comprising structural units having a cyclic carbonate ester structure, structural units represented by the following formula, and structural units having an acid-unstable group, and an acid generator.

[0121] [In the formula, R ２ X represents an alkyl group having 1 to 6 carbon atoms, a hydrogen atom, or a halogen atom, which may have a halogen atom. １ These are single bonds, -CO-O-* or -CO-NR ４ - represents *, where * represents a 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 the group consisting of hydroxyl groups and carboxyl groups.

[0122] Examples of resist films include the following:

[0123] A resist film comprising a base resin containing repeating units represented by the following formula (a1) and / or repeating units represented by the following formula (a2), and repeating units that generate acid bonded to the polymer main chain upon exposure.

[0124] (In equations (a1) and (a2), R Ａ Each of these is independently either a hydrogen atom or a methyl group. １ and R ２ These are each independently tertiary alkyl groups having 4 to 6 carbon atoms. ３ Each of these is independently either a fluorine atom or a methyl group. m is an integer from 0 to 4. １ X is a linking group having 1 to 12 carbon atoms, containing a single bond, a phenylene group or a naphthylene group, or at least one selected from an ester bond, a lactone ring, a phenylene group, and a naphthylene group. ２ (These are single bonds, ester bonds, or amide bonds.)

[0125] Examples of resist materials include the following:

[0126] A resist material comprising a polymer having repeating units represented by the following formula (b1) or formula (b2).

[0127] (In equations (b1) and (b2), R Ａ X is a hydrogen atom or a methyl group. １ X is a single bond or an ester group. ２ X 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 portion of the methylene groups constituting the alkylene group may be substituted with an ether group, an ester group, or a lactone ring-containing group, and X ２ At least one hydrogen atom in 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 some of the methylene groups constituting the alkylene group may be substituted with an ether group or an ester group. １ ~Rf ４ Each of these is independently a hydrogen atom, a fluorine atom, or a trifluoromethyl group, but at least one is a fluorine atom or a trifluoromethyl group. Also, Rf １ and Rf ２ These may combine to form a carbonyl group. １ ~R ５ Each of these 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 some 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 some 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 sulfonic acid ester group. １ and R ２These may combine to form a ring with the sulfur atom to which they are bonded.

[0128] A resist material comprising a base resin containing a polymer having repeating units represented by the following formula (a).

[0129] (In formula (a), R Ａ R is a hydrogen atom or a methyl group. １ R is a hydrogen atom or an acid-unstable group. ２ This is a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, or a halogen atom other than bromine. １ This is a linear, branched, or cyclic alkylene group having 1 to 12 carbon atoms, which may contain a single bond or a phenylene group, or an ester group or a lactone ring. ２ is -O-, -O-CH ２ It is - or -NH-. m is an integer from 1 to 4. u is an integer from 0 to 3. However, m + u is an integer from 1 to 4.

[0130] A resist composition that generates acid upon exposure and whose solubility in a developer changes due to the action of the acid, comprising a base component (A) whose solubility in a developer changes due to the action of the acid and a fluorine additive component (F) that exhibits decomposition in an alkaline developer, wherein the fluorine additive component (F) contains a fluororesin component (F1) having a constituent unit (f1) containing a base-dissociable group and a constituent unit (f2) containing a group represented by the following general formula (f2-r-1), the resist composition.

[0131] [In formula (f2-r-1), Rf ２１ Each of these 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. * represents a bond.

[0132] The aforementioned constituent unit (f1) includes a constituent unit represented by the following general formula (f1-1) or a constituent unit represented by the following general formula (f1-2).

[0133] [In formulas (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 that does not have an acid-dissociable site. A ａｒｙｌ X is a divalent aromatic cyclic group which may have substituents. ０１ R is a single bond or a divalent linking group. ２ These are, independently, organic groups that contain a fluorine atom.

[0134] The resist composition may be a metal-containing resist. Metal-containing resists are also called metal oxide resists (MORs), and a typical example is a tin oxide-based resist. Examples of metal oxide resist materials include a coating composition containing a metal oxo-hydroxo network having an organic ligand via a metal-carbon bond and / or metal-carboxylate bond, as described in Japanese Patent Application Publication No. 2019-113855. An example of a metal-containing resist uses a peroxo ligand as a radiosensitizing stabilizing ligand. Details of peroxo-based metal oxo-hydroxo compounds are described in the patent document described in paragraph

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

[0135] A coating comprising a metal oxo-hydroxo network having organic ligands via metal-carbon bonds and / or metal-carboxylate bonds.

[0136] Inorganic oxo / hydroxo-based compositions.

[0137] A coating solution comprising an organic solvent; a first organometallic composition comprising formula R ｚ SnO （２－（ｚ／２）－（ｘ／２）） (OH) ｘ (Here, 0 < z ≤ 2 and 0 < (z + x) ≤ 4), equation R'ｎ SnX ４－ｎ A first organometallic composition represented by (where n = 1 or 2), or a mixture thereof, where R and R' are independently hydrocarbyl groups having 1 to 31 carbon atoms, and X is a ligand or a combination thereof having a hydrolyzable bond to Sn; and a hydrolyzable metal compound of the formula MX' ｖ A coating solution comprising a hydrolyzable metal compound represented by (where 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 or combination thereof having a hydrolyzable M-X bond).

[0138] Organic solvent and formula RSnO （３／２－ｘ／２） (OH) ｘ A coating solution comprising a first organometallic compound represented by the formula (wherein 0 < x < 3), wherein the solution contains about 0.0025 M to about 1.5 M of tin, and R is an alkyl group or cycloalkyl group having 3 to 31 carbon atoms, wherein the alkyl group or cycloalkyl group is bonded to tin at a secondary or tertiary carbon atom.

[0139] An aqueous solution of an inorganic pattern-forming precursor comprising a mixture of water, a metal suboxide cation, a polyatomic inorganic anion, and a radiation-sensitive ligand containing a peroxide group.

[0140] Other examples of metal-containing resists include the compositions described in Japanese Patent Publication No. 2011-253185, WO2015 / 026482, WO2016 / 065120, WO2017 / 066319, WO2017 / 156388, WO2018 / 031896, Japanese Patent Publication No. 2020-122959, Japanese Patent Publication No. 2020-122960, WO2019 / 099981, WO2019 / 199467, WO2019 / 195522, WO2019 / 195522, WO2020 / 210660, WO2021 / 011367, and WO2021 / 016229. These contents are incorporated into this specification to the same extent as if they were all explicitly stated.

[0141] The method for forming a metal-containing resist film from a metal-containing resist is not particularly limited, and includes a method of applying a coating-type resist material (a composition for forming a metal-containing resist film), which is a metal-containing resist, and firing it.

[0142] Furthermore, the metal-containing resist film may be formed by vapor deposition. An example of a method for forming a metal-containing resist film by vapor deposition is the method described in Japanese Patent Application Publication No. 2017-116923. The contents of Japanese Patent Application Publication No. 2017-116923 are incorporated herein to the same extent as if they were fully disclosed. In Japanese Patent Application Publication No. 2017-116923, the metal-containing resist film in the present invention is referred to as a metal oxide-containing film.

[0143] Irradiation with light or an electron beam is performed, for example, through a mask (reticle) for forming a predetermined pattern. For example, i-rays, KrF excimer lasers, ArF excimer lasers, EUV (extreme ultraviolet) or EB (electron beams) are used. The resist underlayer film forming composition of the present invention is preferably applied for EB (electron beam) or EUV (extreme ultraviolet: 13.5 nm) irradiation, and more preferably for EUV (extreme ultraviolet) exposure. The electron beam irradiation energy and the amount of light exposure are not particularly limited.

[0144] A bake (PEB: Post Exposure Bake) may be performed after irradiation with light or electron beam and before development. The bake 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. The bake 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.

[0145] For development, for example, alkaline developers and organic solvents are used. The development temperature can be, for example, 5°C to 50°C. The development time can be, for example, 10 seconds to 300 seconds. As alkaline developers, aqueous solutions of the following alkalis can be used: inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia; primary amines such as ethylamine and n-propylamine; secondary amines such as diethylamine and di-n-butylamine; tertiary amines such as triethylamine and methyldiethylamine; alcohol amines such as dimethylethanolamine and triethanolamine; quaternary ammonium salts such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline; and cyclic amines such as pyrrole and piperidine. Furthermore, appropriate amounts of alcohols such as isopropyl alcohol and nonionic surfactants can be added to the aqueous solutions of the above alkalis. Among these, preferred developers are aqueous solutions of quaternary ammonium salts, and more preferably aqueous solutions of tetramethylammonium hydroxide and choline. Furthermore, surfactants can also be added to these developers. Alternatively, instead of using an alkaline developer, development can be performed with an organic solvent such as butyl acetate, and the areas of the photoresist where the alkaline dissolution rate has not improved can be developed.

[0146] Organic solvents can be used as the developer for metal-containing resists, and development is performed with the developer (solvent) after irradiation with light or electron beam. As a result, for example, when a negative-type metal-containing resist film is used, the unexposed areas of the metal-containing resist film are removed, and a pattern of the metal-containing resist film is formed. Examples of developers (organic solvents) include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, ethyl methoxyethyl acetate, ethoxyethyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monophenyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-ethyl-3 - Methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl acetate, 4-propoxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate, 3-methyl-3 - Methoxypentyl acetate, 3-methyl-4-methoxypentyl acetate, 4-methyl-4-methoxypentyl acetate, propylene glycol diacetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, ethyl carbonate, propyl carbonate, butyl carbonate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, butyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl propionate, ethyl propionate,Examples include propyl propionate, isopropyl propionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl-3-methoxypropionate, ethyl-3-methoxypropionate, ethyl-3-ethoxypropionate, and propyl-3-methoxypropionate. Furthermore, surfactants can be added to these developers.

[0147] 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. If the inorganic film is formed on the surface of the semiconductor substrate used, the surface of the inorganic film is exposed; if the inorganic film is not formed on the surface of the semiconductor substrate used, the surface of the semiconductor substrate is exposed. After that, the semiconductor substrate is processed by a known method (such as dry etching) to manufacture a semiconductor device.

[0148] The present invention will now be described in detail with reference to examples, but the present invention is not limited to these examples.

[0149] The weight-average molecular weights of the polymers shown in Synthesis Examples 1-5 and Comparative Synthesis Examples 1-2 in this specification were obtained by gel permeation chromatography (hereinafter abbreviated as GPC). A GPC instrument manufactured by Tosoh Corporation was used for the measurement, and the measurement conditions were as follows: GPC column: TSKgel Super-MultiporeHZ-N (2 columns) Column temperature: 40°C Solvent: Tetrahydrofuran (THF) Flow rate: 0.35 ml / min Standard sample: Polystyrene (manufactured by Tosoh Corporation)

[0150] <Synthesis Example 1> Diacetoxypropyl diglycidyl isocyanuric acid was prepared by synthesizing it from tris(2,3-epoxypropyl) isocyanurate in accordance with the method for producing isocyanuric acid derivatives described in Japanese Patent Publication No. 2-279684. 5.00 g of diacetoxypropyl diglycidyl isocyanuric acid (40% propylene glycol monomethyl ether (PGME) solution), 2.77 g of dithiodiglycolic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.32 g of tetrabutylphosphonium bromide (manufactured by Hokko Chemical Industry Co., Ltd.) were added to 9.88 g of propylene glycol monomethyl ether in a reaction vessel and dissolved. After purging the reaction vessel with nitrogen, the reaction was carried out at 105°C for 24 hours to obtain a solution containing polymer 1. GPC analysis revealed that the obtained polymer 1 had a weight-average molecular weight of 2,400 on a standard polystyrene basis and a dispersion degree of 1.9. The structure present in polymer 1 is shown by the following formula.

[0151]

[0152] <Synthesis Example 2> 10.00 g of diacetoxypropyl diglycidyl isocyanuric acid (40% PGME solution), 2.62 g of product name Me-CIC (manufactured by Shikoku Chemicals, Inc.), and 0.22 g of tetrabutylphosphonium bromide (manufactured by Hokko Chemical Industry Co., Ltd.) were added to 21.35 g of propylene glycol monomethyl ether in a reaction vessel and dissolved. After purging the reaction vessel with nitrogen, the mixture was reacted at 140°C for 24 hours to obtain a solution containing polymer 2. GPC analysis revealed that the obtained polymer 2 had a weight-average molecular weight of 2,200 on a standard polystyrene basis and a dispersion degree of 1.7. The structure present in polymer 2 is shown by the following formula.

[0153]

[0154] <Synthesis Example 3> 7.00 g of diacetoxypropyl diglycidyl isocyanuric acid (40% PGME solution), 0.92 g of dithiodiglycolic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.69 g of diiodosalicylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.15 g of tetrabutylphosphonium bromide (manufactured by Hokko Chemical Industry Co., Ltd.) were added to 1.42 g of propylene glycol monomethyl ether in a reaction vessel and dissolved. After purging the reaction vessel with nitrogen, the mixture was reacted at 105°C for 24 hours to obtain a solution containing polymer 3. GPC analysis revealed that the obtained polymer 3 had a weight-average molecular weight of 1,600 on a standard polystyrene basis and a dispersion degree of 1.6. The structure present in polymer 3 is shown by the following formula.

[0155]

[0156] <Synthesis Example 4> 7.00 g of diacetoxypropyl diglycidyl isocyanuric acid (40% PGME solution), 1.30 g of product name Me-CIC (manufactured by Shikoku Chemicals, Inc.), 0.69 g of diiodosalicylic acid (manufactured by Tokyo Chemical Industries, Inc.), and 0.15 g of tetrabutylphosphonium bromide (manufactured by Hokko Chemical Industry Co., Ltd.) were added to 3.27 g of propylene glycol monomethyl ether in a reaction vessel and dissolved. After purging the reaction vessel with nitrogen, the mixture was reacted at 140°C for 24 hours to obtain a solution containing polymer 4. GPC analysis revealed that the obtained polymer 4 had a weight-average molecular weight of 2,200 on a standard polystyrene basis and a dispersion degree of 1.6. The structure present in polymer 4 is shown by the following formula.

[0157]

[0158] <Synthesis Example 5> 8.00 g of diacetoxypropyl diglycidyl isocyanuic acid (40% PGME solution), 0.96 g of isophthalic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.79 g of diiodosalicylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.17 g of tetrabutylphosphonium bromide (manufactured by Hokko Chemical Industry Co., Ltd.) were added to 2.85 g of propylene glycol monomethyl ether in a reaction vessel and dissolved. After purging the reaction vessel with nitrogen, the mixture was reacted at 140°C for 24 hours to obtain a solution containing polymer 5. GPC analysis revealed that the obtained polymer 5 had a weight-average molecular weight of 3,000 on a standard polystyrene basis and a dispersion degree of 2.0. The structure present in polymer 5 is shown by the following formula.

[0159]

[0160] <Comparative Synthesis Example 1> 100.00 g of monoallyl diglycidyl isocyanuric acid (manufactured by Shikoku Chemicals, Inc.), 66.4 g of 5,5-diethylbarbituric acid, and 4.1 g of benzyltriethylammonium chloride were added to 682.00 g of propylene glycol monomethyl ether in a reaction vessel and dissolved. After purging the reaction vessel with nitrogen, the mixture was reacted at 130°C for 24 hours to obtain a solution containing comparative polymer 1. GPC analysis revealed that the obtained comparative polymer 1 had a weight-average molecular weight of 6,800 on a standard polystyrene basis and a dispersion degree of 4.8. The structure present in comparative polymer 1 is shown by the following formula.

[0161]

[0162] <Comparative Synthesis Example 2> 12.00 g of monomethyldiglycidyl isocyanuric acid (manufactured by Shikoku Chemicals, Inc., 30% PGME solution), 4.45 g of product name Me-CIC (manufactured by Shikoku Chemicals, Inc.), and 0.36 g of tetrabutylphosphonium bromide (manufactured by Hokko Chemical Industry Co., Ltd.) were added to 25.18 g of propylene glycol monomethyl ether in a reaction vessel and dissolved. After purging the reaction vessel with nitrogen, the mixture was reacted at 140°C for 24 hours to obtain a solution containing comparative polymer 2. After cooling, turbidity and precipitation were observed in the polymer solution. Due to the turbidity in the solution, it was not used for further evaluation.

[0163] (Preparation of compositions for forming a resist underlayer film) (Examples and comparative examples) The polymers, crosslinking agents, curing catalysts, and solvents obtained in Synthesis Examples 1 to 5 and Comparative Synthesis Example 1 were mixed in the proportions shown in Tables 1 and 2, and the mixtures were filtered through a fluororesin filter with a pore size of 0.1 μm to prepare solutions of compositions for forming a resist underlayer film.

[0164] The abbreviations in Tables 1 and 2 are as follows: PL-LI: Tetramethoxymethylglycoluryl PGME-PL: Imidazo[4,5-d]imidazole-2,5(1H,3H)-dione,tetrahydro-1,3,4,6-tetrakis[(2-methyl-1-methylethylethoxy)methyl]-(see structural formula below)

[0165] PyPSA: Pyridinium-p-hydroxybenzenesulfonic acid PGMEA: Propylene glycol monomethyl ether acetate PGME: Propylene glycol monomethyl ether The amount of each additive is shown in parts by mass, and the solvent is shown in composition ratio.

[0166]

[0167]

[0168] (Elution Test in Photoresist Solvent) The resist underlayer formation compositions of Examples 1-5 and Comparative Example 1 were each coated onto a silicon wafer using a spinner. The silicon wafer was baked on a hot plate at 205°C for 60 seconds to obtain a resist underlayer with a thickness of 5 nm. These resist underlayers were immersed in a mixed solution of propylene glycol monomethyl ether / propylene glycol monomethyl ether = 70 / 30 (volume ratio), which is the solvent used for photoresists. A change in film thickness of less than 5 Å was judged as "good," and a change of 5 Å or more was judged as "poor." The results are shown in Table 3.

[0169]

[0170] (Measurement of etching rate) High-concentration versions of the resist underlayer formation compositions from Examples 1 to 5 and Comparative Example 1 were used to form a resist underlayer with a thickness of 100 nm on a silicon wafer using the same method as described above. The dry etching rate of these resist underlayers was measured using RIE-10NR (manufactured by Samco Co., Ltd.) and CF as the etching gas. ４ The measurements were taken under the conditions used. The dry etching rate of each resist underlayer was calculated when the dry etching rate of Comparative Example 1 was set to 1.00. The results are shown in Table 4 as "relative dry etching rate". In Examples 1 to 5, an improvement in etching rate was confirmed compared to Comparative Example 1, and an improvement in the etching rate of the resist underlayer in the examples was confirmed.

[0171]

[0172] (Resist Patterning Evaluation) [Resist Pattern Formation Test using Electron Beam Lithography System] The resist underlayer formation compositions of the Examples and Comparative Examples were applied to silicon wafers using a spinner. The silicon wafers were baked on a hot plate at 205°C for 60 seconds to obtain a resist underlayer with a thickness of 5 nm. An EUV positive-type resist solution was spin-coated onto the resist underlayer and heated at 110°C for 60 seconds to form an EUV resist film. The resist film was exposed to electron beam lithography (ELS-G130) under predetermined conditions. After exposure, baking (PEB) was performed at 90°C for 60 seconds, cooled to room temperature on a cooling plate, and paddle development was performed for 30 seconds using a 2.38% tetramethylammonium hydroxide aqueous solution (manufactured by Tokyo Ohka Kogyo Co., Ltd., trade name NMD-3) as a photoresist developer. A resist pattern with a line size of 16 nm to 28 nm was formed. A scanning electron microscope (Hitachi High-Technologies Corporation, CG4100) was used to measure the length of the resist pattern. The formation of 24 nm line-and-space (L / S) patterns was evaluated for the photoresist patterns obtained in this manner. Formation of 24 nm L / S patterns was confirmed in all cases of Examples 1 to 5. Furthermore, the charge amount required to form a 24 nm line / 56 nm pitch (line-and-space (L / S = 1 / 1.3)) was defined as the optimal irradiation energy, and the irradiation energy at that time (μC / cm²) was determined. ２ Table 5 shows the minimum CD size in which no collapse is observed within the resist pattern shot. Examples 1 to 5 showed an improvement in the minimum CD size compared to Comparative Example 1.

[0173]

[0174] The present invention provides a resist underlayer film forming composition for forming a resist underlayer film that improves etching speed while maintaining good sensitivity and can form a fine and good resist pattern, as well as a method for manufacturing a resist-patterned substrate using the resist underlayer film forming composition, and a method for manufacturing a semiconductor device.

Claims

1. A composition for forming a resist underlayer film, comprising a polymer (A) having a structure represented by the following formula (1), and a solvent. (In formula (1), R １０１ and R １０２ Each of these independently represents an alkyl group, alkenyl group, alkynyl group, aryl group, aralkyl group, heterocyclic group, or a halogenated, aminated, or nitrated derivative group thereof. * represents a bond.

2. The resist underlayer film forming composition according to claim 1, wherein the polymer (A) is a polymer having a structure represented by the following formula (2). (In formula (2), A independently represents a hydrogen atom, a methyl group, or an ethyl group. １０１ and R １０２ R in equation (1) １０１ and R １０２ It is the same as this. (* represents a bonding operation.) 3. The composition for forming a resist underlayer film according to claim 2, wherein the polymer (A) is a polymer having a structural unit represented by the following formula (3). (In formula (3), A is the same as A in formula (2). R １０１ and R １０２ are the same as R １０１ and R １０２ in formula (1). Q represents a divalent group.) 4. The resist underlayer film forming composition according to claim 3, wherein Q in formula (3) is represented by the following formula (3-1) or formula (3-2). (In formula (3-1), Q １ represents a divalent organic group. n1 and n2 each independently represent 0 or 1. In formula (3-2), X １ Z represents a group expressed by any of the following formulas (3-2-1) to (3-2-3). １ and Z ２ Each of these independently represents a single bond or a group represented by the following formula (3-2-4). * represents a bond. (In formulas (3-2-1) to (3-2-3), R １ and R ２ Each of these independently represents a hydrogen atom, 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, a benzyl group, or a phenyl group, and each of the alkyl groups having 1 to 6 carbon atoms, the benzyl group, and the phenyl group may independently be substituted with a group or atom selected from the group consisting of alkyl groups having 1 to 6 carbon atoms, halogen atoms, alkoxy groups having 1 to 6 carbon atoms, alkoxyalkyl groups having 2 to 6 carbon atoms, nitro groups, cyano groups, hydroxyl groups, and alkylthio groups having 1 to 6 carbon atoms, and R １ and R ２ These may be bonded to each other to form a ring with 3 to 6 carbon atoms. ３ represents 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, a benzyl group, or a phenyl group. The alkyl group having 1 to 6 carbon atoms, the benzyl group, and the phenyl group may each be independently substituted with a group or atom selected from the group consisting of alkyl groups having 1 to 6 carbon atoms, halogen atoms, alkoxy groups having 1 to 6 carbon atoms, alkoxyalkyl groups having 2 to 6 carbon atoms, nitro groups, cyano groups, hydroxyl groups, and alkylthio groups having 1 to 6 carbon atoms. * represents a bond. *1 represents a bond that bonds to a carbon atom in formula (3-2). *2 represents a bond that bonds to a nitrogen atom in formula (3-2). (In formula (3-2-4), m represents an integer from 1 to 4. n represents an integer from 0 to 4. p1 and p2 each independently represent 0 or 1. *3 represents the bond that connects to the nitrogen atom in formula (3-2). *4 represents a bond.) 5. Q in equation (3-1) above １ The resist underlayer film forming composition according to claim 4, wherein the divalent organic group is a divalent group containing a sulfur atom, an alkylene group, an alkenylene group, an alkylylene group, and a divalent group containing an aromatic ring, and the aromatic ring may be substituted with a group or atom 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, a hydroxyl group, a fluoroalkyl group, and an alkylthio group having 1 to 6 carbon atoms.

6. Q in equation (3-1) above １ The resist underlayer film forming composition according to claim 5, wherein the divalent group containing a sulfur atom is represented by the following formula (3-1-1). (In formula (3-1-1), R ３１ , R ３２ , and R ３３ Each of these independently represents a single bond or an alkylene group with 1 to 3 carbon atoms. r represents 0 or 1. * represents a bond.

7. The resist underlayer film forming composition according to claim 3, wherein the polymer has a structure represented by the following formula (E) at its terminal end. (In formula (E), E represents a group having 1 to 20 carbon atoms. n represents 0 or 1. * represents a bond.) 8. The resist underlayer film forming composition according to claim 7, wherein E in formula (E) represents a monovalent group having a ring structure.

9. The resist underlayer film forming composition according to claim 1, wherein the solvent comprises at least one selected from the group consisting of alkylene glycol monoalkyl ethers and monocarboxylic acid esters of alkylene glycol monoalkyl ethers.

10. The resist underlayer film forming composition according to claim 1, further comprising a crosslinking agent.

11. The resist underlayer film forming composition according to claim 10, wherein the crosslinking agent is at least one selected from the group consisting of aminoplast crosslinking agents and phenoplast crosslinking agents.

12. The resist underlayer film forming composition according to claim 1, further comprising a curing catalyst.

13. A composition for forming a resist underlayer film according to claim 1, used in EUV lithography.

14. A resist underlayer film, which is a cured product of a resist underlayer film forming composition according to any one of claims 1 to 13.

15. A laminate comprising a semiconductor substrate and a resist underlayer film according to claim 14.

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

17. A pattern formation method comprising: forming a resist underlayer film on a semiconductor substrate using a resist underlayer film forming composition according to any one of claims 1 to 13; forming a resist film on the resist underlayer film; irradiating the resist film with light or an electron beam, then developing the resist film to obtain a resist pattern; and etching the resist underlayer film using the resist pattern as a mask.

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