Resistor underlayer film formation composition, resistor underlayer film, semiconductor device manufacturing method, and polymer

Abstract

A novel inhibitor underlayer film forming composition is provided, which can reduce the amount of sublimation in the contaminating device, improve the in-plane uniformity of the coated film, and exhibit other good properties such as sufficient resistance even to the solution used in the inhibitor underlayer film. An inhibitor underlayer film forming composition comprising a solvent and a polymer comprising a unit structure (A) as shown in formula (1). (In formula (1), Ar1 and Ar2 each represent a benzene ring or a naphthalene ring, R1 and R2 are groups that replace the hydrogen atoms on the rings of Ar1 and Ar2, R4 is selected from the group consisting of hydrogen atoms, trifluoromethyl groups, aryl groups with 6 to 40 carbon atoms, and heterocyclic groups, R5 is selected from the group consisting of hydrogen atoms, trifluoromethyl groups, aryl groups with 6 to 40 carbon atoms, and heterocyclic groups, and n1 and n2 are integers from 0 to 3.)

Description

Technical Field

[0001] This invention relates to a resist underlayer film forming composition, a sintered product of a coating film composed of the composition (i.e., a resist underlayer film), and a method for manufacturing a semiconductor device using the composition. Prior Technology

[0002] In recent years, there has been a demand for resist underlayer film formation compositions used in lithography processes for manufacturing semiconductor devices that do not cause intermingling with the upper layer, can obtain excellent resist patterns, and can form lithography resist underlayer films with lower dry etching speeds compared to the upper layer (hard mask: coating film or vapor-deposited film) or semiconductor substrate. A polymer containing repeating units of benzene rings or naphthalene rings has been proposed (Patent Document 1). [Previous Technical Documents] [Patent Literature]

[0003] [Patent Document 1] WO 2013 / 047516 A1 Summary of the Invention

[0004] [The problem that the invention aims to solve]

[0005] However, conventional resist underlayer film composition still falls short of requirements for reducing sublimation levels in contaminating devices and improving the in-plane uniformity of the coated film. Furthermore, semiconductor manufacturing processes sometimes involve the use of chemical solutions, which necessitates that the solutions used in the resist underlayer film exhibit sufficient resistance. [Methods used to solve problems]

[0006] This invention addresses the aforementioned problems. Specifically, this invention includes the following: [1] An inhibitor underlayer film forming composition comprising a solvent and a polymer comprising a unit structure (A) as shown in formula (1). (in formula (1),) Ar1 and Ar2 series each represent a benzene ring or a naphthalene ring. Ar1 and Ar2 series can be bonded together by single bonds. R1 and R2 are groups in which hydrogen atoms on the rings of Ar1 and Ar2 are substituted, and are selected from halogen groups, nitro groups, amino groups, cyano groups, alkyl groups with 1 to 10 carbon atoms, alkenyl groups with 2 to 10 carbon atoms, alkynyl groups with 2 to 10 carbon atoms, aryl groups with 6 to 40 carbon atoms, and combinations thereof. Furthermore, the alkyl, alkenyl, alkynyl, and aryl groups may also contain ether bonds, ketone bonds, or ester bonds. R4 is selected from the group consisting of hydrogen atoms, trifluoromethyl groups, aryl groups having 6 to 40 carbon atoms, and heterocyclic groups. The aryl and heterocyclic groups may be substituted with halogen groups, nitro groups, amino groups, cyano groups, trifluoromethyl groups, alkyl groups having 1 to 10 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, alkenyl groups having 2 to 10 carbon atoms, alkynyl groups having 2 to 10 carbon atoms, or aryl groups having 6 to 40 carbon atoms. The alkyl, alkenyl, alkynyl, and aryl groups may also contain ether bonds, ketone bonds, or ester bonds. R5 The group is selected from hydrogen atoms, trifluoromethyl groups, aryl groups having 6 to 40 carbon atoms, and heterocyclic groups. The aryl and heterocyclic groups may be substituted with halogen groups, nitro groups, amino groups, cyano groups, trifluoromethyl groups, alkyl groups having 1 to 10 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, alkenyl groups having 2 to 10 carbon atoms, alkynyl groups having 2 to 10 carbon atoms, or aryl groups having 6 to 40 carbon atoms. Furthermore, the alkyl, alkenyl, alkynyl, and aryl groups may also contain ether bonds, ketone bonds, or ester bonds. Furthermore, the R4 and R5 systems can also form rings together with the carbon atoms they are bonded to. n1 and n2 are each integers from 0 to 3. [2] As in [1], the lower layer film of the inhibitor forms a composition, wherein Ar1 and Ar2 in the above formula (1) are benzene rings. [3] The inhibitor lower film forming composition as in [1] or [2], wherein R5 in formula (1) above is a hydrogen atom, R4 is an aryl group with 6 to 40 carbon atoms, and the aryl group may be replaced by a halogen group, nitro group, amino group, cyano group, trifluoromethyl group, alkyl group with 1 to 10 carbon atoms, alkoxy group with 1 to 10 carbon atoms, alkenyl group with 2 to 10 carbon atoms, alkynyl group with 2 to 10 carbon atoms, or aryl group with 6 to 40 carbon atoms. [4] The inhibitor lower film forming composition of any one of [1] to [3], wherein R5 in the above formula (1) is a hydrogen atom, R4 is an aryl group with 6 to 40 carbon atoms, and the aryl group can be replaced by an aryl group with 6 to 40 carbon atoms. [5] The inhibitor lower film forming composition of any of [1] to [4], wherein R5 in the above formula (1) is a hydrogen atom and R4 is a substituted group composed of a combination of benzene rings. [6] The resistive lower film forming composition of any of [1] to [5] further includes a crosslinking agent. [7] The inhibitor underlayer film forming composition of any of [1] to [6] further includes an acid and / or an acid generating agent. [8] The inhibitor lower film forming composition as in [1], wherein the boiling point of the aforementioned solvent is above 160°C. [9] A resistive underlayer film, which is a sintered product of a coated film composed of a resistive underlayer film forming composition as described in any of [1] to [8].

[10] A method for manufacturing a semiconductor device, comprising: The step of forming a resist underlayer film using any of the resist underlayer film forming compositions in [1] to [8] on a semiconductor substrate; The step of forming a resist film on top of the already formed resist underlayer film; The process of forming a resist pattern by irradiating the formed resist film with light or electron beams and then developing it; The step of patterning is performed by etching the aforementioned resist underlayer film using the already formed resist pattern; and, The process of fabricating a semiconductor substrate using a patterned resist underlayer film.

[11] A method for manufacturing a semiconductor device, comprising: The step of forming a resist underlayer film using any of the resist underlayer film forming compositions in [1] to [8] on a semiconductor substrate; The step of forming a hard mask on top of the already formed resist underlayer film; The step of forming a resist film on top of the already formed hard mask; The process of forming a resist pattern by irradiating the formed resist film with light or electron beams and then developing it; The step of etching a hard mask using a pre-formed resist pattern; The step of etching the aforementioned resist underlayer film via an etched hard mask; and, Steps to remove hard mask.

[12] The method for manufacturing a semiconductor device as described in

[11] further includes: The step of forming a vapor-deposited film (spacer) on the underlying film after the hard mask has been removed; The process of etching to process a pre-formed vapor-deposited film (spacer); The steps for removing the underlying membrane; and The process of processing semiconductor substrates using spacers.

[13] The method of manufacturing a semiconductor device as described in any of

[10] to

[12] , wherein the semiconductor substrate is a stepped substrate.

[14] A polymer comprising the unit structure (A) shown in the following formula (1). (in formula (1),) Ar1 and Ar2 each represent a benzene ring or a naphthalene ring. Ar1 and Ar2 can also be bonded together by single bonds. R1 and R2 are groups in which hydrogen atoms on the rings of Ar1 and Ar2 are substituted, and are selected from halogen groups, nitro groups, amino groups, cyano groups, alkyl groups with 1 to 10 carbon atoms, alkenyl groups with 2 to 10 carbon atoms, alkynyl groups with 2 to 10 carbon atoms, aryl groups with 6 to 40 carbon atoms, and combinations thereof. Furthermore, the alkyl, alkenyl, alkynyl, and aryl groups may also contain ether bonds, ketone bonds, or ester bonds. R4 is a group consisting of a biphenyl group composed of a combination of substituted benzene rings, wherein the benzene ring may be substituted with a halogen group, nitro group, amino group, cyano group, trifluoromethyl group, alkyl group with 1 to 10 carbon atoms, alkoxy group with 1 to 10 carbon atoms, alkenyl group with 2 to 10 carbon atoms, alkynyl group with 2 to 10 carbon atoms, or aryl group with 6 to 40 carbon atoms, and the alkyl, alkenyl, alkynyl, and aryl groups may also contain ether bonds, ketone bonds, or ester bonds. R5 is a hydrogen atom. n1 and n2 are each integers from 0 to 3.

[15] Polymers such as

[14] , wherein Ar1 and Ar2 in the above formula (1) are benzene rings.

[16] Polymers such as

[14] , wherein R4 in the above formula (1) is a substituted biphenyl. [Invention Effects]

[0007] According to the present invention, a novel inhibitor underlayer film forming composition is provided, which can reduce the amount of sublimation of contaminating devices, improve the in-plane uniformity of coating film, and exhibit other good properties such as sufficient resistance even to solutions used in inhibitor underlayer films. Implementation

[0008] <Inhibitor Underlayer Film Formation Composition>

[0009] The inhibitor lower film forming composition of the present invention comprises a solvent and a polymer, wherein the polymer comprises a unit structure (A) as shown in the following formula (1). (in formula (1),) Ar1 and Ar2 series each represent a benzene ring or a naphthalene ring. Ar1 and Ar2 series can be bonded together by single bonds. R1 and R2 are groups in which hydrogen atoms on the rings of Ar1 and Ar2 are substituted, and are selected from halogen groups, nitro groups, amino groups, cyano groups, alkyl groups with 1 to 10 carbon atoms, alkenyl groups with 2 to 10 carbon atoms, alkynyl groups with 2 to 10 carbon atoms, aryl groups with 6 to 40 carbon atoms, and combinations thereof. Furthermore, the alkyl, alkenyl, alkynyl, and aryl groups may also contain ether bonds, ketone bonds, or ester bonds. R4 is selected from the group consisting of hydrogen atoms, trifluoromethyl groups, aryl groups having 6 to 40 carbon atoms, and heterocyclic groups. The aryl and heterocyclic groups may be substituted with halogen groups, nitro groups, amino groups, cyano groups, trifluoromethyl groups, alkyl groups having 1 to 10 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, alkenyl groups having 2 to 10 carbon atoms, alkynyl groups having 2 to 10 carbon atoms, or aryl groups having 6 to 40 carbon atoms. The alkyl, alkenyl, alkynyl, and aryl groups may also contain ether bonds, ketone bonds, or ester bonds. R5 The group is selected from hydrogen atoms, trifluoromethyl groups, aryl groups having 6 to 40 carbon atoms, and heterocyclic groups. The aryl and heterocyclic groups may be substituted with halogen groups, nitro groups, amino groups, cyano groups, trifluoromethyl groups, alkyl groups having 1 to 10 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, alkenyl groups having 2 to 10 carbon atoms, alkynyl groups having 2 to 10 carbon atoms, or aryl groups having 6 to 40 carbon atoms. Furthermore, the alkyl, alkenyl, alkynyl, and aryl groups may also contain ether bonds, ketone bonds, or ester bonds. Furthermore, the R4 and R5 systems can also form rings together with the carbon atoms they are bonded to. n1 and n2 are each integers from 0 to 3.

[0010] <Polymer containing the unit structure (A) shown in formula (1)> Ar1 and Ar2 each represent a benzene ring or a naphthalene ring. Ar1 and Ar2 can be bonded together via single bonds, for example, to form a carbazole skeleton. Ar1 and Ar2 are preferably both benzene rings.

[0011] R1 and R2 are groups that replace the hydrogen atoms on the rings of Ar1 and Ar2, respectively, selected from halogen groups, nitro groups, amino groups, cyano groups, alkyl groups with 1 to 10 carbon atoms, alkenyl groups with 2 to 10 carbon atoms, alkynyl groups with 2 to 10 carbon atoms, aryl groups with 6 to 40 carbon atoms, and combinations thereof. The alkyl, alkenyl, alkynyl, and aryl groups may also contain ether bonds, ketone bonds, or ester bonds.

[0012] Examples of halogen groups include fluorine, chlorine, bromine, and iodine.

[0013] Examples of alkyl groups having 1 to 10 carbon atoms include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, 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, 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, etc.

[0014] Alternatively, it can be a cyclic alkyl group, such as cyclopropyl, cyclobutyl, 1-methyl-cyclopropyl, 2-methyl-cyclopropyl, cyclopentyl, 1-methyl-cyclobutyl, 2-methyl-cyclobutyl, 3-methyl-cyclobutyl, 1,2-dimethyl-cyclopropyl, 2,3-dimethyl-cyclopropyl, 1-ethyl-cyclopropyl, 2-ethyl-cyclopropyl, cyclohexyl, 1-methyl-cyclopentyl, 2-methyl-cyclopentyl, 3-methyl-cyclopentyl, 1-ethyl-cyclobutyl, 2-ethyl-cyclobutyl, 3-ethyl-cyclobutyl, 1,2-dimethyl-cyclobutyl, 1,3-dimethyl-cyclopropyl Butyl, 2,2-dimethyl-cyclobutyl, 2,3-dimethyl-cyclobutyl, 2,4-dimethyl-cyclobutyl, 3,3-dimethyl-cyclobutyl, 1-n-propyl-cyclopropyl, 2-n-propyl-cyclopropyl, 1-i-propyl-cyclopropyl, 2-i-propyl-cyclopropyl, 1,2,2-trimethyl-cyclopropyl, 1,2,3-trimethyl-cyclopropyl, 2,2,3-trimethyl-cyclopropyl, 1-ethyl-2-methyl-cyclopropyl, 2-ethyl-1-methyl-cyclopropyl, 2-ethyl-2-methyl-cyclopropyl, and 2-ethyl-3-methyl-cyclopropyl, etc.

[0015] Examples of alkenyl groups having 2 to 10 carbon atoms include vinyl, 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 alkenyl, 3-methyl-1-butenyl, 3-methyl-2-butenyl, 3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl, 1-i-propylvinyl, 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-s-butylvinyl, 1,3-di Methyl-1-butenyl, 1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl, 1-i-butylvinyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 2-i-propyl-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-t-Butylvinyl, 1-Methyl-1-ethyl-2-propenyl, 1-Ethyl-2-methyl-1-propenyl, 1-Ethyl-2-methyl-2-propenyl, 1-I-propyl-1-propenyl, 1-I-propyl-2-propenyl, 1-Methyl-2-cyclopentenyl, 1-Methyl-3-cyclopentenyl, 2-Methyl-1-cyclopentenyl, 2-Methyl-2-cyclopentenyl Alkenyl, 2-methyl-3-cyclopentenyl, 2-methyl-4-cyclopentenyl, 2-methyl-5-cyclopentenyl, 2-methylene-cyclopentyl, 3-methyl-1-cyclopentenyl, 3-methyl-2-cyclopentenyl, 3-methyl-3-cyclopentenyl, 3-methyl-4-cyclopentenyl, 3-methyl-5-cyclopentenyl, 3-methylene-cyclopentenyl, 1-cyclohexenyl, 2-cyclohexenyl, and 3-cyclohexenyl, etc.

[0016] Examples of alkynyl groups with 2 to 10 carbon atoms include ethynyl, 1-propynyl, and 2-propynyl.

[0017] Examples of aryl groups with 6 to 40 carbon atoms include phenyl, benzyl, naphthyl, anthracene, phenanthrene, naphthacenyl, triphenylenyl, pyrene, and chrysenyl.

[0018] The aforementioned alkyl, alkenyl, alkynyl, and aryl groups may also include ether bonds (-O-), ketone bonds (-CO-), or ester bonds (-COO-, -OCO-).

[0019] R4 is selected from the group consisting of hydrogen atoms, trifluoromethyl, aryl groups having 6 to 40 carbon atoms, and heterocyclic groups, wherein the aryl and heterocyclic groups may be substituted by halogen groups, nitro groups, amino groups, cyano groups, trifluoromethyl groups, alkyl groups having 1 to 10 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, alkenyl groups having 2 to 10 carbon atoms, alkynyl groups having 2 to 10 carbon atoms, or aryl groups having 6 to 40 carbon atoms, and the alkyl, alkenyl, alkynyl, and aryl groups may also contain ether bonds, ketone bonds, or ester bonds. Furthermore, R5 is selected from the group consisting of hydrogen atoms, trifluoromethyl, aryl groups having 6 to 40 carbon atoms, and heterocyclic groups. The aryl and heterocyclic groups may be substituted by halogen groups, nitro groups, amino groups, cyano groups, trifluoromethyl groups, alkyl groups having 1 to 10 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, alkenyl groups having 2 to 10 carbon atoms, alkynyl groups having 2 to 10 carbon atoms, or aryl groups having 6 to 40 carbon atoms. The alkyl, alkenyl, alkynyl, and aryl groups may also contain ether bonds, ketone bonds, or ester bonds.

[0020] Heterocyclic groups refer to substituents derived from heterocyclic compounds. Specific examples include thiophene, furanyl, pyridinyl, pyrimidinyl, pyrazinyl, pyrroloyl, oxazolyl, thiazolyl, imidazolyl, quinolinyl, carbazoleyl, quinazolinyl, purine, indoleazinyl, benzothiophene, benzofuranyl, indole, acridineyl, isoindole, benzimidazolyl, isoquinolinyl, quinoxalinyl, terpineyl, pteridineyl, cristatyl (benzopiperanyl), and isocrifuranyl (benzopiperanyl). Xantonyl, thiazolyl, pyrazolyl, imidazolinyl, azineyl, among which thienyl, furanyl, pyridinyl, pyrimidinyl, pyrazinyl, pyrroleyl, oxazolyl, thiazolyl, imidazolyl, quinolinyl, carbazoleyl, quinazolinyl, purineyl, indoleazineyl, benzothienyl, benzofuranyl, indoleyl, and azineyl are preferred, with thienyl, furanyl, pyridinyl, pyrimidinyl, pyrroleyl, oxazolyl, thiazolyl, imidazolyl, and carbazoleyl being the most preferred.

[0021] As alkoxy groups having 1 to 10 carbon atoms, examples include alkyl groups having an ether-containing oxygen atom (-O-) bonded to the terminal carbon atom of the aforementioned alkyl groups having 1 to 10 carbon atoms. Examples of such alkoxy groups include methoxy, ethoxy, n-propoxy, i-propoxy, cyclopropoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy, cyclobutoxy, 1-methyl-cyclopropoxy, 2-methyl-cyclopropoxy, 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, 1,1-diethyl-n-propoxy, cyclopentoxy, 1-methyl-cyclobutoxy, 2-methyl-cyclobutoxy, 3-methyl-cyclobutoxy, 1,2-dimethyl-cyclopropoxy, 2,3-dimethyl-cyclopropoxy, 1-ethyl-cyclopropoxy, 2-ethyl-cyclopropoxy, etc.

[0022] The R4 and R5 systems can also form rings (e.g., cycloids) with the carbon atoms they are bonded to.

[0023] n1 and n2 are each integers from 0 to 3.

[0024] Among the polymers containing the unit structure (A) shown in formula (1) above, some preferred examples are as follows. • A polymer of the unit structure (A) of formula (1) above, wherein R5 is a hydrogen atom, R4 is an aryl group having 6 to 40 carbon atoms, and the aryl group may be replaced by a halogen group, nitro group, amino group, cyano group, trifluoromethyl group, alkyl group having 1 to 10 carbon atoms, alkoxy group having 1 to 10 carbon atoms, alkenyl group having 2 to 10 carbon atoms, alkynyl group having 2 to 10 carbon atoms, or aryl group having 6 to 40 carbon atoms. • A polymer of the unit structure (A) shown in formula (1) above, which contains R5 as a hydrogen atom, R4 as an aryl group having 6 to 40 carbon atoms, and the aryl group may be replaced by an aryl group having 6 to 40 carbon atoms. • A polymer of the unit structure (A) shown in formula (1) above, which contains R5 as a hydrogen atom and R4 as a substitutable group composed of a combination of benzene rings, or a polymer of formula (1) above. • A polymer of the unit structure (A) of formula (1) above, which contains R5 as a hydrogen atom and R4 as a group consisting of a biphenyl group composed of a combination of substituted benzene rings, or a polymer of formula (1) above. • A polymer comprising R5 as a hydrogen atom, R4 as a group consisting of a combination of substituted benzene rings comprising a biphenyl group, and Ar1 and Ar2 as the unit structure (A) of the benzene ring shown in formula (1) above, or a polymer shown in formula (1) above. • A polymer containing a hydrogen atom at R5 and a substituted biphenyl as shown in formula (1) above, or a polymer as shown in formula (1) above. • A polymer containing the unit structure (A) of formula (1) above, where R5 is a hydrogen atom, R4 is a biphenyl, and Ar1 and Ar2 are benzene rings or naphthalene rings, or a polymer of formula (1) above.

[0025] Solvent As a solvent for the resist underlayer film forming composition of the present invention, any solvent capable of dissolving the compound shown in formula (1) above can be used without particular limitation. In particular, since the resist underlayer film forming composition of the present invention is used in a uniform solution state, it is recommended to use solvents generally used in the photolithography process when considering its coating performance.

[0026] Examples of such solvents include methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, methyl isobutyl methanol, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxylate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutyrate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3... Ethyl ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether, ethyl lactate, propyl lactate, isopropyl lactate, butyl lactate, lactic acid Isobutyl ester, methyl formate, ethyl formate, propyl formate, isopropyl formate, butyl formate, isobutyl formate, amyl formate, isoamyl formate, methyl acetate, ethyl acetate, amyl acetate, isoamyl acetate, hexyl acetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, butyl propionate, isobutyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, isopropyl butyrate, butyl butyrate, isobutyl butyrate, ethyl hydroxyethyl acetate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutyrate, ethyl methoxyethyl acetate, ethyl ethoxyethyl acetate, 3- Methyl methoxypropionate, ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-methoxybutylacetate, 3-methoxypropylacetate, 3-methyl-3-methoxybutylacetate, 3-methyl-3-methoxybutylpropionate, 3-methyl-3-methoxybutylbutyrate, methyl acetoacetate, toluene, xylene, methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone, 2-heptanone, 3-heptanone, 4-heptanone, cyclohexanone, N,N-dimethylformamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpyrrolidone, 4-methyl-2-pentanol, and γ-butyrolactone, etc. These solvents can be used alone or in combination of two or more.

[0027] Alternatively, the following compounds described in WO2018 / 131562A1 may also be used. (In formula (i), R1, R2 and R3 each represent alkyl groups with 1 to 20 carbon atoms that can be interrupted by oxygen atoms, sulfur atoms or amide bonds. They can be the same or different from each other, and can also be bonded to each other to form a ring structure.)

[0028] Examples of alkyl groups having 1 to 20 carbon atoms include straight-chain or branched alkyl groups, which may or may not have substituents. Examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, isohexyl, n-heptyl, n-octyl, cyclohexyl, 2-ethylhexyl, n-nonyl, isononyl, p-tert-butylcyclohexyl, n-decyl, n-dodecylnonyl, undecyl, dodecyl, tridecyl, tetradecyl, decadecyl, hexadecyl, hexadecyl, heptadecanyl, octadecyl, nonadecanyl, and icosyl. Alkyl groups having 1 to 12 carbon atoms are preferred, alkyl groups having 1 to 8 carbon atoms are more preferred, and alkyl groups having 1 to 4 carbon atoms are even more preferred.

[0029] Examples of alkyl groups with 1 to 20 carbon atoms that can be interrupted by oxygen, sulfur, or amide bonds include, for example, those containing the structural units -CH2-O-, -CH2-S-, -CH2-NHCO-, or -CH2-CONH-. -O-, -S-, -NHCO-, or -CONH- can be one or more units in the aforementioned alkyl groups. Specific examples of alkyl groups with 1 to 20 carbon atoms interrupted by -O-, -S-, -NHCO-, or -CONH- units include: methoxy, ethoxy, propoxy, butoxy, methylthio, ethylthio, propylthio, butylthio, methylcarbonylamino, ethylcarbonylamino, propylcarbonylamino, butylcarbonylamino, methylaminocarbonyl, ethylaminocarbonyl, propylaminocarbonyl, butylaminocarbonyl, etc.; and methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, or octadecyl, respectively substituted with methoxy, ethoxy, propoxy, butoxy, methylthio, ethylthio, propylthio, butylthio, methylcarbonylamino, ethylcarbonylamino, methylaminocarbonyl, ethylaminocarbonyl, etc. Methoxy, ethoxy, methylthio, and ethylthio are preferred, with methoxy and ethoxy being more particularly desirable.

[0030] These solvents, due to their relatively high boiling points, are also effective in imparting high embeddability or high planarization to the inhibitor underlayer film forming composition.

[0031] The following shows a specific example of a preferred compound as shown in formula (i).

[0032] Of the above, 3-methoxy-N,N-dimethylpropionic acid, N,N-dimethylisobutylamide, and The following formula: The compound shown is preferred, and the compound shown in formula (i) is particularly preferred to be 3-methoxy-N,N-dimethylpropionic acid and N,N-dimethylisobutylamide.

[0033] These solvents can be used alone or in combination of two or more. Solvents with a boiling point above 160°C are preferred, including propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, butyl lactate, cyclohexanone, 3-methoxy-N,N-dimethylpropionic acid, N,N-dimethylisobutylamide, 2,5-dimethylhexane-1,6-dimethyldiacetate (DAH; CAS, 89182-68-3), and 1,6-diethoxyhexane (CAS, 6222-17-9). Propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and N,N-dimethylisobutylamide are particularly preferred.

[0034] These solvent systems can be used alone or in combination of two or more. The proportion of solid components of the organic solvent removed from the aforementioned composition is, for example, 0.5% to 30% by mass, preferably 0.8% to 15% by mass.

[0035] <Any ingredient> The inhibitor lower film forming composition of the present invention may also contain at least one of the following as an optional component: crosslinking agent, acid and / or acid generating agent, hot acid generating agent and surfactant.

[0036] (Cross-linking agent) The inhibitor-forming composition of the present invention may further contain a crosslinking agent. Preferably, a crosslinking compound having at least two crosslinking-forming substituents is used as the aforementioned crosslinking agent. Examples include melamine compounds, substituted urea compounds, and phenolic compounds, or polymer systems thereof, having crosslinking-forming substituents such as hydroxymethyl and methoxymethyl. Specifically, compounds such as methoxymethylated ethynylurea, butoxymethylated ethynylurea, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzoguanamine, and butoxymethylated benzoguanamine can be exemplified by, for example, tetramethoxymethylethynylurea (e.g., PL-LI (Chemical Co., Ltd.) methoxymethyl)ethynylurea), tetrabutoxymethylethynylurea, and hexamethoxymethylmelamine. Furthermore, as substituted urea compounds, compounds such as methoxymethylated urea, butoxymethylated urea, or methoxymethylated thiourea can be exemplified by, for example, tetramethoxymethylurea and tetrabutoxymethylurea. Condensations of these compounds can also be used. As phenolic compounds, examples include tetrahydroxymethylbiphenol, tetramethoxymethylbiphenol, tetrahydroxymethylbisphenol, tetramethoxymethylbisphenol, and compounds shown in the following formulas.

[0037] As a crosslinking agent, compounds having at least two epoxy groups can also be used. Examples of such compounds include, for instance, cyanuric acid trioxide (2,3-epoxypropyl), 1,4-butanediol diglycidyl ether, 1,2-epoxy-4-(epoxyethyl)cyclohexane, glycerol triglycidyl ether, diethylene glycol diglycidyl ether, 2,6-diglycidylphenyl glycidyl ether, 1,1,3-tris(p-(2,3-epoxypropoxy)phenyl)propane, 1,2-cyclohexanedicarboxylic acid diglycidyl ester, 4,4'-methylenebis(N,N-diglycidylaniline), 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylic acid ester, trimethylolethane triglycidyl ether, bisphenol A-diglycidyl ether, etc. (Stock) Daicel's Epolead [Registered Trademark] GT-401, same as GT-403, same as GT-301, same as GT-302, Ceroxide [Registered Trademark] 2021, same as 3000; Mitsubishi Chemical (Stock)'s 1001, 1002, 1003, 1004, 1007, 1009, 1010, 828, 807, 152, 154, 180S75, 871, 872; Nippon Kayaku (Stock)'s EPPN201, same as 202, EOCN-102, same as 103S, same as 104S, same as 1020, same as 1025, same as 1027; Nagase Chemical (Stock)'s Denacol [Registered Trademarks] EX-252, EX-611, EX-612, EX-614, EX-622, EX-411, EX-512, EX-522, EX-421, EX-313, EX-314, EX-321; CY175, CY177, CY179, CY182, CY184, CY192 manufactured by BASF JAPAN; Epiclon200, 400, 7015, 835LV, 850CRP manufactured by DIC. As compounds having at least two epoxy groups, epoxy resins having amine groups can also be used. Examples of such epoxy resins include YH-434 and YH-434L (manufactured by Shin-Nippon Chemical Epoxy Manufacturing Co., Ltd.).

[0038] As the aforementioned crosslinking agent, compounds having at least two terminal isocyanate groups can also be used. Examples of such compounds include Takenate B-830 and B-870N manufactured by Mitsui Chemicals, Ltd., and VESTANAT B1358 / 100 manufactured by Evonik Degussa.

[0039] Alternatively, compounds having at least two vinyl ether groups can be used as the aforementioned crosslinking agent. Examples of such compounds include bis(4-(vinyloxymethyl)cyclohexylmethyl)glutarate, tri(ethylene glycol) divinyl ether, divinyl adipate, diethylene glycol divinyl ether, 1,2,4-tris(4-vinyloxybutyl)trimethacrylate, 1,3,5-tris(4-vinyloxybutyl)trimethacrylate, bis(4-(vinyloxy)butyl)terephthalate, bis(4-(vinyloxy)butyl)isophthalate, ethylene glycol divinyl ether, 1,4-butanediol divinyl ether, tetramethylene glycol divinyl ether, tetraethylene glycol divinyl ether, neopentyl glycol divinyl ether, trimethylolpropane trivinyl ether, trimethylolethane trivinyl ether, hexanediol divinyl ether, 1,4-cyclohexanediol divinyl ether, tetraethylene glycol divinyl ether, pentaerythritol divinyl ether, pentaerythritol trivinyl ether, and cyclohexanediethanol divinyl ether.

[0040] Furthermore, a crosslinking agent with high heat resistance can be used as the aforementioned crosslinking agent. Preferably, a compound containing a crosslinking substituent with an aromatic ring (e.g., benzene ring, naphthalene ring) is used as the crosslinking agent with high heat resistance.

[0041] Examples of such compounds include compounds having a partial structure of formula (4) below, or polymers or oligomers having repeating units of formula (5) below. R11, R12, R13, and R14 are hydrogen atoms or alkyl groups having 1 to 10 carbon atoms, and the above examples can be used for these alkyl systems. n1 is an integer from 1 to 4, n2 is an integer from 1 to (5-n1), and (n1+n2) represents an integer from 2 to 5. n3 is an integer from 1 to 4, n4 is from 0 to (4-n3), and (n3+n4) represents an integer from 1 to 4. Oligopolymers and polymer systems can be used in the range of 2 to 100 or 2 to 50 repeating unit structures.

[0042] The compounds, polymers, and oligomers of formulas (4) and (5) are as exemplified below.

[0043] The aforementioned compounds are available as products of Asahi Organic Materials Co., Ltd. and Honshu Chemical Industry Co., Ltd. For example, among the aforementioned crosslinking agents, the compound of formula (4-23) is available as the trade name TMOM-BP of Honshu Chemical Industry Co., Ltd., and the compound of formula (4-24) is available as the trade name TM-BIP-A of Asahi Organic Materials Co., Ltd. The amount of crosslinking agent added varies depending on the coating solvent used, the substrate used, the required solution viscosity, the required film shape, etc., and is 0.001% by mass or more, 0.01% by mass or more, 0.05% by mass or more, 0.5% by mass or more, or 1.0% by mass or more, or less than 80% by mass, less than 50% by mass, less than 40% by mass, less than 20% by mass, or less than 10% by mass relative to the total solids content. These crosslinking agents can also cause crosslinking reactions due to self-condensation, but when crosslinking substituents are present in the polymer of the present invention, they can cause crosslinking reactions with these crosslinking substituents.

[0044] One type of crosslinking agent selected from these various crosslinking agents can be added, or two or more types can be combined and added.

[0045] (Acids and / or their salts and / or acid-generating agents) The inhibitor lower film forming composition of the present invention may contain an acid and / or its salt and / or an acid generating agent.

[0046] Examples of acids include carboxylic acid compounds such as p-toluenesulfonic acid, trifluoromethanesulfonic acid, salicylic acid, 5-sulfosalicylic acid, 4-phenolsulfonic acid, camphorsulfonic acid, 4-chlorobenzenesulfonic acid, benzenedisulfonic acid, 1-naphthalenesulfonic acid, citric acid, benzoic acid, hydroxybenzoic acid, and naphtholic acid, as well as inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid. Salts of the aforementioned acids may also be used as salts. The use of salts is not limited to any particular type; salts of ammonia derivatives such as trimethylamine salts and triethylamine salts, or salts of pyridine derivatives and morpholine derivatives, may also be suitable. The acid or its salt may be used alone or in combination of two or more. The amount of the blend is typically 0.0001 to 20% by mass relative to the total solids content, preferably 0.0005 to 10% by mass, and more preferably 0.01 to 5% by mass.

[0047] Examples of acid-generating agents include thermal acid-generating agents and photoacid-generating agents. Examples of heat-generating acid agents include 2,4,4,6-tetrabromocyclohexadienone, benzoin toluene sulfonate, 2-nitrobenzyl toluene sulfonate, K-PURE [registered trademark] CXC-1612, CXC-1614, TAG-2172, TAG-2179, TAG-2678, TAG2689, TAG2700 (manufactured by King Industries), and SI-45, SI-60, SI-80, SI-100, SI-110, SI-150 (manufactured by Sanshin Chemical Industry Co., Ltd.). Others include the fourth-order ammonium salt of trifluoroacetic acid and alkyl sulfonic acid esters.

[0048] The photoacid generator produces acid during the exposure of the resist. Therefore, it can adjust the acidity of the lower film. This is a method used to match the acidity of the lower film with that of the upper resist. Furthermore, by adjusting the acidity of the lower film, the pattern shape of the resist formed on the upper layer can be adjusted. Examples of photoacid generators included in the resist lower film forming composition of the present invention include onium salt compounds, sulfonium imine compounds, and disulfonyldiazomethane compounds.

[0049] Examples of onium salt compounds include onium salts such as diphenylmonium hexafluorophosphate, diphenylmonium trifluoromethane sulfonate, diphenylmonium nonafluoron-butane sulfonate, diphenylmonium perfluoron-octane sulfonate, diphenylmonium camphor sulfonate, bis(4-tert-butylphenyl)monium camphor sulfonate, and bis(4-tert-butylphenyl)monium trifluoromethane sulfonate, as well as strontium salt compounds such as triphenylstrontium hexafluoroantimonate, triphenylstrontium nonafluoron-butane sulfonate, triphenylstrontium camphor sulfonate, and triphenylstrontium trifluoromethane sulfonate.

[0050] Examples of sulfonylimine compounds include N-(trifluoromethanesulfonoxy)butadieneimine, N-(nonafluoron-butanesulfonoxy)butadieneimine, N-(camphorsulfonoxy)butadieneimine, and N-(trifluoromethanesulfonoxy)naphthylimine.

[0051] Examples of disulfonyldiazomethane compounds include, for example, bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(2,4-dimethylbenzenesulfonyl)diazomethane, and methylsulfonyl-p-toluenesulfonyldiazomethane.

[0052] Acid-generating agents can be used in combination, either alone or in combination of two or more. When using an acid-generating agent, the proportion is 0.01 to 10 parts by mass, or 0.1 to 8 parts by mass, or 0.5 to 5 parts by mass relative to 100 parts by mass of the solid component of the lower layer film forming composition of the inhibitor.

[0053] (surfactants) In order to prevent pinholes or streaks and improve the coating properties for uneven surfaces, the lower film forming composition of the inhibitor of the present invention may incorporate a surfactant. Examples of surfactants include, for instance, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene hexadecyl ether, and polyoxyethylene oleyl ether; polyoxyethylene alkyl aryl ethers such as polyoxyethylene octylphenyl ether and polyoxyethylene nonylphenyl ether; polyoxyethylene-polyoxypropylene block copolymers; sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan monooleate, sorbitan trioleate, and sorbitan tristearate; and polyoxyethylene sorbitan monolaurate, poly… Nonionic surfactants such as polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate, as well as polyoxyethylene sorbitan fatty acid esters; Eftop [registered trademark] EF301, same as EF303, same as EF352 (Mitsubishi Materials Electronics & Chemicals Co., Ltd.); Megafac [registered trademark] F171, same as F173, same as R-30, same as R-30-N, same as R-40, same as R-40-LM (DIC Co., Ltd.); Fluorad Fluoropolymers such as FC430, FC431 (manufactured by Sumitomo 3M), Asahiguard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, and SC106 (manufactured by Asahi Glass), and organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.) may be added. One type of surfactant selected from these surfactants may be added, or two or more may be added in combination. The aforementioned surfactant content ratio, relative to the solid content of the solvent after removal from the lower film-forming composition of the inhibitor of the present invention, is, for example, 0.01% by mass to 5% by mass.

[0054] The resist underlayer film forming composition of the present invention can also be further supplemented with light absorbers, rheology modifiers, adhesion promoters, etc. Rheology modifiers are effective in improving the flowability of the underlayer film forming composition. Adhesion promoters are effective in improving the adhesion between the semiconductor substrate or resist and the underlayer film.

[0055] (Light absorber) As light absorbers, commercially available light absorbers listed in publications such as "Technology and Market of Industrial Pigments" (CMC publication) or "Dye Handbook" (organic synthetic chemists' association) are suitable, such as CI Disperse Yellow 1, 3, 4, 5, 7, 8, 13, 23, 31, 49, 50, 51, 54, 60, 64, 66, 68, 79, 82, 88, 90, 93, 102, 114 and 124; CI Disperse Orange 1, 5, 13, 25, 29, 30, 31, 44, 57, 72 and 73; CI Disperse Red 1, 5, 7, 13, 17, 19, 43, 50, 54, 58, 65, 72, 73, 88, 117, 137, 143. 199 and 210; CI Disperse Violet 43; CI Disperse Blue 96; CI Fluorescent Brighteners 112, 135 and 163; CI Solvent Orange 2 and 45; CI Solvent Red 1, 3, 8, 23, 24, 25, 27 and 49; CI Pigment Green 10; CI Pigment Brown 2, etc. Typically, the above-mentioned light absorbers are incorporated at a proportion of 10% by mass or less, preferably 5% by mass or less, relative to the total solids content of the composition forming the lower layer film of the resist.

[0056] (Rheology modifier) Rheology modifiers are mainly added to improve the flowability of the resistive underlayer film composition, especially during the baking process, to enhance the uniformity of the resistive underlayer film thickness or to improve the filling effect of the resistive underlayer film composition inside the pores. Specific examples include phthalic acid derivatives such as dimethyl phthalate, diethyl phthalate, diisobutyl phthalate, dihexyl phthalate, and butyl isodecyl phthalate; adipic acid derivatives such as di-n-butyl adipate, diisobutyl adipate, isooctyl adipate, and octyl decyl adipate; maleic acid derivatives such as di-n-butyl maleate, diethyl maleate, and dinonyl maleate; oleic acid derivatives such as methyl oleate, butyl oleate, and tetrahydrofurfuryl oleate; and stearic acid derivatives such as n-butyl stearate and glyceryl stearate. In contrast to the all-solid composition of the resistive underlayer film, these rheology modifiers are typically blended in a proportion of less than 30% by mass.

[0057] (Followed by the supplement) Next, the additives are mainly used to improve the adhesion between the substrate or the resist and the underlying film, especially during development, to prevent the resist from peeling off. Specific examples include chlorosilanes such as trimethylchlorosilane, dimethylhydroxymethylchlorosilane, methyldiphenylchlorosilane, and chloromethyldimethylchlorosilane; alkoxysilanes such as trimethylmethoxysilane, dimethyldiethoxysilane, methyldimethoxysilane, dimethylhydroxymethylethoxysilane, diphenyldimethoxysilane, and phenyltriethoxysilane; hexamethyldisilazane; N,N'-bis(trimethylsilyl)urea; dimethyltrimethylsilylamine; and trimethylsilylimidazolium. The additives include silanes such as azoles, hydroxymethyltrichlorosilanes, γ-chloropropyltrimethoxysilanes, γ-aminopropyltriethoxysilanes, and γ-epoxypropoxypropyltrimethoxysilanes; heterocyclic compounds such as benzotriazoles, benzimidazoles, indazoles, imidazoles, 2-mercaptobenzimidazoles, 2-mercaptobenzothiazoles, 2-mercaptobenzoxazoles, urea, thiouracil, mercaptoimidazoles, and mercaptopyrimidines; or ureas such as 1,1-dimethylurea and 1,3-dimethylurea; or thiourea compounds. These adsorption aids are typically incorporated in a proportion of less than 5% by mass, preferably less than 2% by mass, relative to the all-solid component of the inhibitor-forming film composition.

[0058] The solid content of the inhibitor underlayer film-forming composition of the present invention is typically made to be 0.1 to 70% by mass, preferably 0.1 to 60% by mass. The solid content refers to the percentage of all components contained in the inhibitor underlayer film-forming composition after removing the solvent. The proportion of the aforementioned polymer in the solid content is preferably in the following order: 1 to 100% by mass, 1 to 99.9% by mass, 50 to 99.9% by mass, 50 to 95% by mass, and 50 to 90% by mass.

[0059] One measure for evaluating whether the inhibitor underlayer membrane formation composition is a homogeneous solution is to observe the permeability of a specific microfilter. The inhibitor underlayer membrane formation composition of the present invention will present a homogeneous solution state when passing through a microfilter with an aperture of 0.1 μm.

[0060] Examples of materials for the aforementioned microfilters include fluorinated resins such as PTFE (polytetrafluoroethylene) and PFA (tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer), PE (polyethylene), UPE (ultra-high molecular weight polyethylene), PP (polypropylene), PSF (polyurethane), PES (polyether ether), and nylon, with PTFE (polytetrafluoroethylene) being the most preferred.

[0061] <Bottom Layer Film of Resistor> The resistive underlayer film system can be formed using the resistive underlayer film forming composition of the present invention as follows. The resist underlayer film formation composition of the present invention is coated onto a substrate used in the manufacture of semiconductor devices (e.g., silicon wafer substrate, silicon dioxide substrate (SiO2 substrate), silicon nitride substrate (SiN substrate), silicon oxide nitride substrate (SiON substrate), titanium nitride substrate (TiN substrate), tungsten substrate (W substrate), glass substrate, ITO substrate, polyimide substrate, and low-k material coated substrate, etc.) using a suitable coating method such as a spin coater or coater. The resist underlayer film is then formed by firing using a heating means such as a heating plate. The firing conditions can be appropriately selected from a firing temperature of 80°C to 600°C and a firing time of 0.3 to 60 minutes. A firing temperature of 150°C to 350°C and a firing time of 0.5 to 2 minutes are preferred. Air or inert gases such as nitrogen or argon can be used as the ambient gas during firing. Here, the thickness of the underlying film is, for example, 10 to 1000 nm, or 20 to 500 nm, or 30 to 400 nm, or 50 to 300 nm. Furthermore, if a quartz substrate is used as the substrate, a replica of the quartz transfer mold (mold replica) can be produced.

[0062] Furthermore, an inorganic resist underlayer film (hard mask) can also be formed on the organic resist underlayer film of the present invention. For example, in addition to the method of forming the silicon-containing resist underlayer film (inorganic resist underlayer film) composition described in WO2009 / 104552A1 by spin coating, Si-based inorganic material films can also be formed by CVD or the like. Moreover, the hard mask of the present invention includes either a silicon hard mask or a CVD film.

[0063] Alternatively, an adhesion layer and / or a silicon oxide layer containing 99% by mass or less, or 50% by mass or less, of Si can be formed on the resist underlayer film of the present invention by coating or vapor deposition. For example, in addition to the adhesion layer described in Japanese Patent Application Publication No. 2013-202982 or Japanese Patent No. 5827180, and the silicon-containing resist underlayer film (inorganic resist underlayer film) formation composition described in WO2009 / 104552A1, it is also possible to form a Si-based inorganic material film by CVD or the like.

[0064] Furthermore, by coating the resist lower layer film forming composition of the present invention onto a semiconductor substrate (so-called high-low difference substrate) containing a portion having a height difference and a portion not having a height difference, and then firing it, a resist lower layer film that reduces the height difference between the portion having a height difference and the portion not having a height difference can be formed.

[0065] <Semiconductor Device Manufacturing Methods> The method for manufacturing the semiconductor device of the present invention includes: The steps of forming a resist underlayer film using the resist underlayer film formation composition of the present invention on a semiconductor substrate, The step of forming a resist film on top of the already formed resist underlayer film. The process of forming a resist pattern by irradiating the formed resist film with light or electron beams and developing it. The patterning step involves etching the underlying resist film using the pre-formed resist pattern, and... The process of fabricating a semiconductor substrate using a patterned resist underlayer film.

[0066] The method for manufacturing the semiconductor device of the present invention includes: The steps of forming a resist underlayer film using the resist underlayer film formation composition of the present invention on a semiconductor substrate, The step of forming a hard mask on top of the already formed resist underlayer film. The step of forming a resist film on top of the existing hard mask. The process of forming a resist pattern by irradiating the formed resist film with light or electron beams and developing it. The steps of etching the aforementioned resist underlayer film using the formed resist pattern, and Steps to remove hard mask.

[0067] The better series also includes: The step of forming a vapor-deposited film (spacer) on the underlying film after the hard mask has been removed. The processing steps involve etching the already formed vapor-deposited film (spacer). The steps for removing the underlying membrane, and The process of processing semiconductor substrates using spacers.

[0068] The aforementioned semiconductor substrate can also be a substrate with a high-low difference.

[0069] The steps for forming the resist underlayer film using the resist underlayer film forming composition of the present invention are as described above.

[0070] Subsequently, a resist film, such as a photoresist layer, is formed on the lower resist film. The photoresist layer can be formed by a well-known method, namely, by coating a photoresist composition solution onto the lower film and firing it. The thickness of the photoresist film is, for example, 50 to 10000 nm, or 100 to 2000 nm, or 200 to 1000 nm.

[0071] As a photoresist formed on the lower layer of the resist film, there are no particular limitations as long as it is photosensitized by light used for exposure. Both negative and positive photoresists can be used. Examples include: positive photoresists composed of phenolic resin and 1,2-naphthoquinone diazidesulfonate; chemically amplified photoresists composed of a binder having a group that increases the alkali dissolution rate due to acid decomposition and a photoacid generator; chemically amplified photoresists composed of a low-molecular-weight compound that increases the alkali dissolution rate of the photoresist due to acid decomposition and an alkali-soluble binder and a photoacid generator; and chemically amplified photoresists composed of a binder having a group that increases the alkali dissolution rate of the photoresist due to acid decomposition and a low-molecular-weight compound that increases the alkali dissolution rate of the photoresist due to acid decomposition and a photoacid generator. Examples include Shipley's APEX-E, Sumitomo Chemical Industries Co., Ltd.'s PAR710, and Shin-Etsu Chemical Industries Co., Ltd.'s SEPR430. For example, Proc. SPIE, Vol. 3999, 330-334 (2000) and Proc. SPIE, Vol. Fluorine-containing polymer photoresist as described in 3999, 357-364 (2000), or Proc. SPIE, Vol. 3999, 365-374 (2000).

[0072] Next, a resist pattern is formed by irradiation with light or electron beams and development. First, exposure is performed using a specified mask. Exposure is conducted using near-ultraviolet, far-ultraviolet, or extreme ultraviolet light (e.g., EUV (wavelength 13.5 nm)). Specifically, excimer lasers such as KrF (wavelength 248 nm), ArF (wavelength 193 nm), and F2 (wavelength 157 nm) can be used. Among these, ArF (wavelength 193 nm) and EUV (wavelength 13.5 nm) are preferred. After exposure, post-exposure baking may be performed as necessary. Post-exposure baking can be performed under suitable conditions ranging from 70°C to 150°C and 0.3 to 10 minutes.

[0073] Furthermore, in this invention, an electron beam lithography resist can be used instead of a photoresist. As an electron beam resist, either a negative or positive type can be used. Examples include: a chemically amplifying resist composed of an acid-generating agent and a binder having a base that changes the rate of alkali dissolution due to acid decomposition; a chemically amplifying resist composed of an alkali-soluble binder, an acid-generating agent, and a low-molecular-weight compound that changes the rate of alkali dissolution due to acid decomposition; a chemically amplifying resist composed of an acid-generating agent, a binder having a base that changes the rate of alkali dissolution due to acid decomposition, and a low-molecular-weight compound that changes the rate of alkali dissolution due to acid decomposition; a non-chemically amplifying resist composed of a binder having a base that changes the rate of alkali dissolution due to electron beam decomposition; and a non-chemically amplifying resist composed of a binder having a portion where the rate of alkali dissolution changes due to electron beam cutting. The use of such electron wire resists can also form resist patterns in the same way as when using photoresist as an irradiation source with electron wires.

[0074] Alternatively, to maintain or improve high resolution or wide depth of focus, the substrate with the resist film already formed can be immersed in a liquid medium for exposure. In this case, the resist underlayer film is also required to be resistant to the liquid medium used, but the resist underlayer film forming composition of the present invention can also form a resist underlayer film that meets such requirements.

[0075] Next, development is performed using a developer. In this way, for example, when using positive photoresist, the exposed portion of the photoresist is removed to form a photoresist pattern. Examples of developing solutions include alkaline aqueous solutions such as alkali metal hydroxides like potassium hydroxide and sodium hydroxide, aqueous solutions of tetramethylammonium hydroxide, tetraethylammonium hydroxide, and tetramethylammonium hydroxide (such as choline), and aqueous solutions of amines like ethanolamine, propylamine, and ethylenediamine. Furthermore, surfactants may be added to these developing solutions. Suitable developing conditions are a temperature of 5 to 50°C and a development time of 10 to 600 seconds.

[0076] Furthermore, the pattern of the photoresist (upper layer) formed by this operation is used as a protective film to remove the inorganic lower layer (intermediate layer). Next, the film composed of the patterned photoresist and the inorganic lower layer (intermediate layer) is used as a protective film to remove the organic lower layer (lower layer). Finally, the patterned inorganic lower layer (intermediate layer) and organic lower layer (lower layer) are used as protective films to process the semiconductor substrate.

[0077] First, the inorganic lower layer (intermediate layer) with the photoresist removed is removed by dry etching to expose the semiconductor substrate. Dry etching of the inorganic lower layer can be performed using gases such as tetrafluoromethane (CF4), perfluorocyclobutane (C4F8), perfluoropropane (C3F8), trifluoromethane, carbon monoxide, argon, oxygen, nitrogen, sulfur hexafluoride, difluoromethane, nitrogen trifluoride, chlorine trifluoride, chlorine, trichloroborane, and dichloroborane. Halogen-based gases are preferred for dry etching of the inorganic lower layer, while fluorine-based gases are even more desirable. Examples of fluorine-based gases include tetrafluoromethane (CF4), perfluorocyclobutane (C4F8), perfluoropropane (C3F8), trifluoromethane, and difluoromethane (CH2F2).

[0078] Subsequently, the organic underlayer is removed using a protective film consisting of patterned photoresist and an inorganic underlayer. The organic underlayer (underlayer) is preferably removed by dry etching with an oxygen-based gas. This is because inorganic underlayers containing numerous silicon atoms are difficult to remove using dry etching with an oxygen-based gas.

[0079] Furthermore, wet etching may be performed to simplify the process steps or reduce damage to the substrate. However, by using the resist underlayer film formation composition of the present invention, a resist underlayer film that exhibits sufficient resistance to the solvent used can also be formed.

[0080] Finally, the semiconductor substrate is processed. The semiconductor substrate is preferably processed using dry etching with fluorine-based gases. Examples of fluorine-based gases include tetrafluoromethane (CF4), perfluorocyclobutane (C4F8), perfluoropropane (C3F8), trifluoromethane, and difluoromethane (CH2F2).

[0081] Furthermore, before the formation of the photoresist, an organic antireflective film can be formed on the upper layer of the resist film. There are no particular restrictions on the composition of the antireflective film used here, and any of the components commonly used in the lithography process can be selected. Moreover, the commonly used methods, for example, can be used to form the antireflective film by coating and firing using a spin coater or a coating machine.

[0082] This invention allows for the deposition of an organic underlayer film on a substrate, followed by the deposition of an inorganic underlayer film, and then the deposition of photoresist. This narrows the pattern width of the photoresist, and to prevent pattern collapse, substrate processing becomes possible even with a thin photoresist coating by selecting an appropriate etching gas. For example, a fluorine-based gas with a sufficiently fast etching rate for the photoresist can be used to process the resist underlayer film; a fluorine-based gas with a sufficiently fast etching rate for the inorganic underlayer film can be used to process the substrate; and an oxygen-based gas with a sufficiently fast etching rate for the organic underlayer film can be used to process the substrate.

[0083] The resist underlayer film formed by the resist underlayer film forming composition may absorb light depending on the wavelength of the light used in the photolithography process. In this case, it can function as an anti-reflective film that prevents reflected light from the substrate. Furthermore, the underlayer film formed by the resist underlayer film forming composition of the present invention can also function as a hard mask. The underlayer film of the present invention can also be used as: a layer to prevent interaction between the substrate and the photoresist; a layer that prevents adverse effects on the substrate caused by the material used for the photoresist or substances generated during photoresist exposure; a layer that prevents the diffusion of substances generated by the substrate during heating and firing onto the upper photoresist; and a barrier layer for reducing the toxic effects of the photoresist layer caused by the dielectric layer of the semiconductor substrate.

[0084] Furthermore, the lower layer film formed by the resist lower layer film composition can be used as an embedded material suitable for via holes used in dual damascene processes, and can fill the holes without gaps. It can also be used as a planarizing material for planarizing the surface of semiconductor substrates with uneven surfaces. [Example]

[0085] The present invention will be described in more detail below with reference to the embodiments and the like, but the present invention is not limited to the embodiments and the like in any way. The apparatus shown is for measuring the weight-average molecular weight of the compounds obtained in the following synthetic examples. Device: HLC-8320GPC manufactured by Tosoh Corporation GPC tubing: TSKgel Super-MultiporeHZ-N (2 tubes) Column temperature: 40℃ Flow rate: 0.35 mL / min Solution: THF Standard sample: polystyrene

[0086] <Synthesis example 1> In a flask, 10.00 g of diphenylamine (manufactured by Tokyo Chemical Industry Co., Ltd., hereinafter referred to as DPA), 9.23 g of 1-naphthal (manufactured by Tokyo Chemical Industry Co., Ltd.), 1.14 g of methanesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd., hereinafter referred to as MSA), and 47.52 g of propylene glycol monomethyl ether acetate (hereinafter referred to as PGMEA) were placed. The mixture was then heated to 120°C under nitrogen for approximately 2 hours. After the reaction was stopped, the resin (1-1) was obtained by precipitating it with methanol and drying it. The weight-average molecular weight (Mw) obtained by GPC, converted to polystyrene, was approximately 2,500. The obtained resin was dissolved in cyclohexanone (hereinafter referred to as CYH), and ion exchange was performed using a cation exchange resin and anion exchange resin for 4 hours to obtain a solution of the desired compound.

[0087]

[0088] <Synthesis example 2> In a flask, 10.00 g of DPA, 10.77 g of 4-phenylbenzaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.28 g of MSA, and 63.16 g of PGMEA were placed. The mixture was then heated to 115°C under nitrogen for approximately 4 hours. After the reaction was stopped, the resin (1-2) was precipitated with methanol and dried to obtain resin. The weight-average molecular weight (Mw) obtained by GPC, converted to polystyrene, was approximately 5,700. The obtained resin was dissolved in PGMEA, and ion exchange was performed using cation exchange resin and anion exchange resin for 4 hours to obtain a solution of the desired compound.

[0089]

[0090] <Synthesis example 3> In a flask, 10.00 g of DPA, 7.10 g of 4-methylbenzaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.28 g of MSA, and 52.15 g of PGMEA were placed. The mixture was then heated to 115°C under nitrogen for approximately 5 hours. After the reaction was stopped, the resin (1-3) was obtained by precipitating it with methanol and drying it. The weight-average molecular weight (Mw) obtained by GPC, converted to polystyrene, was approximately 4,500. The obtained resin was dissolved in PGMEA, and ion exchange was performed using cation exchange resin and anion exchange resin for 4 hours to obtain a solution of the desired compound.

[0091]

[0092] <Synthesis example 4> In a flask, 10.00 g of DPA, 7.34 g of 4-fluorobenzaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.28 g of MSA, and 70.50 g of PGMEA were placed. The mixture was then heated under nitrogen until reflux and allowed to react for approximately 4 hours. After the reaction was stopped, the resin was precipitated using methanol and dried to obtain resin (1-4). The weight-average molecular weight (Mw) obtained by GPC, converted to polystyrene, was approximately 5,700. The obtained resin was dissolved in PGMEA, and ion exchange was performed using cation exchange resin and anion exchange resin for 4 hours to obtain a solution of the desired compound.

[0093]

[0094] <Synthesis example 5> In a flask, 10.00 g of DPA, 9.59 g of 4-tert-butylbenzaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.57 g of MSA, and 80.62 g of PGMEA were placed. The mixture was then heated under nitrogen until reflux and allowed to react for approximately 8 hours. After the reaction was stopped, the resin (1-5) was obtained by precipitating it with methanol and drying it. The weight-average molecular weight (Mw) obtained by GPC, converted to polystyrene, was approximately 4,500. The obtained resin was dissolved in PGMEA, and ion exchange was performed using cation exchange resin and anion exchange resin for 4 hours to obtain a solution of the desired compound.

[0095]

[0096] <Synthesis example 6> In a flask, 10.00 g of DPA, 10.65 g of 9-fumonisin (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.84 g of MSA, and 23.49 g of CYH were placed. The mixture was then heated under nitrogen until reflux and allowed to react for approximately 2.5 hours. After the reaction was stopped, the resin (1-6) was obtained by precipitating it with methanol and drying it. The weight-average molecular weight (Mw) obtained by GPC, converted to polystyrene, was approximately 1,300. The obtained resin was dissolved in PGMEA, and ion exchange was performed using cation exchange resin and anion exchange resin for 4 hours to obtain a solution of the desired compound.

[0097]

[0098] <Synthesis Example 7> In a flask, 10.00 g of DPA, 13.61 g of 1-pyrenecarboxaldehyde, 1.14 g of MSA, 46.19 g of PGMEA, and 11.59 g of N-methyl-2-pyrrolidone were placed. The mixture was then heated to 120°C under nitrogen for approximately 7.5 hours. After the reaction was stopped, the resin (1-7) was precipitated with methanol and dried to obtain resin. The weight-average molecular weight (Mw) obtained by GPC, converted to polystyrene, was approximately 1,400. The obtained resin was dissolved in CYH, and ion exchange was performed using cation exchange resin and anion exchange resin for 4 hours to obtain a solution of the desired compound.

[0099]

[0100] <Synthesis example 8> In a flask, 10.00 g of N-phenyl-1-naphthylamine (manufactured by Tokyo Chemical Industry Co., Ltd., hereinafter referred to as PNA), 4.84 g of benzaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.88 g of MSA, and 36.67 g of PGMEA were placed. The mixture was then heated under nitrogen until reflux and allowed to react for approximately 15 minutes. After the reaction was stopped, the resin (1-8) was obtained by precipitating it with methanol and drying it. The weight-average molecular weight (Mw) obtained by GPC, converted to polystyrene, was approximately 5,900. The obtained resin was dissolved in CYH, and ion exchange was performed using cation exchange resin and anion exchange resin for 4 hours to obtain a solution of the desired compound.

[0101]

[0102] <Synthesis Example 9> In a flask, 10.00 g of PNA, 7.12 g of 1-naphthal (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.91 g of p-toluenesulfonic acid monohydrate (manufactured by Kanto Chemical Co., Ltd.), and 21.03 g of 1,4-dioxane were placed. The mixture was then heated to 110°C under nitrogen for approximately 12 hours. After the reaction was stopped, the resin (1-9) was obtained by precipitating it with methanol and drying it. The weight-average molecular weight (Mw) obtained by GPC, converted to polystyrene, was approximately 1,400. The obtained resin was dissolved in PGMEA, and ion exchange was performed using cation exchange resin and anion exchange resin for 4 hours to obtain a solution of the desired compound.

[0103]

[0104] <Synthesis example 10> In a flask, 8.00 g of PNA, 8.47 g of 1-pyrenecarboxaldehyde, 1.04 g of p-toluenesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 16.26 g of toluene, and 16.26 g of 1,4-dioxane were placed. The mixture was then heated under nitrogen until reflux and allowed to react for approximately 19.5 hours. After the reaction was stopped, the resin (1-10) was obtained by precipitating it with methanol and drying. The weight-average molecular weight (Mw) obtained by GPC, converted to polystyrene, was approximately 1,200. The obtained resin was dissolved in cyclohexanone (hereinafter referred to as CYH), and ion exchange was performed using cation exchange resin and anion exchange resin for 4 hours to obtain a solution of the desired compound.

[0105]

[0106] <Synthesis Example 11> In a flask, 15.00 g of PNA, 12.47 g of 4-phenylbenzaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.33 g of MSA, and 41.70 g of PGMEA were placed. The mixture was then heated to 115°C under nitrogen for approximately 2 hours. After the reaction was stopped, the resin (1-11) was obtained by precipitating it with methanol and drying it. The weight-average molecular weight (Mw) obtained by GPC, converted to polystyrene, was approximately 2,600. The obtained resin was dissolved in PGMEA, and ion exchange was performed using cation exchange resin and anion exchange resin for 4 hours to obtain a solution of the desired compound.

[0107]

[0108] <Synthesis example 12> 35.00 g of carbazole (manufactured by Tokyo Chemical Industry Co., Ltd., hereinafter referred to as Cz), 32.72 g of 1-naphthal (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.01 g of MSA, and 162.71 g of PGMEA were placed in a flask. The mixture was then heated to 120°C under nitrogen for approximately 7 hours. After the reaction was stopped, the precipitate was obtained by precipitating the compound with methanol and drying it to obtain compound (1-12). The weight-average molecular weight (Mw) obtained by GPC, converted to polystyrene, was approximately 2,600. The obtained resin was dissolved in PGMEA, and ion exchange was performed using a cation exchange resin and anion exchange resin for 4 hours to obtain a solution of the desired compound.

[0109]

[0110] <Synthesis Example 13> In a flask, 15.00 g of Cz, 16.36 g of 4-phenylbenzaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.43 g of MSA, and 47.69 g of PGMEA were placed. The mixture was then heated to 115°C under nitrogen for approximately 4.5 hours. After the reaction was stopped, the precipitate was obtained by precipitating the compound with methanol and drying it to obtain compound (1-13). The weight-average molecular weight (Mw) obtained by GPC, converted to polystyrene, was approximately 3,600. The obtained resin was dissolved in PGMEA, and ion exchange was performed using cation exchange resin and anion exchange resin for 4 hours to obtain a solution of the desired compound.

[0111]

[0112] <Synthesis Example 14> In a flask, 7.00 g of Cz, 9.72 g of 1-pyrenecarboxaldehyde, 1.59 g of p-toluenesulfonic acid monohydrate (manufactured by Tokyo Chemical Industry Co., Ltd.), and 27.48 g of PGMEA were placed. The mixture was then heated under nitrogen until reflux and allowed to react for approximately 1 hour. After the reaction was stopped, the precipitate was obtained by precipitating the compound with methanol and drying it to obtain compound (1-14). The weight-average molecular weight (Mw) obtained by GPC, converted to polystyrene, was approximately 1,300. The obtained resin was dissolved in CYH, and ion exchange was performed using cation exchange resin and anion exchange resin for 4 hours to obtain a solution of the desired compound.

[0113]

[0114] <Synthesis Example 15> In a flask, 8.00 g of Cz, 8.63 g of 9-fumonisin (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.30 g of MSA, and 18.93 g of PGMEA were placed. The mixture was then heated under nitrogen until reflux for approximately 1.5 hours. The resin (1-15) was obtained by precipitating the resin with methanol and drying it. The weight-average molecular weight (Mw) obtained by GPC, converted to polystyrene, was approximately 2,600. The obtained resin was dissolved in PGMEA, and ion exchange was performed using cation exchange resin and anion exchange resin for 4 hours to obtain the desired polymer solution.

[0115]

[0116] <Synthesis Example 16> In a flask, 8.00 g of Cz, 0.77 g of 1-naphthol (manufactured by Tokyo Chemical Industry Co., Ltd.), 9.59 g of 9-fenestrant (manufactured by Tokyo Chemical Industry Co., Ltd.), 1.28 g of MSA, and 36.46 g of PGMEA were placed. The mixture was then heated under nitrogen until reflux, and after approximately 13 hours, the resin was precipitated using methanol and dried to obtain resin (1-16). The weight-average molecular weight (Mw) obtained by GPC, converted to polystyrene, was approximately 2,800. The obtained resin was dissolved in PGMEA, and ion exchange was performed using cation exchange resin and anion exchange resin for 4 hours to obtain the desired polymer solution.

[0117]

[0118] <Synthesis Example 17> Add 6.00 g of Cz and p-naphthol benzyl alcohol (p-) to the flask. Naphtholbenzein (manufactured by Fujifilm and Wako Pure Chemical Industries, Ltd.) 4.48 g, 9-fentanyl (manufactured by Tokyo Chemical Industry Co., Ltd.) 8.63 g, MSA 1.15 g, and PGMEA 30.39 g. Subsequently, the mixture was heated under nitrogen until reflux for approximately 14.5 hours. The resin was then precipitated using methanol and dried to obtain resin (1-17). The weight-average molecular weight (Mw) obtained by GPC, converted to polystyrene, was approximately 3,000. The obtained resin was dissolved in PGMEA, and ion exchange was performed using cation exchange resin and anion exchange resin for 4 hours to obtain the desired polymer solution.

[0119]

[0120] <Comparative Synthesis Example 1> In a flask, 8.00 g of N-ethylcarbazole (manufactured by Tokyo Chemical Industry Co., Ltd.), 4.35 g of benzaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.59 g of MSA, and 30.19 g of PGMEA were placed. The mixture was then heated under nitrogen until reflux and allowed to react for approximately 3 hours. After the reaction was stopped, the precipitate was obtained by precipitating the compound with methanol and drying it to obtain compound (2-1). The weight-average molecular weight (Mw) obtained by GPC, converted to polystyrene, was 950. The obtained resin was dissolved in CYH, and ion exchange was performed using cation exchange resin and anion exchange resin for 4 hours to obtain a solution of the desired compound.

[0121]

[0122] <Comparative Synthesis Example 2> In a flask, 10.00 g of triphenylamine (manufactured by Tokyo Chemical Industry Co., Ltd.), 7.43 g of 4-phenylbenzaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.39 g of MSA, and 53.46 g of PGMEA were placed. The mixture was then heated to 100°C under nitrogen for approximately 15 hours. After the reaction was stopped, the precipitate was obtained by precipitating the compound with methanol and drying it to obtain compound (2-2). The weight-average molecular weight (Mw) obtained by GPC, converted to polystyrene, was 1,900. The obtained resin was dissolved in CYH, and ion exchange was performed using cation exchange resin and anion exchange resin for 4 hours to obtain a solution of the desired compound.

[0123]

[0124] <Comparative Synthesis Example 3> In a flask, 10.00 g of TEP-TPA (manufactured by Asahi Organics Co., Ltd.), 4.48 g of benzaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.81 g of MSA, and 35.67 g of PGME were placed. The mixture was then heated under nitrogen until reflux and allowed to react for approximately 4 hours. After the reaction was stopped, the precipitate was obtained by precipitating the precipitate with a methanol / water mixture and drying it to obtain compound (2-1). The weight-average molecular weight (Mw) obtained by GPC, converted to polystyrene, was 195,000. The obtained resin was dissolved in PGME, and ion exchange was performed using a cation exchange resin and anion exchange resin for 4 hours to obtain a solution of the desired compound.

[0125]

[0126] <Comparative Synthesis Example 4> In a flask, 10.00 g of 1,5-dihydroxynaphthalene (manufactured by Tokyo Chemical Industry Co., Ltd.), 6.62 g of benzaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.), 1.20 g of MSA, and 41.58 g of PGMEA were placed. The mixture was then heated under nitrogen until reflux was reached, allowing the reaction to proceed for approximately 1.5 hours. After the reaction was stopped, the precipitate was obtained by precipitating the compound with methanol and drying it to obtain compound (2-2). The weight-average molecular weight (Mw) obtained by GPC, converted to polystyrene, was 5,300. The obtained resin was dissolved in PGMEA, and ion exchange was performed using cation exchange resin and anion exchange resin for 4 hours to obtain a solution of the desired compound.

[0127]

[0128] <Comparative Synthesis Example 5> In a flask, 20.00 g of 9,9-bis(4-hydroxyphenyl)benzaldehyde, 6.06 g of benzaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.), 1.10 g of MSA, and 40.73 g of PGMEA were placed. The mixture was then heated under nitrogen until reflux for approximately 6.5 hours. After the reaction was stopped, the precipitate was obtained by precipitating the precipitate with a methanol / water mixture and drying it to obtain compounds (2-3). The weight-average molecular weight (Mw) obtained by GPC, converted to polystyrene, was 3,850. The obtained resin was dissolved in PGMEA, and ion exchange was performed using a cation exchange resin and anion exchange resin for 4 hours to obtain a solution of the desired compound.

[0129]

[0130] <Example 1> In Synthesis Example 1, a resin solution (solid content 18.14% by mass) was obtained. 3.21g of this resin solution was dissolved by adding 0.15g of PL-LI (manufactured by Mizuki Chemical Co., Ltd.), 1.09g of PGME containing 2% by mass TAG2689 (manufactured by King Industries), 0.06g of PGMEA containing 1% by mass surfactant (manufactured by DIC, MegafacR-40), 2.79g of PGMEA, 1.78g of PGME, and 5.92g of CYH. The solution was then filtered using a polytetrafluoroethylene microfilter with a pore size of 0.1μm to prepare a solution of the inhibitor lower membrane formation composition.

[0131] <Example 2> In Synthesis Example 2, a resin solution (solid content 20.53% by mass) was obtained. 30.43g of this resin solution was dissolved by adding 0.15g of PL-LI, 2% by mass pyridinium p-toluenesulfonic acid (manufactured by Tsui Chemicals Co., Ltd.) containing 11.71g of PGME, 0.62g of PGMEA containing 1% by mass surfactant, 63.98g of PGMEA, 55.11g of PGME, and 66.59g of CYH. The solution was then filtered using a polytetrafluoroethylene microfilter with a pore size of 0.1μm to prepare a solution of the inhibitor lower membrane formation composition.

[0132] <Example 3> In Synthesis Example 3, a resin solution (solid content 20.08% by mass) was obtained. 1.56g of PL-LI, 11.71g of PGME containing 2% by mass of p-toluenesulfonic acid pyridine salt, 0.62g of PGMEA containing 1% by mass of surfactant, 129.88g of PGMEA, and 55.11g of PGME were added to 31.11g of this resin solution to dissolve it. The solution was then filtered using a polytetrafluoroethylene microfilter with a pore size of 0.1μm to prepare a solution of the inhibitor lower membrane formation composition.

[0133] <Example 4> In Synthesis Example 4, a resin solution (solid content 20.35% by mass) was obtained. 30.70g of this resin solution was dissolved by adding 1.56g of PL-LI, 11.71g of PGME containing 2% by mass of p-toluenesulfonic acid pyridine salt, 0.62g of PGMEA containing 1% by mass of surfactant, 130.29g of PGMEA, and 55.11g of PGME. The solution was then filtered using a polytetrafluoroethylene microfilter with a pore size of 0.1μm to prepare a solution of the inhibitor lower membrane formation composition.

[0134] <Example 5> In Synthesis Example 5, a resin solution (solid content 20.88% by mass) was obtained. 1.56g of PL-LI, 11.71g of PGME containing 2% by mass of p-toluenesulfonic acid pyridine salt, 0.62g of PGMEA containing 1% by mass of surfactant, 130.07g of PGMEA, and 55.11g of PGME were added to 29.92g of this resin solution to dissolve it. The solution was then filtered using a polytetrafluoroethylene microfilter with a pore size of 0.1μm to prepare a solution of the inhibitor lower membrane formation composition.

[0135] <Example 6> In Synthesis Example 6, a resin solution (solid content 19.94% by mass) was obtained. 31.33g of this resin solution was dissolved by adding 1.56g of PL-LI, 11.71g of PGME containing 2% by mass of p-toluenesulfonic acid pyridine salt, 0.62g of PGMEA containing 1% by mass of surfactant, 129.66g of PGMEA, and 55.11g of PGME. The solution was then filtered using a polytetrafluoroethylene microfilter with a pore size of 0.1μm to prepare a solution of the inhibitor lower membrane formation composition.

[0136] <Example 7> In Synthesis Example 7, a resin solution (solid content 19.78% by mass) was obtained. 2.35g of this resin solution was dissolved by adding 0.12g of PL-LI, 0.87g of PGME containing 2% by mass TAG2689, 0.05g of PGMEA containing 1% by mass surfactant, 2.83g of PGMEA, 2.02g of PGME, and 6.75g of CYH. The solution was then filtered using a polytetrafluoroethylene microfilter with a pore size of 0.1μm to prepare a solution of the inhibitor lower membrane formation composition.

[0137] <Example 8> In Synthesis Example 8, a resin solution (solid content 17.72% by mass) was obtained. 2.63g of this resin solution was dissolved by adding 0.12g of PL-LI, 0.87g of PGME containing 2% by mass TAG2689, 0.05g of PGMEA containing 1% by mass surfactant, 2.83g of PGMEA, 2.02g of PGME, and 6.48g of CYH. The solution was then filtered using a polytetrafluoroethylene microfilter with a pore size of 0.1μm to prepare a solution of the inhibitor lower membrane formation composition.

[0138] <Example 9> In Synthesis Example 9, a resin solution (30.00% by mass of solids) was obtained. 0.12g of PL-LI, 0.87g of PGME containing 2% by mass of TAG2689, 0.05g of PGMEA containing 1% by mass of surfactant, 8.95g of PGMEA, and 3.46g of PGME were added to 1.55g of this resin solution to dissolve it. The solution was then filtered using a polytetrafluoroethylene microfilter with a pore size of 0.1μm to prepare a solution of the inhibitor lower membrane formation composition.

[0139] <Example 10> In Synthesis Example 10, a resin solution (30.00% by mass of solids) was obtained. 0.12g of PL-LI, 0.87g of PGME containing 2% by mass of TAG2689, 0.05g of PGMEA containing 1% by mass of surfactant, 2.83g of PGMEA, 2.02g of PGME, and 7.55g of CYH were added to 1.55g of this resin solution to dissolve it. The solution was then filtered using a polytetrafluoroethylene microfilter with a pore size of 0.1μm to prepare a solution of the inhibitor lower membrane formation composition.

[0140] <Example 11> In Synthesis Example 11, a resin solution (solid content 21.70% by mass) was obtained. 0.86g of PL-LI, 3.24g of PGME containing 2% by mass of p-toluenesulfonic acid pyridine salt, 0.43g of PGMEA containing 1% by mass of surfactant, 41.89g of PGMEA, 40.25g of PGME, and 43.43g of CYH were added to 19.90g of this resin solution to dissolve it. The solution was then filtered using a polytetrafluoroethylene microfilter with a pore size of 0.1μm to prepare a solution of the inhibitor lower membrane formation composition.

[0141] <Example 12> In Synthesis Example 12, a resin solution (solid content 30.30% by mass) was obtained. 0.12g of PL-LI, 0.87g of PGME containing 2% by mass TAG2689, 0.05g of PGMEA containing 1% by mass surfactant, 8.96g of PGMEA, and 3.46g of PGME were added to 1.54g of this resin solution to dissolve it. The solution was then filtered using a polytetrafluoroethylene microfilter with a pore size of 0.1μm to prepare a solution of the inhibitor lower membrane formation composition.

[0142] <Example 13> In Synthesis Example 13, a resin solution (solid content 21.56% by mass) was obtained. 0.14g of PL-LI, 0.55g of PGME containing 2% by mass TAG2689, 0.06g of PGMEA containing 1% by mass surfactant, 11.45g of PGMEA, and 5.25g of PGME were added to 2.55g of this resin solution to dissolve it. The solution was then filtered using a polytetrafluoroethylene microfilter with a pore size of 0.1μm to prepare a solution of the inhibitor lower membrane formation composition.

[0143] <Example 14> In Synthesis Example 14, a resin solution (solid content 20.71% by mass) was obtained. 2.25g of this resin solution was dissolved by adding 0.12g of PL-LI, 0.87g of PGME containing 2% by mass TAG2689, 0.05g of PGMEA containing 1% by mass surfactant, 2.83g of PGMEA, 2.02g of PGME, and 6.86g of CYH. The solution was then filtered using a polytetrafluoroethylene microfilter with a pore size of 0.1μm to prepare a solution of the inhibitor lower membrane formation composition.

[0144] <Example 15> In Synthesis Example 15, a resin solution (30.00% by mass of solids) was obtained. 0.12g of PL-LI, 0.87g of PGME containing 2% by mass of TAG2689, 0.05g of PGMEA containing 1% by mass of surfactant, 8.95g of PGMEA, and 3.46g of PGME were added to 1.55g of this resin solution to dissolve it. The solution was then filtered using a polytetrafluoroethylene microfilter with a pore size of 0.1μm to prepare a solution of the inhibitor lower membrane formation composition.

[0145] <Example 16> In Synthesis Example 16, a resin solution (solid content 16.73% by mass) was obtained. 4.08g of this resin solution was dissolved by adding 0.10g of PL-LI, 0.68g of PGME containing 2% by mass of p-toluenesulfonic acid pyridine salt, 0.07g of PGMEA containing 1% by mass of surfactant, 9.97g of PGMEA, and 5.09g of PGME. The solution was then filtered using a polytetrafluoroethylene microfilter with a pore size of 0.1μm to prepare a solution of the inhibitor lower membrane formation composition.

[0146] <Example 17> In Synthesis Example 17, a resin solution (solid content 16.96% by mass) was obtained. 4.03g of this resin solution was dissolved by adding 0.10g of PL-LI, 0.68g of PGME containing 2% by mass of p-toluenesulfonic acid pyridine salt, 0.07g of PGMEA containing 1% by mass of surfactant, 10.0g of PGMEA, and 5.09g of PGME. The solution was then filtered using a polytetrafluoroethylene microfilter with a pore size of 0.1μm to prepare a solution of the inhibitor lower membrane formation composition.

[0147] <Comparative Example 1> In Comparative Synthesis Example 1, a resin solution (solid content 18.47% by mass) was obtained. 2.52g of this resin solution was dissolved by adding 0.12g of PL-LI, 0.87g of PGME containing 2% by mass TAG2689, 0.05g of PGMEA containing 1% by mass surfactant, 2.83g of PGMEA, 2.02g of PGME, and 6.58g of CYH. The solution was then filtered using a 0.1μm polytetrafluoroethylene microfilter to prepare a solution of the inhibitor lower membrane formation composition.

[0148] <Comparative Example 2> In Comparative Synthesis Example 2, a resin solution (solid content 18.08% by mass) was obtained. 2.58g of this resin solution was dissolved by adding 0.12g of TMOM-BP (manufactured by Honshu Chemical Industry Co., Ltd.), 0.87g of PGME containing 2% by mass of p-toluenesulfonic acid pyridine salt, 0.05g of PGMEA containing 1% by mass of surfactant, 1.89g of PGMEA, 3.02g of PGME, and 11.5g of CYH. The solution was then filtered using a 0.1μm diameter polytetrafluoroethylene microfilter to prepare a solution of the inhibitor lower membrane formation composition.

[0149] <Comparative Example 3> In Comparative Synthesis Example 3, a resin solution (solid content 15.22% by mass) was obtained. 3.06g of this resin solution was dissolved by adding 0.12g of PL-LI, 0.87g of PGME containing 2% by mass of p-toluenesulfonic acid pyridine salt, 0.05g of PGMEA containing 1% by mass of surfactant, 5.77g of PGMEA, and 10.13g of PGME. The solution was then filtered using a polytetrafluoroethylene microfilter with a pore size of 0.1μm to prepare a solution of the inhibitor lower membrane formation composition.

[0150] <Comparative Example 4> In Comparative Synthesis Example 4, a resin solution (solid content 18.21% by mass) was obtained. 2.56g of this resin solution was dissolved by adding 0.12g of PL-LI, 0.87g of PGME containing 2% by mass of p-toluenesulfonic acid pyridine salt, 0.05g of PGMEA containing 1% by mass of surfactant, 1.89g of PGMEA, and 14.51g of PGME. The solution was then filtered using a polytetrafluoroethylene microfilter with a pore size of 0.1μm to prepare a solution of the inhibitor lower membrane formation composition.

[0151] <Comparative Example 5> In Comparative Synthesis Example 5, a resin solution (solid content 20.18% by mass) was obtained. 2.31 g of this resin solution was dissolved by adding 0.12 g of PL-LI, 0.87 g of PGME containing 2% by mass of p-toluenesulfonic acid pyridine salt, 0.05 g of PGMEA containing 1% by mass of surfactant, 11.69 g of PGMEA, and 4.96 g of PGME. The solution was then filtered using a polytetrafluoroethylene microfilter with a pore size of 0.1 μm to prepare a solution of the inhibitor lower membrane formation composition.

[0152] <Comparative Example 6> In Comparative Synthesis Example 3, a resin solution (solid content 15.22% by mass) was obtained. 3.06g of this resin solution was dissolved by adding 0.12g of PL-LI, 0.87g of PGME containing 2% by mass TAG2689, 0.05g of PGMEA containing 1% by mass surfactant, 5.77g of PGMEA, and 10.13g of PGME. The solution was then filtered using a polytetrafluoroethylene microfilter with a pore size of 0.1μm to prepare a solution of the inhibitor lower membrane formation composition.

[0153] <Comparative Example 7> In Comparative Synthesis Example 4, a resin solution (solid content 18.21% by mass) was obtained. 2.56g of this resin solution was dissolved by adding 0.12g of PL-LI, 0.87g of PGME containing 2% by mass TAG2689, 0.05g of PGMEA containing 1% by mass surfactant, 1.89g of PGMEA, and 14.51g of PGME. The solution was then filtered using a polytetrafluoroethylene microfilter with a pore size of 0.1μm to prepare a solution of the inhibitor lower membrane formation composition.

[0154] <Comparative Example 8> In Comparative Synthesis Example 5, a resin solution (solid content 20.18% by mass) was obtained. 2.31 g of this resin solution was dissolved by adding 0.12 g of PL-LI, 0.87 g of PGME containing 2% by mass TAG2689, 0.05 g of PGMEA containing 1% by mass surfactant, 11.69 g of PGMEA, and 4.96 g of PGME. The solution was then filtered using a polytetrafluoroethylene microfilter with a pore size of 0.1 μm to prepare a solution of the inhibitor lower membrane formation composition.

[0155] (Precipitation test of inhibitor solvent) Solutions of the resist underlayer film formation compositions prepared in Comparative Examples 1-8 and Examples 1-17 were coated onto silicon wafers using a spin coater. The wafers were then heated on a hot plate at 240°C for 60 seconds or 350°C for 60 seconds to form resist underlayer films (65 nm thick). These resist underlayer films were then impregnated with a general-purpose diluent of PGME / PGMEA = 7 / 3. The resist underlayer films were insoluble, confirming sufficient curing properties.

[0156] (Measurement of sublimation content) The amount of sublimation was measured using the sublimation measuring apparatus described in International Publication No. 2007 / 111147. Sublimation refers to the components that escape from the film into the atmosphere during firing. The resist lower layer film forming compositions prepared in Comparative Examples 1-2 and Examples 1-17 were coated on silicon wafers and fired at 240°C for 60 seconds. The amount of sublimation was measured when the film thickness reached 65 nm. Compared to the comparative examples, those with less sublimation were defined as "0".

[0157]

[0158] The comparative example has a high amount of sublimation, which raises concerns about potential device contamination. On the other hand, the embodiment has a low amount of sublimation, thereby suppressing device contamination.

[0159] (Coating performance test) The solutions of the resist underlayer film formation compositions prepared in Comparative Examples 1-2 and Examples 1-17 were coated onto silicon wafers using a spin coater, and then fired at 240°C for 60 seconds on a hot plate to form the resist underlayer film. Subsequently, the film thickness of the resist underlayer film was measured, and the value was calculated based on "film thickness deviation (maximum film thickness - minimum film thickness) / average film thickness × 100". A low value indicates good coatability. For the corresponding comparative examples, good coatability was judged as "0".

[0160]

[0161] (Drug resistance test) The solutions of the resist underlayer film formation compositions prepared in Comparative Examples 1-6 and Examples 1-17 were coated onto SiON using a spin coater. The resist underlayer film (65 nm thick) was formed by firing at 240°C for 60 seconds or 350°C for 60 seconds on a hot plate. A silicon hard mask layer (20 nm thick) and a resist layer (AR2772JN-14, manufactured by JSR Corporation, 120 nm thick) were formed on top of this layer. The resist pattern was obtained by exposure and development at a wavelength of 193 nm using the mask. Subsequently, the resist pattern was transferred to the resist underlayer film by dry etching using a fluorine-based gas and an oxygen-based gas using an etching apparatus manufactured by Lam Research Corporation. The pattern shape was confirmed using a CG-4100 manufactured by Hitachi Technology Corporation, confirming a line pattern of 50 nm.

[0162] The patterned wafers obtained here were diced and immersed in SARC-410 (manufactured by Entegris Japan Co., Ltd.) heated to 30°C. After immersion, the wafers were removed, rinsed with water, and dried. The wafers were observed using a scanning electron microscope (Regulus 8240) to confirm whether the pattern shape formed by the resist underlayer had deteriorated or collapsed. No deterioration or collapse of the pattern shape was observed, indicating high resistance to the chemical solution. In contrast, cases where no deterioration or collapse of the pattern shape occurred even after prolonged immersion in the chemical solution were classified as "0".

[0163] [Industrial Applicability]

[0164] Therefore, the material of this patent, due to its low sublimation content, can suppress equipment contamination. Because of the low sublimation content, its coatability is also excellent. Furthermore, the polymer with a low hydroxyl content can still prevent pattern deterioration or collapse after chemical treatment. Therefore, as a material with high resistance to alkaline solutions, it is also suitable for processes using chemical solutions.

Claims

1. A resistive underlayer film forming composition comprising a solvent and a polymer comprising a unit structure (A) as shown in formula (1); 1. In formula (1), Ar1 and Ar2 each represent a benzene ring, R1 and R2 are each groups that substitute hydrogen atoms on the rings of Ar1 and Ar2, and are selected from halogen groups, cyano groups, alkyl groups with 2 to 10 carbon atoms, alkenyl groups with 2 to 10 carbon atoms, alkynyl groups with 2 to 10 carbon atoms, aryl groups with 6 to 40 carbon atoms, and combinations thereof, R4 is an aryl group with 6 to 40 carbon atoms, and the aryl group is substituted by a halogen group, cyano group, alkyl group with 5 to 10 carbon atoms, alkoxy group with 1 to 10 carbon atoms, alkenyl group with 2 to 10 carbon atoms, alkynyl group with 2 to 10 carbon atoms, or aryl group with 6 to 40 carbon atoms; R5 is a hydrogen atom, and n1 and n2 are each integers from 0 to 3.

2. The inhibitor underlayer film forming composition of claim 1, wherein R4 in the above formula (1) is an aryl group having 6 to 40 carbon atoms, and the aryl group is replaced by an aryl group having 6 to 40 carbon atoms.

3. The inhibitor underlayer film forming composition as claimed in claim 1 or 2, wherein R4 in the above formula (1) is a substituted group consisting of a combination of benzene rings.

4. The resistive underlayer film forming composition as claimed in claim 1 or 2, further comprising a crosslinking agent.

5. The resistive underlayer film forming composition as claimed in claim 1 or 2, further comprising an acid and / or an acid generating agent.

6. The composition of the lower layer film forming of the inhibitor as claimed in claim 1, wherein the boiling point of the aforementioned solvent is above 160°C.

7. A resistive underlayer film, which is a sintered product of a coated film composed of a resistive underlayer film forming composition as claimed in any one of claims 1 to 6.

8. A method for manufacturing a semiconductor device, comprising: a step of forming a resist underlayer film on a semiconductor substrate using a resist underlayer film forming composition as described in any one of claims 1 to 6; a step of forming a resist film on the formed resist underlayer film; a step of forming a resist pattern by irradiating the formed resist film with light or electron lines and performing development; a step of patterning the resist underlayer film by etching the formed resist pattern; and a step of processing a semiconductor substrate using the patterned resist underlayer film.

9. A method for manufacturing a semiconductor device, comprising: forming a resist underlayer film on a semiconductor substrate using a resist underlayer film forming composition as described in any one of claims 1 to 6; forming a hard mask on the formed resist underlayer film; forming a resist film on the formed hard mask; forming a resist pattern by irradiating the formed resist film with light or electron lines and developing it; etching the hard mask through the formed resist pattern; etching the aforementioned resist underlayer film through the etched hard mask; and removing the hard mask.

10. The method for manufacturing a semiconductor device as claimed in claim 9, further comprising: a step of forming a vapor-deposited film on a lower layer film after the hard mask has been removed; a step of processing the formed vapor-deposited film by etching; a step of removing the lower layer film; and a step of processing a semiconductor substrate by vapor-depositing the film.

11. A method for manufacturing a semiconductor device as claimed in any one of claims 8 to 10, wherein the semiconductor substrate is a stepped substrate.

12. A polymer comprising the unit structure (A) shown in formula (1); 12. In formula (1), Ar1 and Ar2 each represent a benzene ring, R1 and R2 each represent a group in which hydrogen atoms on the rings of Ar1 and Ar2 are substituted, and are selected from halogen groups, cyano groups, alkyl groups with 2 to 10 carbon atoms, alkenyl groups with 2 to 10 carbon atoms, alkynyl groups with 2 to 10 carbon atoms, aryl groups with 6 to 40 carbon atoms, and combinations thereof, R4 is a group consisting of a combination of substituted benzene rings including biphenyl, and the benzene ring is substituted by halogen groups, cyano groups, alkyl groups with 5 to 10 carbon atoms, alkoxy groups with 1 to 10 carbon atoms, alkenyl groups with 2 to 10 carbon atoms, alkynyl groups with 2 to 10 carbon atoms, or aryl groups with 6 to 40 carbon atoms, R5 is a hydrogen atom, and n1 and n2 are each integers from 0 to 3.

13. The polymer of claim 12, wherein R4 in formula (1) above is a substituted biphenyl.