Resist underlayer film-forming composition

Abstract

To provide a new resist underlayer film-forming composition capable of giving a hydrophobic underlayer film having high adhesiveness to an upper layer film and hardly peeled off, having good coatability and exhibiting sufficient resistance even to a chemical liquid.SOLUTION: A resist underlayer film-forming composition includes a polymer containing a structural unit represented by formula (1) and / or formula (2). (Ar1 and Ar2 represent a benzene ring or a naphthalene ring, Ar3 represents an aromatic compound having 6 to 60 carbon atoms which may contain a nitrogen atom, and R3 and R8 represent an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, or a combination thereof. ) SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a resist underlayer film-forming composition, a resist underlayer film that is a fired product of a coating film made of the composition, and a method for manufacturing a semiconductor device using the composition. [Background technology]

[0002] In recent years, there has been a demand for resist underlayer film-forming compositions for use in lithography processes for manufacturing semiconductor devices that are free from intermixing with upper layers, can produce excellent resist patterns, and can form resist underlayer films for lithography that have a lower dry etching rate than the upper layers (hard masks: coated or vapor-deposited films) and semiconductor substrates. For this purpose, the use of polymers having repeating units containing benzene rings or naphthalene rings has been proposed (Patent Document 1). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] WO 2013 / 047516 A1 Summary of the Invention [Problem to be solved by the invention]

[0004] However, conventional resist underlayer film-forming compositions have still not satisfied the requirements of exhibiting a high pure water contact angle, being able to provide a hydrophobic underlayer film that has high adhesion to an overlayer film and is resistant to peeling, and having good coatability, etc. Furthermore, in semiconductor manufacturing processes, treatments with chemical solutions are sometimes performed, and therefore the resist underlayer film is sometimes required to exhibit sufficient resistance to the chemical solutions used. [Means for solving the problem]

[0005] The present invention is intended to solve the above problems. That is, the present invention includes the following. [1] A solvent and a compound represented by the following formula (1) and / or the following formula (2): [ka] (In the formula, Ar 1 , and Ar 2 represents a benzene ring or a naphthalene ring, respectively, and Ar 1 , and Ar 2 may be bonded via a single bond, Ar 3 represents an aromatic compound having 6 to 60 carbon atoms which may contain a nitrogen atom, R 1 , and R 2 are Ar 1 , and Ar 2 is a group substituting a hydrogen atom on the ring of formula (I), and is selected from the group consisting of a halogen group, a nitro group, an amino group, a cyano group, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, and combinations thereof, and the alkyl group, the alkenyl group, the alkenyl group, and the aryl group may contain an ether bond, a ketone bond, or an ester bond; R 3 , and R 8 is selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, and combinations thereof, and the alkyl group, the alkenyl group, the alkynyl group, and the aryl group may contain an ether bond, a ketone bond, or an ester bond, and the aryl group may be substituted with an alkyl group having 1 to 10 carbon atoms substituted with a hydroxyl group; R 4 , and R 6is selected from the group consisting of a hydrogen atom, a trifluoromethyl group, an aryl group having 6 to 40 carbon atoms, and a heterocyclic group, and the aryl group and the heterocyclic group are optionally substituted with a halogen group, a nitro group, an amino group, a cyano group, a trifluoromethyl group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, or an aryl group having 6 to 40 carbon atoms, and the alkyl group, the alkenyl group, the alkynyl group, and the aryl group may contain an ether bond, a ketone bond, or an ester bond; R 5 , and R 7 is selected from the group consisting of a hydrogen atom, a trifluoromethyl group, an aryl group having 6 to 40 carbon atoms, and a heterocyclic group, and the aryl group and the heterocyclic group are optionally substituted with a halogen group, a nitro group, an amino group, a cyano group, a trifluoromethyl group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, or an aryl group having 6 to 40 carbon atoms, and the alkyl group, the alkenyl group, the alkynyl group, and the aryl group may contain an ether bond, a ketone bond, or an ester bond; and R 4 and R 5 and R 6 and R 7 may form a ring together with the carbon atom to which they are attached. n1 and n2 are each an integer from 0 to 3, n3 is 1 or more, and Ar 3 is an integer equal to or less than the number of substituents that can be substituted for n4 is 0 or 1, but when n4 is 0, R 8 Ar 3 It bonds to the nitrogen atom in A resist underlayer film-forming composition comprising a polymer containing a unit structure (A) represented by the following formula: [2] In the above formula (1), Ar 1 , and Ar 2 is a benzene ring. [3] In the above formula (2), Ar 3 is an optionally substituted benzene ring, naphthalene ring, or phenylindole ring. [4] In the above formula (1) or (2), R 4 , and R 6 is an aryl group having 6 to 40 carbon atoms, R 5 , and R 7 is a hydrogen atom The resist underlayer film-forming composition according to any one of [1] to [3]. [5] In the above formula (1) or (2), R 4 , and R 6 is an aromatic hydrocarbon group having 6 to 16 carbon atoms The resist underlayer film-forming composition according to any one of [1] to [4]. [6] The resist underlayer film forming composition according to any one of [1] to [5], further comprising a crosslinking agent. [7] The resist underlayer film forming composition according to any one of [1] to [6], further comprising an acid and / or an acid generator. [8] The resist underlayer film forming composition according to [1], wherein the boiling point of the solvent is 160°C or higher. [9] A resist underlayer film which is a fired product of a coating film comprising the resist underlayer film-forming composition according to any one of [1] to [8].

[10] A step of forming a resist underlayer film on a semiconductor substrate using the resist underlayer film-forming composition according to any one of [1] to [8]. 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 an electron beam and developing it; a step of etching and patterning the resist underlayer film through the formed resist pattern; and A process of processing a semiconductor substrate through a patterned resist underlayer film A method for manufacturing a semiconductor device comprising:

[11] A step of forming a resist underlayer film on a semiconductor substrate using the resist underlayer film-forming composition according to any one of [1] to [8]. forming a hard mask on the formed resist underlayer film; forming a resist film on the formed hard mask; a step of forming a resist pattern by irradiating the formed resist film with light or an electron beam and developing it; Etching the hard mask through the formed resist pattern; Etching the resist underlayer film through the etched hard mask; and Step of removing the hard mask A method for manufacturing a semiconductor device comprising:

[12] Furthermore, forming a vapor-deposited film (spacer) on the underlayer film from which the hard mask has been removed; a step of processing the formed vapor-deposited film (spacer) by etching; removing the underlayer film; and A process of processing a semiconductor substrate using spacers The method for manufacturing a semiconductor device according to

[11] , comprising:

[13] The method for manufacturing a semiconductor device according to any one of

[10] to

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

[0006] According to the present invention, there is provided a novel resist underlayer film-forming composition that satisfies the requirements of being able to provide a hydrophobic underlayer film that exhibits a high pure water contact angle, has high adhesion to an overlayer film, and is resistant to peeling, and has good coatability, and that can also exhibit other favorable properties, such as sufficient resistance to chemical solutions used in resist underlayer films. DETAILED DESCRIPTION OF THE INVENTION

[0007] <Resist Underlayer Film-Forming Composition> The resist underlayer film-forming composition according to the present invention comprises a solvent and a compound represented by the following formula (1) and / or the following formula (2): [ka] (In the formula, Ar 1 , and Ar 2 represents a benzene ring or a naphthalene ring, respectively, and Ar 1 , and Ar 2 may be bonded via a single bond, Ar 3 represents an aromatic compound having 6 to 60 carbon atoms which may contain a nitrogen atom, R 1 , and R 2 are Ar 1 , and Ar 2 is a group substituting a hydrogen atom on the ring of formula (I), and is selected from the group consisting of a halogen group, a nitro group, an amino group, a cyano group, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, and combinations thereof, and the alkyl group, the alkenyl group, the alkenyl group, and the aryl group may contain an ether bond, a ketone bond, or an ester bond; R 3 , and R 8 is selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, and combinations thereof, and the alkyl group, the alkenyl group, the alkynyl group, and the aryl group may contain an ether bond, a ketone bond, or an ester bond; R 4 , and R 6is selected from the group consisting of a hydrogen atom, a trifluoromethyl group, an aryl group having 6 to 40 carbon atoms, and a heterocyclic group, and the aryl group and the heterocyclic group are optionally substituted with a halogen group, a nitro group, an amino group, a cyano group, a trifluoromethyl group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, or an aryl group having 6 to 40 carbon atoms, and the alkyl group, the alkenyl group, the alkynyl group, and the aryl group may contain an ether bond, a ketone bond, or an ester bond; R 5 , and R 7 is selected from the group consisting of a hydrogen atom, a trifluoromethyl group, an aryl group having 6 to 40 carbon atoms, and a heterocyclic group, and the aryl group and the heterocyclic group are optionally substituted with a halogen group, a nitro group, an amino group, a cyano group, a trifluoromethyl group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, or an aryl group having 6 to 40 carbon atoms, and the alkyl group, the alkenyl group, the alkynyl group, and the aryl group may contain an ether bond, a ketone bond, or an ester bond; and R 4 and R 5 and R 6 and R 7 may form a ring together with the carbon atom to which they are attached. n1 and n2 are each an integer from 0 to 3, n3 is 1 or more, and Ar 3 is an integer equal to or less than the number of substituents that can be substituted for n4 is 0 or 1, but when n4 is 0, R 8 Ar 3 It bonds to the nitrogen atom in It contains a unit structure (A) represented by:

[0008] <Polymer containing unit structure (A) represented by formula (1) and / or formula (2)> Ar 1 , and Ar2 respectively represent a benzene ring or a naphthalene ring. Ar 1 and Ar 2 may be bonded via a single bond, and can form, for example, a carbazole skeleton. Ar 1 , and Ar 2 are preferably both benzene rings.

[0009] Ar 3 represents an aromatic compound having 6 to 60 carbon atoms which may contain a nitrogen atom. Specific examples include benzene, styrene, toluene, xylene, mesitylene, cumene, indene, naphthalene, biphenyl, azulene, anthracene, phenanthrene, naphthacene, triphenylene, pyrene, chrysene, fluorene, 9,9-diphenylfluorene, 9,9-dinaphthylfluorene, indole, phenylindole, purine, quinoline, isoquinoline, quinuclidine, acridine, phenazine, and carbazole.

[0010] R 1 , and R 2 are Ar 1 , and Ar 2 and is a group substituted for a hydrogen atom on the ring of the formula (I) above, selected from the group consisting of a halogen group, a nitro group, an amino group, a cyano group, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, and combinations thereof, and the alkyl group, the alkenyl group, the alkynyl group, and the aryl group may contain an ether bond, a ketone bond, or an ester bond.

[0011] Also, R 3 , and R 8is selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, and combinations thereof, and the alkyl group, the alkenyl group, the alkynyl group, and the aryl group may contain an ether bond, a ketone bond, or an ester bond, and the aryl group may be substituted with an alkyl group having 1 to 10 carbon atoms substituted with a hydroxyl group (i.e., the aryl group may have a hydroxyalkyl group having 1 to 10 carbon atoms as a substituent). When the aryl group is substituted with an alkyl group substituted with a hydroxyl group, the hydroxyl group is preferably substituted at the benzyl position, and the aryl group also includes those in which aromatic rings are connected to each other by a methine group substituted with a hydroxyl group (i.e., -Ar-C(OH)X 1 X 2 , Ar is an aryl group, X 1 and X 2 is a hydrogen atom or any organic group, preferably X 1 , X 2 (either of these is an aromatic group).

[0012] Halogen groups include fluorine, chlorine, bromine, and iodine.

[0013] Examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, an s-butyl group, a t-butyl group, an n-pentyl group, a 1-methyl-n-butyl group, a 2-methyl-n-butyl group, a 3-methyl-n-butyl group, a 1,1-dimethyl-n-propyl group, a 1,2-dimethyl-n-propyl group, a 2,2-dimethyl-n-propyl group, a 1-ethyl-n-propyl group, an n-hexyl group, a 1-methyl-n-pentyl group, a 2-methyl-n-pentyl ... a 1,1-dimethyl-n-butyl group, a 2,2-dimethyl-n-propyl group, a 1,1-dimethyl-n-propyl group, a 1,1-dimethyl-n-propyl group, a 1,2-dimethyl-n-propyl group, a 2,2-dimethyl-n-propyl group, a 1, Examples include a 1-n-pentyl group, a 4-methyl-n-pentyl group, a 1,1-dimethyl-n-butyl group, a 1,2-dimethyl-n-butyl group, a 1,3-dimethyl-n-butyl group, a 2,2-dimethyl-n-butyl group, a 2,3-dimethyl-n-butyl group, a 3,3-dimethyl-n-butyl group, a 1-ethyl-n-butyl group, a 2-ethyl-n-butyl group, a 1,1,2-trimethyl-n-propyl group, a 1,2,2-trimethyl-n-propyl group, a 1-ethyl-1-methyl-n-propyl group, and a 1-ethyl-2-methyl-n-propyl group.

[0014] It may also be a cyclic alkyl group, for example, a cyclopropyl group, a cyclobutyl group, a 1-methyl-cyclopropyl group, a 2-methyl-cyclopropyl group, a cyclopentyl group, a 1-methyl-cyclobutyl group, a 2-methyl-cyclobutyl group, a 3-methyl-cyclobutyl group, a 1,2-dimethyl-cyclopropyl group, a 2,3-dimethyl-cyclopropyl group, a 1-ethyl-cyclopropyl group, a 2-ethyl-cyclopropyl group, a cyclohexyl group, a 1-methyl-cyclopentyl group, a 2-methyl-cyclopentyl group, a 3-methyl-cyclopentyl group, a 1-ethyl-cyclobutyl group, a 2-ethyl-cyclobutyl group, a 3-ethyl-cyclobutyl group, a 1,2-dimethyl-cyclobutyl group, a 1,3 ...,3-dimethyl-cyclopropyl group, a 2,3-dimethyl-cyclopropyl group, a 2,3-dimethyl-cyclopropyl group, a 2,3-dimethyl-cyclopropyl group, a 2,3-dimethyl-cyclopropyl group, a 2,3-dimethyl-cyclopropyl group, a 2,3-dimethyl-cyclopropyl group, a 2,3-dimethyl-cyclopropyl group, a 2,3-dimethyl-cyclopropyl group, a 2,3-dimethyl-cyclopropyl group, a 2,3-dimethyl-cyclopropyl group, a 2,3-dimethyl-cyclopropyl group Examples of such cyclopropyl groups include 1-n-ethyl-cyclobutyl group, 2,2-dimethyl-cyclobutyl group, 2,3-dimethyl-cyclobutyl group, 2,4-dimethyl-cyclobutyl group, 3,3-dimethyl-cyclobutyl group, 1-n-propyl-cyclopropyl group, 2-n-propyl-cyclopropyl group, 1-i-propyl-cyclopropyl group, 2-i-propyl-cyclopropyl group, 1,2,2-trimethyl-cyclopropyl group, 1,2,3-trimethyl-cyclopropyl group, 2,2,3-trimethyl-cyclopropyl group, 1-ethyl-2-methyl-cyclopropyl group, 2-ethyl-1-methyl-cyclopropyl group, 2-ethyl-2-methyl-cyclopropyl group, and 2-ethyl-3-methyl-cyclopropyl group.

[0015] Examples of the alkenyl group having 2 to 10 carbon atoms include ethenyl, 1-propenyl, 2-propenyl, 1-methyl-1-ethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl, 1-ethylethenyl, 1-methyl-1-propenyl, 1-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-n-propylethenyl, 1-methyl-1-butenyl, 1-methyl-2-butenyl, and 1-methyl-3-butenyl. ethenyl group, 2-ethyl-2-propenyl group, 2-methyl-1-butenyl group, 2-methyl-2-butenyl group, 2-methyl-3-butenyl group, 3-methyl-1-butenyl group, 3-methyl-2-butenyl group, 3-methyl-3-butenyl group, 1,1-dimethyl-2-propenyl group, 1-i-propylethenyl group, 1,2-dimethyl-1-propenyl group, 1,2-dimethyl-2-propenyl group, 1-cyclopentenyl group, 2-cyclopentenyl group, 3-cyclopentenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group xenyl group, 1-methyl-1-pentenyl group, 1-methyl-2-pentenyl group, 1-methyl-3-pentenyl group, 1-methyl-4-pentenyl group, 1-n-butylethenyl group, 2-methyl-1-pentenyl group, 2-methyl-2-pentenyl group, 2-methyl-3-pentenyl group, 2-methyl-4-pentenyl group, 2-n-propyl-2-propenyl group, 3-methyl-1-pentenyl group, 3-methyl-2-pentenyl group, 3-methyl-3-pentenyl group, 3-methyl-4-pentenyl group, 3-ethyl-3-butenyl group, 4-methyl-1-pentenyl group, 4-methyl-2-pentenyl group, 4-methyl-3-pentenyl group, 4-methyl-4-pentenyl group, 1,1-dimethyl-2-butenyl group, 1,1-dimethyl-3-butenyl group, 1,2-dimethyl-1-butenyl group, 1,2-dimethyl-2-butenyl group, 1,2-dimethyl-3-butenyl group, 1-methyl-2-ethyl-2-propenyl group, 1-s-butylethenyl group, 1,3-dimethyl-1-butenyl group, 1,3-dimethyl-2-butenyl group, 1,3-dimethyl-3-butenyl group, 1-i-butylethenyl group, 2,2-dimethyl-3-butenyl group, 2,3-dimethyl-1-butenyl group, 2,3-dimethyl-2-butenyl group, 2,3-dimethyl-3-butenyl group, 2-i-propyl-2-propenyl group, 3,3-dimethyl-1-butenyl group, 1-ethyl-1-butenyl group, 1-ethyl-2-butenyl group, 1-ethyl-3-butenyl group, 1-n-propyl-1-propenyl group, 1-n-propyl-2-propenyl group, 2-ethyl-1-butenyl group, 2-ethyl-2-butenyl group, 2-ethyl-3-butenyl group, 1,1,2-trimethyl-2-propenyl group, 1-t-butylethenyl group, 1-methyl-1-ethyl-2-propenyl group, 1-ethyl-2-methyl-1-propenyl group, 1-ethyl-2-methyl-2-propenyl group, 1-i-propyl-1-propenyl group Examples of the alkyl group include phenyl group, 1-i-propyl-2-propenyl group, 1-methyl-2-cyclopentenyl group, 1-methyl-3-cyclopentenyl group, 2-methyl-1-cyclopentenyl group, 2-methyl-2-cyclopentenyl group, 2-methyl-3-cyclopentenyl group, 2-methyl-4-cyclopentenyl group, 2-methyl-5-cyclopentenyl group, 2-methylene-cyclopentyl group, 3-methyl-1-cyclopentenyl group, 3-methyl-2-cyclopentenyl group, 3-methyl-3-cyclopentenyl group, 3-methyl-4-cyclopentenyl group, 3-methyl-5-cyclopentenyl group, 3-methylene-cyclopentyl group, 1-cyclohexenyl group, 2-cyclohexenyl group, and 3-cyclohexenyl group.

[0016] Examples of the alkynyl group having 2 to 10 carbon atoms include an ethynyl group, a 1-propynyl group, and a 2-propynyl group.

[0017] Examples of the aryl group having 6 to 40 carbon atoms include a phenyl group, a benzyl group, a naphthyl group, an anthracenyl group, a phenanthrenyl group, a naphthacenyl group, a triphenylenyl group, a pyrenyl group, and a chrysenyl group.

[0018] The alkyl group, alkenyl group, alkynyl group, and aryl group may contain an ether bond (-O-), a ketone bond (-CO-), or an ester bond (-COO-, -OCO-).

[0019] R 4 , and R 6 is selected from the group consisting of a hydrogen atom, a trifluoromethyl group, an aryl group having 6 to 40 carbon atoms, and a heterocyclic group, and the aryl group and the heterocyclic group are optionally substituted with a halogen group, a nitro group, an amino group, a cyano group, a trifluoromethyl group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, or an aryl group having 6 to 40 carbon atoms, and the alkyl group, the alkenyl group, the alkynyl group, and the aryl group may contain an ether bond, a ketone bond, or an ester bond.

[0020] Also, R 5 , and R 7 is selected from the group consisting of a hydrogen atom, a trifluoromethyl group, an aryl group having 6 to 40 carbon atoms, and a heterocyclic group, and the aryl group and the heterocyclic group are optionally substituted with a halogen group, a nitro group, an amino group, a cyano group, a trifluoromethyl group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, or an aryl group having 6 to 40 carbon atoms, and the alkyl group, the alkenyl group, the alkynyl group, and the aryl group may contain an ether bond, a ketone bond, or an ester bond.

[0021] The heterocyclic group is a substituent derived from a heterocyclic compound, and specific examples thereof include a thiophene group, a furan group, a pyridine group, a pyrimidine group, a pyrazine group, a pyrrole group, an oxazole group, a thiazole group, an imidazole group, a quinoline group, a carbazole group, a quinazoline group, a purine group, an indolizine group, a benzothiophene group, a benzofuran group, an indole group, an acridine group, an isoindole group, a benzimidazole group, an isoquinoline group, a quinoxaline group, a cinnoline group, a pteridine group, a chromene group (benzopyran group), an isochromene group (benzopyran group), a xanthene group, Examples of such groups include a thiazole group, a pyrazole group, an imidazoline group, and an azine group. Among these, a thiophene group, a furan group, a pyridine group, a pyrimidine group, a pyrazine group, a pyrrole group, an oxazole group, a thiazole group, an imidazole group, a quinoline group, a carbazole group, a quinazoline group, a purine group, an indolizine group, a benzothiophene group, a benzofuran group, an indole group, and an acridine group are preferred, and a thiophene group, a furan group, a pyridine group, a pyrimidine group, a pyrrole group, an oxazole group, a thiazole group, an imidazole group, and a carbazole group are most preferred.

[0022] Examples of the alkoxy group having 1 to 10 carbon atoms include a group in which an etheric oxygen atom (—O—) is bonded to the terminal carbon atom of the alkyl group having 1 to 10 carbon atoms. Examples of such an alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, a cyclopropoxy group, an n-butoxy group, an i-butoxy group, an s-butoxy group, a t-butoxy group, a cyclobutoxy group, a 1-methyl-cyclopropoxy group, a 2-methyl-cyclopropoxy group, an n-pentoxy group, a 1-methyl-n-butoxy group, a 2-methyl-n-butoxy group, a 3-methyl-n-butoxy group, a 1,1-dimethyl-n-propoxy group, Examples include a 1,2-dimethyl-n-propoxy group, a 2,2-dimethyl-n-propoxy group, a 1-ethyl-n-propoxy group, a 1,1-diethyl-n-propoxy group, a cyclopentoxy group, a 1-methyl-cyclobutoxy group, a 2-methyl-cyclobutoxy group, a 3-methyl-cyclobutoxy group, a 1,2-dimethyl-cyclopropoxy group, a 2,3-dimethyl-cyclopropoxy group, a 1-ethyl-cyclopropoxy group, and a 2-ethyl-cyclopropoxy group.

[0023] R 4 and R 5 and R 6 and R 7 may form a ring (eg, a fluorene ring) together with the carbon atom to which they are attached.

[0024] n1 and n2 each represent an integer of 0 to 3, preferably an integer of 0 to 2, more preferably an integer of 0 to 1, and most preferably 0.

[0025] n3 is 1 or more, preferably 2 or more, and Ar 3 is an integer equal to or smaller than the number of substituents that can be substituted for, preferably an integer of 6 or smaller, more preferably an integer of 4 or smaller, and most preferably an integer of 2 or smaller.

[0026] Among the compounds represented by the above formula (1) or formula (2), some preferred ones are as follows. ·Ar 1 , and Ar 2is a benzene ring. ·Ar 3 is an optionally substituted benzene ring, naphthalene ring, diphenylfluorene ring, or phenylindole ring. ·R 4 , and R 6 is an aryl group having 6 to 40 carbon atoms, and R 5 , and R 7 is a hydrogen atom. ·R 4 , and R 6 is an aromatic hydrocarbon group having 6 to 16 carbon atoms,

[0027] <Solvent> The solvent for the resist underlayer film-forming composition of the present invention is not particularly limited, as long as it can dissolve the compound represented by the above formula (1) or the above formula (2). In particular, since the resist underlayer film-forming composition of the present invention is used in the state of a homogeneous solution, in consideration of its coating performance, it is recommended to use a solvent that is generally used in lithography processes in combination with the composition.

[0028] Examples of such solvents include methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, methyl isobutyl carbinol, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoether 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 ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-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, isobutyl lactate, 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 hydroxyacetate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutyrate, ethyl methoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-methoxybutyl acetate, 3-methoxypropyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl Examples of suitable solvents include 3-methyl-3-methoxybutylpropionate, 3-methyl-3-methoxybutyl butyrate, 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. These solvents can be used alone or in combination of two or more.

[0029] In addition, the following compounds described in WO2018 / 131562A1 can also be used. [ka] (R in formula (i) 1 , R 2 and R 3 each represents a hydrogen atom, an oxygen atom, a sulfur atom, or an alkyl group having 1 to 20 carbon atoms which may be interrupted by an amide bond, and may be the same or different and may be bonded to each other to form a ring structure.

[0030] Examples of the alkyl group having 1 to 20 carbon atoms include linear or branched alkyl groups that may or may not have a substituent, such as a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, n-hexyl group, isohexyl group, n-heptyl group, n-octyl group, cyclohexyl group, 2-ethylhexyl group, n-nonyl group, isononyl group, p-tert-butylcyclohexyl group, n-decyl group, n-dodecylnonyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, and eicosyl group. Preferably, it is an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, and even more preferably an alkyl group having 1 to 4 carbon atoms.

[0031] Examples of alkyl groups having 1 to 20 carbon atoms interrupted by an oxygen atom, a sulfur atom, or an amide bond include those containing the structural unit -CH2-O-, -CH2-S-, -CH2-NHCO-, or -CH2-CONH-. The -O-, -S-, -NHCO-, or -CONH- may be present in one unit or in two or more units in the alkyl group. Specific examples of alkyl groups having 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, butyl ... and the like, and further, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, or octadecyl groups, each of which is substituted with a methoxy, ethoxy, propoxy, butoxy, methylthio, ethylthio, propylthio, butylthio, methylcarbonylamino, ethylcarbonylamino, methylaminocarbonyl, ethylaminocarbonyl, or the like. Preferred are methoxy, ethoxy, methylthio, and ethylthio groups, and more preferred are methoxy and ethoxy groups.

[0032] These solvents have a relatively high boiling point, and are therefore effective in imparting high embedding properties and high planarization properties to the resist underlayer film-forming composition.

[0033] Specific examples of preferred compounds represented by formula (i) are shown below. [ka]

[0034] Among the above, 3-methoxy-N,N-dimethylpropionamide, N,N-dimethylisobutyramide, and The following formula: [ka] Compounds represented by the formula (i) are preferably 3-methoxy-N,N-dimethylpropionamide and N,N-dimethylisobutyramide.

[0035] These solvents can be used alone or in combination. Among these solvents, those with a boiling point of 160°C or higher are preferred, including propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, butyl lactate, cyclohexanone, 3-methoxy-N,N-dimethylpropionamide, N,N-dimethylisobutyramide, 2,5-dimethylhexane-1,6-diyl diacetate (DAH; cas. 89182-68-3), and 1,6-diacetoxyhexane (cas. 6222-17-9). Particularly preferred are propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and N,N-dimethylisobutyramide.

[0036] These solvents can be used alone or in combination of two or more. The solid content of the composition excluding the organic solvent is, for example, 0.5 to 30% by mass, preferably 0.8 to 15% by mass.

[0037] <Optional ingredients> The resist underlayer film-forming composition of the present invention may further contain, as an optional component, at least one of a crosslinking agent, an acid and / or an acid generator, a thermal acid generator, and a surfactant.

[0038] (Crosslinking agent) The resist underlayer film-forming composition of the present invention may further contain a crosslinking agent. A crosslinking compound having at least two crosslink-forming substituents is preferably used as the crosslinking agent. Examples of the crosslinking agent include melamine-based compounds, substituted urea-based compounds, and phenol-based compounds, or polymers thereof, each having a crosslink-forming substituent such as a methylol group or a methoxymethyl group. Specific examples of the substituted urea compounds include methoxymethylated glycoluril, butoxymethylated glycoluril, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzoguwanamine, and butoxymethylated benzoguwanamine. Examples of the substituted urea compounds include methoxymethylated urea, butoxymethylated urea, and methoxymethylated thiourea. Examples of the substituted urea compounds include tetramethoxymethyl urea and tetrabutoxymethyl urea. Condensates of these compounds can also be used. Examples of the phenolic compounds include tetrahydroxymethyl biphenol, tetramethoxymethyl biphenol, tetrahydroxymethyl bisphenol, tetramethoxymethyl bisphenol, and compounds represented by the following formula: [ka] [ka]

[0039] The crosslinking agent may also be a compound having at least two epoxy groups. Examples of such compounds include tris(2,3-epoxypropyl)isocyanurate, 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-epoxycyclohexanecarboxylate, trimethylolethane triglycidyl ether, bisphenol-A diglycidyl ether, and Epolead (registered trademark) GT-401, GT-403, GT-301, and GT-30 manufactured by Daicel Corporation. 2. Celloxide (registered trademark) 2021, 3000; 1001, 1002, 1003, 1004, 1007, 1009, 1010, 828, 807, 152, 154, 180S75, 871, 872 manufactured by Mitsubishi Chemical Corporation; EPPN201, 202, EOCN-102, 103S, 104S, 1020, 1025, 1027 manufactured by Nippon Kayaku Co., Ltd.; and Denacol (registered trademark) EX-25 manufactured by Nagase ChemteX Corporation. Examples of epoxy resins include EX-2, EX-611, EX-612, EX-614, EX-622, EX-411, EX-512, EX-522, EX-421, EX-313, EX-314, and EX-321; BASF Japan Ltd.'s CY175, CY177, CY179, CY182, CY184, and CY192; and DIC Corporation's Epiclon 200, 400, 7015, 835LV, and 850CRP. The compound having at least two epoxy groups can also be an epoxy resin having an amino group. Examples of such epoxy resins include YH-434 and YH-434L (manufactured by Shin-Nichika Epoxy Manufacturing Co., Ltd.).

[0040] The crosslinking agent may also be a compound having at least two blocked isocyanate groups, such as Takenate (registered trademark) B-830 and B-870N manufactured by Mitsui Chemicals, Inc., and VESTANAT (registered trademark) B1358 / 100 manufactured by Evonik Degussa.

[0041] The crosslinking agent may also be a compound having at least two vinyl ether groups. Examples of such compounds include bis(4-(vinyloxymethyl)cyclohexylmethyl)glutarate, tri(ethylene glycol) divinyl ether, adipic acid divinyl ester, diethylene glycol divinyl ether, 1,2,4-tris(4-vinyloxybutyl) trimellitate, 1,3,5-tris(4-vinyloxybutyl) trimellitate, 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 cyclohexanedimethanol divinyl ether.

[0042] In addition, a crosslinking agent having high heat resistance can be used as the crosslinking agent. As a crosslinking agent having high heat resistance, a compound containing a crosslink-forming substituent having an aromatic ring (e.g., a benzene ring or a naphthalene ring) in the molecule can be preferably used.

[0043] This compound may be a compound having a partial structure of the following formula (4), or a polymer or oligomer having a repeating unit of the following formula (5). [ka] Above R 11 , R 12 , R 13 , and R 14 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and the alkyl groups mentioned above can be used. n1 is an integer of 1 to 4, n2 is an integer of 1 to (5-n1), and (n1+n2) is an integer of 2 to 5. n3 is an integer of 1 to 4, n4 is an integer of 0 to (4-n3), and (n3+n4) is an integer of 1 to 4. Oligomers and polymers having a repeating unit structure number of 2 to 100 or 2 to 50 can be used.

[0044] Examples of the compounds, polymers and oligomers of formula (4) and formula (5) are shown below. [ka] [ka] [ka]

[0045] The above compounds are available as products of Asahi Organic Chemicals Co., Ltd. and Honshu Chemical Industry Co., Ltd. For example, among the above crosslinking agents, the compound of formula (4-23) is available from Honshu Chemical Industry Co., Ltd. under the trade name TMOM-BP, and the compound of formula (4-24) is available from Asahi Organic Chemicals Co., Ltd. under the trade name TM-BIP-A. 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., but 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, and 80% by mass or less, 50% by mass or less, 40% by mass or less, 20% by mass or less, or 10% by mass or less, based on the total solids content. These crosslinking agents may cause a crosslinking reaction by self-condensation, but when crosslinkable substituents are present in the polymer of the present invention, they can cause a crosslinking reaction with those crosslinkable substituents.

[0046] One type selected from these various crosslinking agents may be added, or two or more types may be added in combination.

[0047] (Acid and / or its salt and / or acid generator) The resist underlayer film forming composition according to the present invention may contain an acid and / or a salt thereof and / or an acid generator.

[0048] Examples of the acid 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 naphthalenecarboxylic acid; and inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid. The salt may be a salt of the above-mentioned acid, and is not limited thereto, but ammonia derivative salts such as trimethylamine salts and triethylamine salts, pyridine derivative salts, morpholine derivative salts, etc. may be suitably used. The acid and / or its salt may be used singly or in combination of two or more kinds, and the amount of the acid and / or its salt to be added is usually 0.0001 to 20% by mass, preferably 0.0005 to 10% by mass, and more preferably 0.01 to 5% by mass, based on the total solid content.

[0049] Examples of the acid generator include a thermal acid generator and a photoacid generator. Examples of thermal acid generators include 2,4,4,6-tetrabromocyclohexadienone, benzoin tosylate, 2-nitrobenzyl tosylate, K-PURE (registered trademark) CXC-1612, CXC-1614, TAG-2172, TAG-2179, TAG-2678, TAG2689, and TAG2700 (manufactured by King Industries), and SI-45, SI-60, SI-80, SI-100, SI-110, and SI-150 (manufactured by Sanshin Chemical Industry Co., Ltd.), as well as quaternary ammonium salts of trifluoroacetic acid and organic alkyl sulfonates.

[0050] Photoacid generators generate acid when the resist is exposed to light. This allows the acidity of the underlayer film to be adjusted. This is one way to match the acidity of the underlayer film to that of the upper layer resist. Adjusting the acidity of the underlayer film also allows for adjustment of the pattern shape of the upper layer resist. Examples of the photoacid generator contained in the resist underlayer film-forming composition of the present invention include onium salt compounds, sulfonimide compounds, and disulfonyldiazomethane compounds.

[0051] Examples of the onium salt compound include iodonium salt compounds such as diphenyliodonium hexafluorophosphate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-normal butanesulfonate, diphenyliodonium perfluoro-normal octanesulfonate, diphenyliodonium camphorsulfonate, bis(4-tert-butylphenyl)iodonium camphorsulfonate, and bis(4-tert-butylphenyl)iodonium trifluoromethanesulfonate; and sulfonium salt compounds such as triphenylsulfonium hexafluoroantimonate, triphenylsulfonium nonafluoro-normal butanesulfonate, triphenylsulfonium camphorsulfonate, and triphenylsulfonium trifluoromethanesulfonate.

[0052] Examples of the sulfonimide compound include N-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluoronormalbutanesulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, and N-(trifluoromethanesulfonyloxy)naphthalimide.

[0053] Examples of disulfonyldiazomethane compounds include bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(2,4-dimethylbenzenesulfonyl)diazomethane, and methylsulfonyl-p-toluenesulfonyldiazomethane.

[0054] The acid generators may be used singly or in combination of two or more. When an acid generator is used, the proportion thereof 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 content of the resist underlayer film-forming composition.

[0055] (surfactant) The resist underlayer film-forming composition of the present invention may contain a surfactant to further improve coating properties against surface irregularities without generating pinholes, striations, etc. Examples of surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether; polyoxyethylene alkylaryl ethers such as polyoxyethylene octylphenyl ether and polyoxyethylene nonylphenyl ether; polyoxyethylene-polyoxypropylene block copolymers; sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, and sorbitan tristearate; polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, and polyoxyethylene sorbitan monostearate; nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate, etc.; F-TOP (registered trademark) EF301, EF303, EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.); Megafac (registered trademark) F171, F173, R-30, R-30-N, R-40, R-40 Examples of suitable surfactants include fluorine-based surfactants such as Fluorad FC-LM (manufactured by DIC Corporation), Fluorad FC430 and FC431 (manufactured by Sumitomo 3M Limited), Asahiguard (registered trademark) AG710, Surflon (registered trademark) S-382, SC101, SC102, SC103, SC104, SC105, and SC106 (manufactured by Asahi Glass Co., Ltd.), and organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.). One surfactant selected from these surfactants may be added, or two or more surfactants may be added in combination. The content of the surfactant is, for example, 0.01 to 5% by mass based on the solid content of the resist underlayer film-forming composition of the present invention, excluding the solvent described below.

[0056] The resist underlayer film-forming composition of the present invention may further contain a light absorber, a rheology modifier, an adhesion promoter, etc. The rheology modifier is effective in improving the fluidity of the underlayer film-forming composition. The adhesion promoter is effective in improving the adhesion between the semiconductor substrate or resist and the underlayer film.

[0057] (light absorber) Examples of the light-absorbing agent include commercially available light-absorbing agents described in "Technology and Market of Industrial Dyes" (CMC Publishing) and "Dye Handbook" (edited by the Society of Organic Synthetic Chemistry), 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; and CI Fluorescent Brightening Agent. Suitable examples of the light absorbent that can be used include CI Solvent Orange 2 and 45, CI Solvent Red 1, 3, 8, 23, 24, 25, 27 and 49, CI Pigment Green 10, and CI Pigment Brown 2. The light absorbent is typically blended in an amount of 10% by mass or less, and preferably 5% by mass or less, based on the total solids content of the resist underlayer film-forming composition.

[0058] (Rheology modifier) Rheology modifiers are added primarily to improve the fluidity of the resist underlayer film-forming composition, particularly in the baking process, to improve the film thickness uniformity of the resist underlayer film and the ability of the resist underlayer film-forming composition to fill holes. 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, diisooctyl adipate, and octyldecyl 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. These rheology modifiers are typically added in an amount of less than 30% by mass based on the total solids content of the resist underlayer film-forming composition.

[0059] (adhesion aid) The adhesion promoter is added mainly for the purpose of improving the adhesion between the substrate or resist and the resist underlayer film-forming composition, and particularly to prevent the resist from peeling off during development. Specific examples include chlorosilanes such as trimethylchlorosilane, dimethylmethylolchlorosilane, methyldiphenylchlorosilane, and chloromethyldimethylchlorosilane; alkoxysilanes such as trimethylmethoxysilane, dimethyldiethoxysilane, methyldimethoxysilane, dimethylmethylolethoxysilane, diphenyldimethoxysilane, and phenyltriethoxysilane; silazanes such as hexamethyldisilazane, N,N'-bis(trimethylsilyl)urea, dimethyltrimethylsilylamine, and trimethylsilylimidazole; methyloltrimethylsilane; and methyltrimethylsilane. Examples of suitable adhesion aids include silanes such as chlorosilane, γ-chloropropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and γ-glycidoxypropyltrimethoxysilane; heterocyclic compounds such as benzotriazole, benzimidazole, indazole, imidazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, urazole, thiouracil, mercaptoimidazole, and mercaptopyrimidine; and urea or thiourea compounds such as 1,1-dimethylurea and 1,3-dimethylurea. These adhesion aids are typically blended in an amount of less than 5% by mass, and preferably less than 2% by mass, based on the total solids content of the resist underlayer film-forming composition.

[0060] The solid content of the resist underlayer film-forming composition according to the present invention is usually 0.1 to 70% by mass, preferably 0.1 to 60% by mass. The solid content is the content of all components of the resist underlayer film-forming composition excluding the solvent. The proportion of the polymer in the solid content is preferably 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, in that order.

[0061] One measure for evaluating whether a resist underlayer film-forming composition is in a uniform solution state is to observe its passability through a specific microfilter. The resist underlayer film-forming composition of the present invention passes through a microfilter with a pore size of 0.1 μm and exhibits a uniform solution state.

[0062] Examples of the microfilter material include fluorine-based resins such as PTFE (polytetrafluoroethylene) and PFA (tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer), PE (polyethylene), UPE (ultra-high molecular weight polyethylene), PP (polypropylene), PSF (polysulfone), PES (polyethersulfone), and nylon, with PTFE (polytetrafluoroethylene) being preferred.

[0063] <Resist Underlayer Film> The resist underlayer film can be formed as follows using the resist underlayer film-forming composition according to the present invention. The resist underlayer film-forming composition of the present invention is applied to a substrate used in the manufacture of a semiconductor device (e.g., a silicon wafer substrate, a silicon dioxide substrate (SiO2 substrate), a silicon nitride substrate (SiN substrate), a silicon oxynitride substrate (SiON substrate), a titanium nitride substrate (TiN substrate), a tungsten substrate (W substrate), a glass substrate, an ITO substrate, a polyimide substrate, or a substrate coated with a low dielectric constant material (low-k material)) by an appropriate application method such as a spinner or coater, and then baked using a heating means such as a hot plate to form a resist underlayer film. Baking conditions are appropriately selected from a baking temperature of 80°C to 600°C and a baking time of 0.3 to 60 minutes. Preferably, the baking temperature is 150°C to 350°C and the baking time is 0.5 to 2 minutes. The atmospheric gas during baking may be air, or an inert gas such as nitrogen or argon may also be used. Here, the thickness of the formed underlayer film is, for example, 10 to 1000 nm, 20 to 500 nm, 30 to 400 nm, or 50 to 300 nm. Furthermore, if a quartz substrate is used as the substrate, a replica of the quartz imprint mold (mold replica) can be produced.

[0064] Furthermore, an inorganic resist underlayer film (hard mask) can be formed on the organic resist underlayer film according to the present invention. For example, a silicon-containing resist underlayer film (inorganic resist underlayer film)-forming composition described in WO2009 / 104552A1 can be formed by spin coating, or a Si-based inorganic material film can be formed by a CVD method or the like. Note that the hard mask in the present invention includes both a silicon hard mask and a CVD film.

[0065] Furthermore, an adhesion layer and / or a silicone 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, an adhesion layer can be formed by spin coating using the adhesion layer described in JP-A-2013-202982 and Japanese Patent No. 5827180, or a silicon-containing resist underlayer film (inorganic resist underlayer film)-forming composition described in WO2009 / 104552A1, or a Si-based inorganic material film can be formed by CVD or the like.

[0066] Furthermore, by applying the resist underlayer film-forming composition according to the present invention to a semiconductor substrate having a portion with a step and a portion without a step (a so-called stepped substrate) and baking it, it is possible to form a resist underlayer film in which the step between the portion with a step and the portion without a step is reduced.

[0067] <Method of manufacturing a semiconductor device> The method for manufacturing a semiconductor device according to the present invention includes the steps of: forming a resist underlayer film on a semiconductor substrate using the resist underlayer film-forming composition according to the present invention; 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 an electron beam and developing it; a step of etching and patterning the resist underlayer film through the formed resist pattern; and A process of processing a semiconductor substrate through a patterned resist underlayer film Includes:

[0068] The method for manufacturing a semiconductor device according to the present invention includes the steps of: forming a resist underlayer film on a semiconductor substrate using the resist underlayer film-forming composition according to the present invention; forming a hard mask on the formed resist underlayer film; forming a resist film on the formed hard mask; a step of forming a resist pattern by irradiating the formed resist film with light or an electron beam and developing it; Etching the hard mask through the formed resist pattern; Etching the resist underlayer film through the etched hard mask; and Step of removing the hard mask Includes:

[0069] Preferably, further forming a vapor-deposited film (spacer) on the underlayer film from which the hard mask has been removed; a step of processing the formed vapor-deposited film (spacer) by etching; removing the underlayer film; and A process of processing a semiconductor substrate using spacers Includes:

[0070] The semiconductor substrate may be a stepped substrate.

[0071] The step of forming a resist underlayer film using the resist underlayer film-forming composition according to the present invention is as described above.

[0072] A resist film, such as a photoresist layer, is then formed on the resist underlayer film. The photoresist layer can be formed by a well-known method, i.e., by coating a photoresist composition solution on the underlayer film and baking it. The photoresist film thickness is, for example, 50 to 10,000 nm, or 100 to 2,000 nm, or 200 to 1,000 nm.

[0073] The photoresist formed on the resist underlayer film is not particularly limited as long as it is sensitive to the light used for exposure. Both negative and positive photoresists can be used. Examples include positive photoresists composed of a novolak resin and a 1,2-naphthoquinone diazide sulfonic acid ester; chemically amplified photoresists composed of a binder having a group that decomposes in the presence of acid to increase the alkaline dissolution rate and a photoacid generator; chemically amplified photoresists composed of a low-molecular-weight compound that decomposes in the presence of acid to increase the alkaline dissolution rate of the photoresist, an alkali-soluble binder, and a photoacid generator; and chemically amplified photoresists composed of a binder having a group that decomposes in the presence of acid to increase the alkaline dissolution rate of the photoresist, a low-molecular-weight compound that decomposes in the presence of acid to increase the alkaline dissolution rate of the photoresist, and a photoacid generator. Examples include APEX-E (trade name) manufactured by Shipley Chemical Co., Ltd., PAR710 (trade name) manufactured by Sumitomo Chemical Co., Ltd., and SEPR430 (trade name) manufactured by Shin-Etsu Chemical Co., Ltd. Further examples include fluorine-containing polymer photoresists such as those described in Proc. SPIE, Vol. 3999, 330-334 (2000), Proc. SPIE, Vol. 3999, 357-364 (2000), and Proc. SPIE, Vol. 3999, 365-374 (2000).

[0074] Next, a resist pattern is formed by irradiation with light or electron beams and development. First, exposure is performed through a predetermined mask. Near ultraviolet, far ultraviolet, or extreme ultraviolet (e.g., EUV (wavelength 13.5 nm)) is used for exposure. Specifically, KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), and F2 excimer laser (wavelength 157 nm) can be used. Among these, ArF excimer laser (wavelength 193 nm) and EUV (wavelength 13.5 nm) are preferred. After exposure, post-exposure bake can also be performed as needed. The post-exposure bake is performed under conditions appropriately selected from a heating temperature of 70°C to 150°C and a heating time of 0.3 to 10 minutes.

[0075] In addition, in the present invention, a resist for electron beam lithography can be used instead of a photoresist. Either a negative or positive type electron beam resist can be used. Examples of such resists include chemically amplified resists consisting of an acid generator and a binder having a group that decomposes in the presence of acid to change the alkaline dissolution rate; chemically amplified resists consisting of an alkali-soluble binder, an acid generator, and a low-molecular-weight compound that decomposes in the presence of acid to change the alkaline dissolution rate of the resist; chemically amplified resists consisting of an acid generator, a binder having a group that decomposes in the presence of acid to change the alkaline dissolution rate, and a low-molecular-weight compound that decomposes in the presence of acid to change the alkaline dissolution rate of the resist; non-chemically amplified resists consisting of a binder having a group that decomposes in the presence of an electron beam to change the alkaline dissolution rate; and non-chemically amplified resists consisting of a binder having a moiety that is cleaved by an electron beam to change the alkaline dissolution rate. When using these electron beam resists, resist patterns can be formed in the same manner as when using a photoresist using an electron beam as the irradiation source.

[0076] Alternatively, for the purpose of maintaining or improving high resolution and depth of focus, a method can be adopted in which a substrate on which a resist film has been formed is immersed in a liquid medium and exposed to light. In this case, the resist underlayer film is required to have resistance to the liquid medium used, and it is also possible to form a resist underlayer film that meets such requirements using the resist underlayer film-forming composition of the present invention.

[0077] Next, development is carried out with a developer, whereby, for example, when a positive photoresist is used, the photoresist in the exposed portion is removed, and a photoresist pattern is formed. Examples of the developer include aqueous alkaline solutions such as aqueous solutions of alkali metal hydroxides such as potassium hydroxide and sodium hydroxide, aqueous solutions of quaternary ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline, and aqueous solutions of amines such as ethanolamine, propylamine, and ethylenediamine. Furthermore, surfactants and the like can also be added to these developers. Development conditions are appropriately selected from a temperature of 5 to 50°C and a time of 10 to 600 seconds.

[0078] Then, the inorganic lower layer film (middle layer) is removed using the photoresist (upper layer) pattern thus formed as a protective film, and then the organic lower layer film (lower layer) is removed using the film consisting of the patterned photoresist and inorganic lower layer film (middle layer) as a protective film. Finally, the semiconductor substrate is processed using the patterned inorganic lower layer film (middle layer) and organic lower layer film (lower layer) as protective films.

[0079] First, the inorganic underlayer film (intermediate layer) in the area where the photoresist was removed is removed by dry etching to expose the semiconductor substrate. Gases such as tetrafluoromethane (CF), perfluorocyclobutane (C), perfluoropropane (C), trifluoromethane, carbon monoxide, argon, oxygen, nitrogen, sulfur hexafluoride, difluoromethane, nitrogen trifluoride, chlorine trifluoride, chlorine, trichloroborane, and dichloroborane can be used for dry etching of the inorganic underlayer film. A halogen-based gas is preferably used for dry etching of the inorganic underlayer film, and a fluorine-based gas is more preferred. Examples of fluorine-based gases include tetrafluoromethane (CF), perfluorocyclobutane (C), perfluoropropane (C), trifluoromethane, and difluoromethane (CH).

[0080] Thereafter, the organic underlayer film is removed using the patterned photoresist and inorganic underlayer film as a protective film. The organic underlayer film (underlayer) is preferably removed by dry etching using an oxygen-based gas. This is because inorganic underlayer films containing a large amount of silicon atoms are difficult to remove by dry etching using an oxygen-based gas.

[0081] In addition, wet etching treatment may be performed for the purpose of simplifying the process steps and reducing damage to the processed substrate, and the resist underlayer film-forming composition according to the present invention makes it possible to form a resist underlayer film that exhibits sufficient resistance to the chemical solution used.

[0082] Finally, the semiconductor substrate is processed, preferably by dry etching using a fluorine-based gas. Examples of fluorine-based gases include tetrafluoromethane (CF4), perfluorocyclobutane (C4F8), perfluoropropane (C3F8), trifluoromethane, and difluoromethane (CH2F2).

[0083] Furthermore, an organic antireflective coating can be formed on the resist underlayer coating before the formation of the photoresist. The antireflective coating composition used therein is not particularly limited, and any one can be selected from those conventionally used in lithography processes. The antireflective coating can be formed by a conventional method, such as coating with a spinner or coater and baking.

[0084] In the present invention, an organic underlayer film is formed on a substrate, and then an inorganic underlayer film is formed thereon, and a photoresist is then coated on top of that. This narrows the pattern width of the photoresist, and even if a thin layer of photoresist is applied to prevent pattern collapse, the substrate can be processed by selecting an appropriate etching gas. For example, a fluorine-based gas that has a sufficiently high etching rate for the photoresist can be used as an etching gas to process the resist underlayer film, and a fluorine-based gas that has a sufficiently high etching rate for the inorganic underlayer film can be used as an etching gas to process the substrate, and an oxygen-based gas that has a sufficiently high etching rate for the organic underlayer film can be used as an etching gas to process the substrate.

[0085] The resist underlayer film formed from the resist underlayer film-forming composition may also absorb light depending on the wavelength of the light used in the lithography process. In such cases, it can function as an antireflective film that prevents light from being reflected from the substrate. Furthermore, the underlayer film formed from 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 for preventing interaction between the substrate and the photoresist, a layer having the function of preventing adverse effects on the substrate of materials used in the photoresist or substances generated during exposure of the photoresist, a layer having the function of preventing diffusion of substances generated from the substrate during heating and baking into an upper photoresist layer, and a barrier layer for reducing the poisoning effect of the photoresist layer due to a dielectric layer of the semiconductor substrate.

[0086] In addition, an underlayer film formed from the resist underlayer film-forming composition can be applied to a substrate having via holes formed therein for use in a dual damascene process, and can be used as a filling material capable of filling the holes without gaps. It can also be used as a planarizing material for planarizing the surface of an uneven semiconductor substrate. [Example]

[0087] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples. The apparatus used to measure the weight-average molecular weight of the compounds obtained in the following synthesis examples is shown below. Apparatus: Tosoh Corporation HLC-8320GPC GPC column: TSKgel Super-MultiporeHZ-N (2 columns) Column temperature: 40℃ Flow rate: 0.35mL / min Eluent:THF Standard sample: polystyrene

[0088] <Synthesis Example 1> A flask was charged with 35.00 g of diphenylamine (Tokyo Chemical Industry Co., Ltd.), 21.97 g of benzaldehyde (Tokyo Chemical Industry Co., Ltd.), 0.60 g of methanesulfonic acid (Tokyo Chemical Industry Co., Ltd., hereafter referred to as MSA), and 230.25 g of propylene glycol monomethyl ether acetate (hereafter referred to as PGMEA). The mixture was then heated to 115°C under nitrogen and reacted for approximately 7 hours. After the reaction was stopped, the mixture was precipitated with methanol and dried to obtain resin (1-1). The weight-average molecular weight (Mw) measured by GPC in terms of polystyrene was approximately 5,100.

[0089] [ka]

[0090] <Synthesis Example 2> A flask was charged with 35.00 g of carbazole (Tokyo Chemical Industry Co., Ltd.), 32.72 g of 1-naphthaldehyde (Tokyo Chemical Industry Co., Ltd.), 2.01 g of MSA, and 162.71 g of PGMEA. The mixture was then heated to 120°C under nitrogen and reacted for approximately 7 hours. After the reaction was stopped, the mixture was precipitated with methanol and dried to obtain resin (1-2). The weight-average molecular weight (Mw) measured by GPC in terms of polystyrene was approximately 2,600.

[0091] [ka]

[0092] <Synthesis Example 3> A flask was charged with 50.00 g of 2-phenylindole (Tokyo Chemical Industry Co., Ltd.), 40.41 g of 1-naphthaldehyde (Tokyo Chemical Industry Co., Ltd.), 4.97 g of MSA, and 143.07 g of PGMEA. The mixture was then heated to 120°C under nitrogen and reacted for approximately 7 hours. After the reaction was stopped, the mixture was precipitated with methanol and dried to obtain resin (1-3). The weight-average molecular weight (Mw) measured by GPC in terms of polystyrene was approximately 1,700.

[0093] [ka]

[0094] <Synthesis Example 4> A flask was charged with 45.00 g of 1,5-dihydroxynaphthalene (Tokyo Chemical Industry Co., Ltd.), 29.79 g of benzaldehyde (Tokyo Chemical Industry Co., Ltd.), 5.40 g of MSA, and 187.11 g of PGMEA. The mixture was then heated to reflux under nitrogen and reacted for approximately 1.5 hours. After the reaction was stopped, the mixture was diluted with propylene glycol monomethyl ether (PGME), precipitated with water / methanol, and dried to obtain resin (1-4). The weight-average molecular weight (Mw) measured by GPC in terms of polystyrene was approximately 4,600.

[0095] [ka]

[0096] <Synthesis Example 5> A flask was charged with 60.00 g of 9,9-bis(4-hydroxyphenyl)fluorene (Tokyo Chemical Industry Co., Ltd.), 18.17 g of benzaldehyde (Tokyo Chemical Industry Co., Ltd.), 3.29 g of MSA, and 99.56 g of PGMEA. The mixture was then heated to reflux under nitrogen and allowed to react for approximately 4 hours. After the reaction was stopped, the mixture was diluted with PGMEA, precipitated with water / methanol, and dried to obtain resin (1-5). The weight-average molecular weight (Mw) measured by GPC in terms of polystyrene was approximately 4,100.

[0097] [ka]

[0098] <Synthesis Example 6> A flask was charged with 70.00 g of 2,2-biphenol (Tokyo Chemical Industry Co., Ltd.), 29.36 g of 1-naphthaldehyde (Tokyo Chemical Industry Co., Ltd.), 43.28 g of 1-pyrenecarboxylaldehyde (Aldrich), 10.83 g of MSA, and 54.81 g of PGME. The mixture was then heated to 120°C under nitrogen and reacted for 24 hours. After the reaction was stopped, the mixture was precipitated with methanol and dried to obtain resin (1-6). The weight-average molecular weight (Mw) measured by GPC in terms of polystyrene was approximately 5,000.

[0099] [ka]

[0100] <Synthesis Example 7> A flask was charged with 10.00 g of the resin obtained in Synthesis Example 1, 6.97 g of propargyl bromide (Tokyo Chemical Industry Co., Ltd., hereafter referred to as PBr), 2.17 g of tetrabutylammonium iodide (hereafter referred to as TBAI), 21.53 g of tetrahydrofuran (hereafter referred to as THF), and 7.18 g of 25% aqueous sodium hydroxide. The mixture was then heated to 55°C under nitrogen and reacted for approximately 15 hours. After the reaction was stopped, the mixture was repeatedly separated with methyl isobutyl ketone (hereafter referred to as MIBK) and water. The organic layer was concentrated, redissolved in PGMEA, reprecipitated with methanol, and dried to obtain resin (1-7). The weight-average molecular weight (Mw) measured by GPC in terms of polystyrene was approximately 6,100.

[0101] [ka]

[0102] <Synthesis Example 8> A flask was charged with 10.00 g of the resin obtained in Synthesis Example 2, 6.89 g of PBr, 3.21 g of TBAI, 22.61 g of THF, and 7.54 g of 25% aqueous sodium hydroxide. The mixture was then heated to 55°C under nitrogen and reacted for approximately 18 hours. After the reaction was stopped, the mixture was repeatedly separated into MIBK and water. The organic layer was concentrated, redissolved in PGMEA, reprecipitated using methanol, and dried to obtain resin (1-8). The weight-average molecular weight (Mw) measured by GPC in terms of polystyrene was approximately 3,000.

[0103] [ka]

[0104] <Synthesis Example 9> A flask was charged with 15.00 g of the resin obtained in Synthesis Example 3, 10.52 g of PBr, 4.90 g of TBAI, 34.21 g of THF, and 11.40 g of 25% aqueous sodium hydroxide. The mixture was then heated to 55°C under nitrogen and reacted for approximately 15 hours. After the reaction was stopped, the mixture was repeatedly separated into MIBK and water. The organic layer was concentrated, redissolved in PGMEA, reprecipitated using methanol, and dried to obtain resin (1-9). The weight-average molecular weight (Mw) measured by GPC in terms of polystyrene was approximately 1,900.

[0105] [ka]

[0106] <Synthesis Example 10> A flask was charged with 15.00 g of the resin obtained in Synthesis Example 4, 12.57 g of PBr, 5.85 g of tetrabutylammonium bromide (hereinafter referred to as TBAB), 37.60 g of THF, and 12.53 g of 25% aqueous sodium hydroxide. The mixture was then heated to 55°C under nitrogen and reacted for approximately 16 hours. After the reaction was stopped, the mixture was repeatedly separated into MIBK and water. The organic layer was concentrated, redissolved in PGMEA, reprecipitated using water / methanol, and dried to obtain resin (1-10). The weight-average molecular weight (Mw) measured by GPC in terms of polystyrene was approximately 6,900.

[0107] [ka]

[0108] <Synthesis Example 11> A flask was charged with 15.00 g of the resin obtained in Synthesis Example 5, 13.57 g of PBr, 6.32 g of TBAB, 39.25 g of THF, and 13.08 g of 25% aqueous sodium hydroxide. The mixture was then heated to 55°C under nitrogen and reacted for approximately 16 hours. After the reaction was stopped, the mixture was repeatedly separated into MIBK and water. The organic layer was concentrated, redissolved in PGMEA, reprecipitated using water / methanol, and dried to obtain resin (1-11). The weight-average molecular weight (Mw) measured by GPC in terms of polystyrene was approximately 4,600.

[0109] [ka]

[0110] <Synthesis Example 12> A flask was charged with 10.00 g of the resin obtained in Synthesis Example 6, 12.78 g of PBr, 5.86 g of TBAB, 21.48 g of THF, and 7.16 g of 25% aqueous sodium hydroxide solution. The mixture was then heated to 55°C under nitrogen and reacted for approximately 15 hours. After the reaction was stopped, the mixture was repeatedly separated into MIBK and water. The organic layer was concentrated, redissolved in PGMEA, reprecipitated using water / methanol, and dried to obtain resin (1-12). The weight-average molecular weight (Mw) measured by GPC in terms of polystyrene was approximately 6,300.

[0111] [ka]

[0112] <Synthesis Example 13> A flask was charged with 10.00 g of the resin obtained in Synthesis Example 1, 10.99 g of α-chloro-p-xylene (Tokyo Chemical Industry Co., Ltd., hereafter referred to as CMX), 5.77 g of TBAI, 16.06 g of THF, and 10.71 g of 25% aqueous sodium hydroxide solution. The mixture was then heated to 55°C under nitrogen and reacted for approximately 15 hours. After the reaction was stopped, the mixture was repeatedly separated using a mixed solvent of MIBK and cyclohexanone (hereafter referred to as CYH) and water. The organic layer was concentrated, redissolved in CYH, reprecipitated using methanol, and dried to obtain resin (1-13). The weight-average molecular weight (Mw) measured by GPC in terms of polystyrene was approximately 5,500.

[0113] [ka]

[0114] <Synthesis Example 14> A flask was charged with 10.00 g of the resin obtained in Synthesis Example 2, 9.91 g of benzyl bromide (Tokyo Chemical Industry Co., Ltd., hereafter referred to as BBr), 3.21 g of TBAI, 26.01 g of THF, and 8.67 g of 25% aqueous sodium hydroxide solution. The mixture was then heated to 55°C under nitrogen and reacted for approximately 18 hours. After the reaction was stopped, the mixture was repeatedly separated into a mixed solvent of MIBK and CYH and water. The organic layer was concentrated, redissolved in CYH, reprecipitated using methanol, and dried to obtain resin (1-14). The weight-average molecular weight (Mw) measured by GPC in terms of polystyrene was approximately 2,800.

[0115] [ka]

[0116] <Synthesis Example 15> A flask was charged with 10.00 g of the resin obtained in Synthesis Example 6, 15.55 g of BBr, 4.40 g of TBAB, 22.46 g of THF, and 7.49 g of 25% aqueous sodium hydroxide. The mixture was then heated to 55°C under nitrogen and allowed to react for approximately 15 hours. After the reaction was stopped, the mixture was repeatedly separated into a mixed solvent of MIBK and CYH and water. The organic layer was concentrated, redissolved in CYH, reprecipitated using methanol, and dried to obtain resin (1-15). The weight-average molecular weight (Mw) measured by GPC in terms of polystyrene was approximately 6,000.

[0117] [ka]

[0118] Example 1 The resin obtained in Synthesis Example 7 was dissolved in PGMEA, and ion exchange was carried out for 4 hours using a cation exchange resin and an anion exchange resin to obtain a 19.48% compound solution. 0.12 g of PL-LI (manufactured by Midori Chemical Co., Ltd.), 0.36 g of PGME containing 2 mass % pyridinium p-toluenesulfonic acid, 0.05 g of PGMEA containing 1 mass % surfactant (manufactured by DIC Corporation, Megafac R-40), 8.07 g of PGMEA, and 3.97 g of PGME were added to 2.43 g of this resin solution and dissolved, and the mixture was filtered through a polytetrafluoroethylene microfilter with a pore size of 0.1 μm to prepare a solution of a resist underlayer film-forming composition.

[0119] <Example 2> The resin obtained in Synthesis Example 8 was dissolved in PGMEA, and ion exchange was carried out for 4 hours using a cation exchange resin and an anion exchange resin to obtain an 18.63% compound solution. 0.12 g of PL-LI, 0.36 g of PGME containing 2 mass % pyridinium p-toluenesulfonic acid, 0.05 g of PGMEA containing 1 mass % surfactant, 7.96 g of PGMEA, and 3.97 g of PGME were added to 2.54 g of this resin solution and dissolved, and the mixture was filtered through a polytetrafluoroethylene microfilter with a pore size of 0.1 μm to prepare a solution of a resist underlayer film-forming composition.

[0120] Example 3 The resin obtained in Synthesis Example 9 was dissolved in PGMEA, and ion exchange was carried out for 4 hours using a cation exchange resin and an anion exchange resin to obtain a 22.47% compound solution. 0.11 g of PL-LI, 0.85 g of PGME containing 2 mass % pyridinium p-toluenesulfonic acid, 0.06 g of PGMEA containing 1 mass % surfactant, 11.49 g of PGMEA, and 4.95 g of PGME were added to 2.53 g of this resin solution and dissolved, and the mixture was filtered through a polytetrafluoroethylene microfilter with a pore size of 0.1 μm to prepare a solution of a resist underlayer film-forming composition.

[0121] Example 4 The resin obtained in Synthesis Example 10 was dissolved in PGMEA, and ion exchange was carried out for 4 hours using a cation exchange resin and an anion exchange resin to obtain a 19.21% compound solution. 0.17 g of PL-LI, 0.52 g of PGME containing 2 mass % pyridinium p-toluenesulfonic acid, 0.07 g of PGMEA containing 1 mass % surfactant, 13.91 g of PGMEA, and 6.73 g of PGME were added to 3.60 g of this resin solution and dissolved, and the mixture was filtered through a polytetrafluoroethylene microfilter with a pore size of 0.1 μm to prepare a solution of a resist underlayer film-forming composition.

[0122] <Example 5> The resin obtained in Synthesis Example 11 was dissolved in PGMEA, and ion exchange was carried out for 4 hours using a cation exchange resin and an anion exchange resin to obtain a 21.25% compound solution. 0.17 g of PL-LI, 0.52 g of PGME containing 2 mass % pyridinium p-toluenesulfonic acid, 0.07 g of PGMEA containing 1 mass % surfactant, 14.26 g of PGMEA, and 6.73 g of PGME were added to 3.25 g of this resin solution and dissolved, and the solution was filtered through a polytetrafluoroethylene microfilter with a pore size of 0.1 μm to prepare a solution of a resist underlayer film-forming composition.

[0123] Example 6 The resin obtained in Synthesis Example 12 was dissolved in PGMEA, and ion exchange was carried out for 4 hours using a cation exchange resin and an anion exchange resin to obtain a 19.44% compound solution. 0.12 g of PL-LI, 0.36 g of PGME containing 2 mass % pyridinium p-toluenesulfonic acid, 0.05 g of PGMEA containing 1 mass % surfactant, 8.07 g of PGMEA, and 3.97 g of PGME were added to 2.44 g of this resin solution and dissolved, and the solution was filtered through a polytetrafluoroethylene microfilter with a pore size of 0.1 μm to prepare a solution of a resist underlayer film-forming composition.

[0124] Example 7 The resin obtained in Synthesis Example 13 was dissolved in CYH, and ion exchange was carried out for 4 hours using a cation exchange resin and an anion exchange resin to obtain a 19.77% compound solution. 0.12 g of PL-LI, 0.36 g of PGME containing 2 mass % pyridinium p-toluenesulfonic acid, 0.05 g of PGMEA containing 1 mass % surfactant, 2.83 g of PGMEA, 3.53 g of PGME, and 6.72 g of CYH were added to 2.40 g of this resin solution and dissolved, and the mixture was filtered through a polytetrafluoroethylene microfilter with a pore size of 0.1 μm to prepare a solution of a resist underlayer film-forming composition.

[0125] Example 8 The resin obtained in Synthesis Example 14 was dissolved in CYH, and ion exchange was carried out for 4 hours using a cation exchange resin and an anion exchange resin to obtain a 21.63% compound solution. 0.12 g of PL-LI, 0.36 g of PGME containing 2 mass % pyridinium p-toluenesulfonic acid, 0.05 g of PGMEA containing 1 mass % surfactant, 2.83 g of PGMEA, 2.53 g of PGME, and 6.92 g of CYH were added to 2.19 g of this resin solution and dissolved, and the mixture was filtered through a polytetrafluoroethylene microfilter with a pore size of 0.1 μm to prepare a solution of a resist underlayer film-forming composition.

[0126] Example 9 The resin obtained in Synthesis Example 15 was dissolved in CYH, and ion exchange was carried out for 4 hours using a cation exchange resin and an anion exchange resin to obtain a 19.56% compound solution. 0.12 g of PL-LI, 0.36 g of PGME containing 2 mass % pyridinium p-toluenesulfonic acid, 0.05 g of PGMEA containing 1 mass % surfactant, 2.83 g of PGMEA, 2.53 g of PGME, and 6.69 g of CYH were added to 2.42 g of this resin solution and dissolved, and the mixture was filtered through a polytetrafluoroethylene microfilter with a pore size of 0.1 μm to prepare a solution of a resist underlayer film-forming composition.

[0127] <Comparative Example 1> The resin obtained in Synthesis Example 1 was dissolved in PGMEA, and ion exchange was carried out for 4 hours using a cation exchange resin and an anion exchange resin to obtain an 18.73% compound solution. 0.12 g of PL-LI, 0.36 g of PGME containing 2 mass % pyridinium p-toluenesulfonic acid, 0.05 g of PGMEA containing 1 mass % surfactant, 7.98 g of PGMEA, and 3.97 g of PGME were added to 2.53 g of this resin solution and dissolved, and the mixture was filtered through a polytetrafluoroethylene microfilter with a pore size of 0.1 μm to prepare a solution of a resist underlayer film-forming composition.

[0128] <Comparative Example 2> The resin obtained in Synthesis Example 2 was dissolved in PGMEA, and ion exchange was carried out for 4 hours using a cation exchange resin and an anion exchange resin to obtain a 17.08% compound solution. 0.12 g of PL-LI, 0.36 g of PGME containing 2 mass % pyridinium p-toluenesulfonic acid, 0.05 g of PGMEA containing 1 mass % surfactant, 7.73 g of PGMEA, and 3.97 g of PGME were added to 2.77 g of this resin solution and dissolved, and the solution was filtered through a polytetrafluoroethylene microfilter with a pore size of 0.1 μm to prepare a solution of a resist underlayer film-forming composition.

[0129] <Comparative Example 3> The resin obtained in Synthesis Example 3 was dissolved in PGMEA, and ion exchange was carried out for 4 hours using a cation exchange resin and an anion exchange resin to obtain a 20.20% compound solution. 0.10 g of PL-LI, 0.73 g of PGME containing 2 mass % pyridinium p-toluenesulfonic acid, 0.05 g of PGMEA containing 1 mass % surfactant, 0.91 g of PGMEA, 2.16 g of PGME, and 8.64 g of CYH were added to 2.41 g of this resin solution and dissolved, and the mixture was filtered through a polytetrafluoroethylene microfilter with a pore size of 0.1 μm to prepare a solution of a resist underlayer film-forming composition.

[0130] <Comparative Example 4> The resin obtained in Synthesis Example 4 was dissolved in PGME, and ion exchange was carried out for 4 hours using a cation exchange resin and an anion exchange resin to obtain an 18.06% compound solution. 0.17 g of PL-LI, 0.52 g of PGME containing 2 mass % pyridinium p-toluenesulfonic acid, 0.07 g of PGMEA containing 1 mass % surfactant, 7.17 g of PGMEA, and 13.24 g of PGME were added to 3.83 g of this resin solution and dissolved, and the solution was filtered through a polytetrafluoroethylene microfilter with a pore size of 0.1 μm to prepare a solution of a resist underlayer film-forming composition.

[0131] <Comparative Example 5> The resin obtained in Synthesis Example 5 was dissolved in PGMEA, and ion exchange was carried out for 4 hours using a cation exchange resin and an anion exchange resin to obtain a 19.44% compound solution. 0.17 g of PL-LI, 0.52 g of PGME containing 2 mass % pyridinium p-toluenesulfonic acid, 0.07 g of PGMEA containing 1 mass % surfactant, 13.95 g of PGMEA, and 6.73 g of PGME were added to 3.56 g of this resin solution and dissolved, and the solution was filtered through a polytetrafluoroethylene microfilter with a pore size of 0.1 μm to prepare a solution of a resist underlayer film-forming composition.

[0132] <Comparative Example 6> The resin obtained in Synthesis Example 6 was dissolved in PGMEA, and ion exchange was carried out for 4 hours using a cation exchange resin and an anion exchange resin to obtain a 29.80% compound solution. 0.21 g of PL-LI, 0.62 g of PGME containing 2 mass % pyridinium p-toluenesulfonic acid, 0.08 g of PGMEA containing 1 mass % surfactant, 7.73 g of PGMEA, and 3.58 g of PGME were added to 2.78 g of this resin solution and dissolved, and the mixture was filtered through a polytetrafluoroethylene microfilter with a pore size of 0.1 μm to prepare a solution of a resist underlayer film-forming composition.

[0133] (Contact angle measurement) The polymer solutions used in Comparative Examples 1-6 and Examples 1-9 were each applied to a silicon wafer using a spin coater and baked on a hot plate at 160°C for 60 seconds to form a polymer film. The contact angle of the polymer with pure water was then measured using a contact angle meter manufactured by Kyowa Interface Science Co., Ltd. The contact angles of the polymers used in the Examples were compared with those of the polymers used in the Comparative Examples, and cases where the contact angle of the polymer used in the Examples was higher were evaluated as "Good."

[0134] [Table 1]

[0135] When comparing Comparative Example 1 - Example 1 and Example 7, Comparative Example 2 - Example 2 and Example 8, Comparative Example 3 - Example 3, Comparative Example 4 - Example 4, Comparative Example 5 - Example 5, Comparative Example 6 - Example 6 and Example 9, the polymers used in the Examples showed higher contact angles than the polymers used in the Comparative Examples.

[0136] (Test for elution into resist solvent) The resist underlayer film-forming composition solutions prepared in Comparative Examples 1-6 and Examples 1-9 were each applied to a silicon wafer using a spin coater and baked on a hot plate at 240°C for 60 seconds or at 350°C for 60 seconds to form resist underlayer films (film thickness 65 nm). These resist underlayer films were then immersed in a general-purpose thinner, PGME / PGMEA = 7 / 3. The resist underlayer films were insoluble, confirming sufficient curability.

[0137] [Table 2]

[0138] (Coating test) The solutions of the resist underlayer film-forming compositions prepared in Comparative Examples 1-6 and Examples 1-9 were each applied to a silicon wafer using a spin coater and baked on a hot plate at 240°C for 60 seconds or 350°C for 60 seconds to form a resist underlayer film. A coating-type silicon solution was then applied to the upper layer and baked at 215°C for 60 seconds to form a silicon film. The film thickness was then measured and calculated according to the formula: "film thickness variation (maximum film thickness - minimum film thickness) / average film thickness x 100." A low value indicates good coatability. A comparative example with better coatability than the corresponding example was evaluated as "Good."

[0139] [Table 3]

[0140] Comparing Comparative Example 1 - Example 1 and Example 7, Comparative Example 2 - Example 2 and Example 8, Comparative Example 3 - Example 3, Comparative Example 4 - Example 4, Comparative Example 5 - Example 5, Comparative Example 6 - Example 6 and Example 9, the Examples have better coatability than the Comparative Examples. This is because the polymer is hydrophobic, improving coatability.

[0141] (Chemical resistance test) The resist underlayer film-forming composition solutions prepared in Comparative Examples 1-6 and Examples 1-9 were each applied to a SiON substrate using a spin coater. The resist was baked on a hot plate at 240°C for 60 seconds or 350°C for 60 seconds to form a resist underlayer film (65 nm thick). 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 the resist underlayer film. The resist was exposed to light at a wavelength of 193 nm using a mask and developed to obtain a resist pattern. Subsequently, dry etching was performed using a fluorine-based gas and an oxygen-based gas using an etching system manufactured by Lam Research Corporation, and the resist pattern was transferred to the resist underlayer film. The pattern shape was confirmed using a CG-4100 manufactured by Hitachi Technologies, Ltd., and it was confirmed that a 50 nm line pattern had been obtained.

[0142] The patterned wafer obtained here was cut and immersed in SARC-410 (manufactured by Entegris Japan Co., Ltd.) heated to 30°C. After immersion, the wafer was removed, rinsed with water, and dried. The wafer was observed with a scanning electron microscope (Regulus 8240) to check whether the pattern shape formed by the resist underlayer film had deteriorated or whether the pattern had collapsed. If the pattern shape did not deteriorate and no pattern collapse occurred, the chemical resistance was high. If the pattern shape did not deteriorate or pattern collapse occurred even when immersed in the chemical solution for a longer period of time than in a comparative example having a similar structure, it was judged to be "good."

[0143] [Table 4]

[0144] In the case of firing at 240°C, as can be seen from Comparative Example 1-Example 1, Comparative Example 2-Example 2, Comparative Example 3-Example 3, Comparative Example 4-Example 4, Comparative Example 5-Example 5, and Comparative Example 6-Example 6, modifying the amino group or hydroxyl group can improve chemical resistance to alkaline chemical solutions. Furthermore, in the case of firing at a high temperature of 350°C, chemical resistance is similarly improved. Therefore, this material can be used in processes that use chemical solutions. [Industrial Applicability]

[0145] According to the present invention, there is provided a novel resist underlayer film-forming composition that satisfies the requirements of being able to provide a hydrophobic underlayer film that exhibits a high pure water contact angle, has high adhesion to an overlayer film, and is resistant to peeling, and has good coatability, and that can also exhibit other favorable properties, such as sufficient resistance to chemical solutions used in resist underlayer films.

Claims

1. A solvent and a compound represented by the following formula (1) and / or the following formula (2): 【Chemistry 27】 (In the formula, Ar １ , and Ar ２ represents a benzene ring or a naphthalene ring, and Ar １ , and Ar ２ may be bonded via a single bond, Ar ３ represents an aromatic compound having 6 to 60 carbon atoms which may contain a nitrogen atom, R １ , and R ２ are Ar １ , and Ar ２ is a group substituting a hydrogen atom on the ring of formula (I), and is selected from the group consisting of a halogen group, a nitro group, an amino group, a cyano group, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, and combinations thereof, and the alkyl group, the alkenyl group, the alkenyl group, and the aryl group may contain an ether bond, a ketone bond, or an ester bond; R ３ , and R ８ is selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, and combinations thereof, and the alkyl group, the alkenyl group, the alkynyl group, and the aryl group may contain an ether bond, a ketone bond, or an ester bond, and the aryl group may be substituted with an alkyl group having 1 to 10 carbon atoms substituted with a hydroxyl group; R ４ , and R ６ is selected from the group consisting of a hydrogen atom, a trifluoromethyl group, an aryl group having 6 to 40 carbon atoms, and a heterocyclic group, and the aryl group and the heterocyclic group are optionally substituted with a halogen group, a nitro group, an amino group, a cyano group, a trifluoromethyl group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, or an aryl group having 6 to 40 carbon atoms, and the alkyl group, the alkenyl group, the alkynyl group, and the aryl group may contain an ether bond, a ketone bond, or an ester bond; R ５ , and R ７ is selected from the group consisting of a hydrogen atom, a trifluoromethyl group, an aryl group having 6 to 40 carbon atoms, and a heterocyclic group, and the aryl group and the heterocyclic group are optionally substituted with a halogen group, a nitro group, an amino group, a cyano group, a trifluoromethyl group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, or an aryl group having 6 to 40 carbon atoms, and the alkyl group, the alkenyl group, the alkynyl group, and the aryl group may contain an ether bond, a ketone bond, or an ester bond; And R ４ and R ５ and R ６ and R ７ may form a ring together with the carbon atom to which they are attached. n1 and n2 are each an integer of 0 to 3, n3 is 1 or more, and Ar ３ is an integer equal to or less than the number of substituents that can be substituted for n4 is 0 or 1, but when n4 is 0, R ８ is Ar ３ It bonds to the nitrogen atom in A resist underlayer film-forming composition comprising a polymer containing a unit structure (A) represented by the following formula:

2. In the above formula (1), Ar １ , and Ar ２ The resist underlayer film forming composition according to claim 1, wherein is a benzene ring.

3. In the above formula (2), Ar ３ 2. The resist underlayer film forming composition according to claim 1, wherein is an optionally substituted benzene ring, naphthalene ring, diphenylfluorene ring, or phenylindole ring.

4. In the above formula (1) or (2), R ４ , and R ６ is an aryl group having 6 to 40 carbon atoms; R ５ , and R ７ is a hydrogen atom The resist underlayer film forming composition according to any one of claims 1 to 3.

5. In the above formula (1) or (2), R ４ , and R ６ is an aromatic hydrocarbon group having 6 to 16 carbon atoms The resist underlayer film forming composition according to any one of claims 1 to 4.

6. The resist underlayer film forming composition according to any one of claims 1 to 5, further comprising a crosslinking agent.

7. The resist underlayer film forming composition according to any one of claims 1 to 6, further comprising an acid and / or an acid generator.

8. 2. The resist underlayer film forming composition according to claim 1, wherein the boiling point of the solvent is 160°C or higher.

9. A resist underlayer film which is a fired product of a coating film comprising the resist underlayer film-forming composition according to any one of claims 1 to 8.

10. A step of forming a resist underlayer film on a semiconductor substrate using the resist underlayer film-forming composition according to any one of claims 1 to 8; 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 an electron beam and developing it; a step of etching and patterning the resist underlayer film through the formed resist pattern; and A process of processing a semiconductor substrate through a patterned resist underlayer film A method for manufacturing a semiconductor device comprising:

11. A step of forming a resist underlayer film on a semiconductor substrate using the resist underlayer film-forming composition according to any one of claims 1 to 8; forming a hard mask on the formed resist underlayer film; forming a resist film on the formed hard mask; a step of forming a resist pattern by irradiating the formed resist film with light or an electron beam and developing it; Etching the hard mask through the formed resist pattern; Etching the resist underlayer film through the etched hard mask; and Step of removing the hard mask A method for manufacturing a semiconductor device comprising:

12. Furthermore, forming a vapor-deposited film (spacer) on the underlayer film from which the hard mask has been removed; a step of processing the formed vapor-deposited film (spacer) by etching; removing the underlayer film; and A process of processing a semiconductor substrate using spacers The method for manufacturing a semiconductor device according to claim 11, comprising:

13. The method for manufacturing a semiconductor device according to any one of claims 10 to 12, wherein the semiconductor substrate is a stepped substrate.

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