Resist underlayer film-forming composition containing novolac resin

Abstract

The object of the present invention is to provide a composition for forming the following resist underlayer film, wherein the above-mentioned resist underlayer film is not easily mixed when a photoresist composition and different resist underlayer films are stacked, and the filling property of the pattern during firing is improved by improving the thermal reflow property of the polymer. The solution is a composition for forming a resist underlayer film, which contains a phenolic varnish resin containing a structural group (C), and the above-mentioned structural group (C) is formed by the reaction of an aromatic ring of an aromatic compound (A) containing at least 2 amino groups and at least 3 aromatic rings with 6 to 40 carbon atoms, and a vinyl group of an aromatic vinyl compound (B). The above-mentioned structural group (C) is the following formula (1), [In formula (1), R 1 is a divalent group containing at least two amino groups and at least three aromatic rings having 6 to 40 carbon atoms. 1 It is a divalent organic group obtained by removing two hydrogen atoms from the aromatic ring of the compound represented by the following formula (2). 1 It is a divalent organic group obtained by removing two hydrogen atoms from the aromatic ring of N,N'-diphenyl-1,4-phenylenediamine.

Description

Technical Field

[0001] The present invention relates to a resist underlayer film-forming composition for forming a planarized film on a substrate having an uneven surface, and a method for producing a planarized laminated substrate using the resist underlayer film. Background Art

[0002] Microfabrication has been performed by photolithography using a photoresist composition in the manufacture of semiconductor devices. The microfabrication is a method of forming a thin film of a photoresist composition on a substrate to be processed, such as a silicon wafer, irradiating the thin film with active light such as ultraviolet rays through a mask pattern on which a semiconductor device pattern is drawn, developing the thin film, and etching the substrate to be processed, such as a silicon wafer, using the obtained photoresist pattern as a protective film.

[0003] However, in recent years, with the progress of high integration of semiconductor devices, the active light used has also shortened from KrF excimer laser (248nm) to ArF excimer laser (193nm). Along with this, diffuse reflection of active light from the substrate and the influence of standing waves have become major problems, and the method of setting an anti-reflection film between the photoresist and the processed substrate has been widely used.

[0004] In addition, for the purpose of further microfabrication, lithography technology using extreme ultraviolet light (EUV, 13.5nm) and electron beam (EB) has also been developed. For EUV lithography and EB lithography, since diffuse reflection and standing waves from the substrate generally do not occur, a specific anti-reflection film is not required, but as an auxiliary film with the goal of improving the resolution and adhesion of the resist pattern, extensive research has begun on the resist underlayer film.

[0005] However, as the exposure wavelength becomes shorter, the depth of focus decreases, and thus, in order to form a desired resist pattern with good precision, it becomes important to improve the flatness of the film formed on the substrate. In other words, in order to manufacture semiconductor devices with fine design rules, a resist underlayer film that can form a flat coating film without height differences on the substrate becomes essential.

[0006] For example, a composition for forming a resist underlayer film containing a crosslinking compound having an alkoxymethyl group having 2 to 10 carbon atoms and an alkyl group having 1 to 10 carbon atoms is disclosed (see Patent Document 1). The use of this composition shows good embedding properties when applied to a substrate having a hole pattern.

[0007] In addition, a resist underlayer film-forming composition containing a novolac resin using phenylnaphthylamine is disclosed. (See Patent Document 2.)

[0008] Furthermore, a resist underlayer film-forming composition containing a polymer obtained by reacting a novolac resin using phenylnaphthylamine with tert-butoxystyrene is disclosed. (See Patent Document 3)

[0009] Prior art literature

[0010] Patent Literature

[0011] Patent Document 1: International Publication No. 2014 / 208542

[0012] Patent Document 2: International Publication No. 2013 / 047516

[0013] Patent Document 3: International Publication No. 2015 / 151803 Summary of the invention

[0014] Problems to be solved by the invention

[0015] In order to prevent the photoresist composition and different resist underlayer films from mixing during lamination, a self-crosslinking site is introduced into the polymer resin as a main component, or a crosslinking agent, a crosslinking catalyst, etc. are appropriately added, and the composition is fired (baked) at a high temperature to thermally cure the coating film. In this way, the photoresist composition and different resist underlayer films can be laminated without mixing.

[0016] However, since such a thermosetting resist underlayer film-forming composition contains a polymer having a thermally cross-linkable functional group such as a hydroxyl group, a cross-linking agent, and an acid catalyst (acid generator), when it is filled in a pattern (e.g., a hole or a groove structure) formed on a substrate, a cross-linking reaction proceeds by firing, resulting in an increase in viscosity and deterioration in the filling property of the pattern, and the planarization property after film formation is easily reduced.

[0017] In addition, the resist underlayer film is sometimes used to form a silicon hard mask layer on the upper layer by vapor deposition, and heat resistance that can withstand the heat of vapor deposition is also required. In addition, the resist underlayer film is also required to have etching resistance because the substrate below is processed by the transferred pattern.

[0018] The present invention aims to improve the filling property of a pattern during firing by improving the thermal reflow property of a polymer. That is, a composition for forming a resist underlayer film is provided, wherein a substituent such as an alkyl group that can lower the glass transition temperature of the polymer is introduced to improve the thermal reflow property of the polymer, thereby sufficiently reducing the viscosity before the crosslinking reaction during firing begins, and forming a coating film with high planarization property on a substrate.

[0019] Furthermore, the present invention provides a resist underlayer film-forming composition for forming a resist underlayer film having both heat resistance and etching resistance.

[0020] Methods for solving problems

[0021] The present inventors have conducted intensive research to solve the above-mentioned problems, and as a result, have found that by using a novolac resin containing a structural group (C) as follows in a resist underlayer film-forming composition, the filling property of a pattern formed on a substrate can be improved, thereby forming an excellent planarized film. The structural group (C) is formed by reacting an aromatic ring of an aromatic compound (A) which is a novolac resin obtained by reacting a compound containing at least two amino groups and at least three aromatic rings having 6 to 40 carbon atoms with an aldehyde or a ketone, and a vinyl group of an aromatic vinyl compound (B). In addition, it has been found that by introducing an alkyl group or other substituent into the novolac resin, a resist underlayer film-forming composition containing the novolac resin can form a resist underlayer film having both planarization property and heat resistance.

[0022] That is, in the present invention, as a first aspect, is a resist underlayer film-forming composition comprising a novolac resin containing a structural group (C) formed by reacting an aromatic ring of an aromatic compound (A) containing at least two amino groups and at least three aromatic rings having 6 to 40 carbon atoms with a vinyl group of an aromatic vinyl compound (B),

[0023] According to a second aspect, in the resist underlayer film forming composition according to the first aspect, the structural group (C) is the following formula (1):

[0024]

[0025] [In formula (1),

[0026] R 1 is a divalent group containing at least two amino groups and at least three aromatic rings having 6 to 40 carbon atoms,

[0027] R 2 and R 3 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, a heterocyclic group, or a combination thereof, and the alkyl group, the aryl group, and the heterocyclic group are organic groups which may have a halogen atom, a nitro group, an amino group, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, a formyl group, a carboxyl group, an alkoxy group, or a hydroxyl group as a substituent, and R 2 With R 3 can form rings with the carbon atoms to which they are attached,

[0028] T 1 is an arylene group having 6 to 40 carbon atoms,

[0029] T3 represents 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, a hydroxyl group, a cyano group, a nitro group, an amino group, a carboxyl group, an acetyl group, a hydroxymethyl group, a halomethyl group, a -YZ group, a halogen atom, or a combination thereof. Y represents an oxygen atom, a sulfur atom, a carbonyl group, or an ester group, and Z represents an alkyl group having 1 to 10 carbon atoms.

[0030] T 2 represents a hydrogen atom, a methyl group, or a phenyl group.

[0031] m is an integer from 0 to (5+2n),

[0032] n represents the structure as T 1 The degree of fusion of the aromatic rings of the arylene group is defined as

[0033] m1 is an integer from 2 to 3600. ],

[0034] As a third aspect, the resist underlayer film forming composition according to the second aspect, wherein the R 1 is a divalent organic group obtained by removing two hydrogen atoms from the aromatic ring of the compound represented by the following formula (2),

[0035]

[0036] [In formula (2),

[0037] Ar 1 ,Ar 2 and Ar 3 each independently represents a benzene ring or a naphthalene ring,

[0038] R 6 , R 7 and R 8 are each independently a substituent on these rings, and R 6 , R 7 and R 8 are each independently selected from a halogen atom, a nitro group, an amino group, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, and a combination thereof, and the alkyl group, the alkenyl group and the aryl group represent an organic group that may contain an ether bond, a ketone bond, or an ester bond,

[0039] R 4 and R 5 are each independently selected from a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, and a combination thereof, and the alkyl group, the alkenyl group, and the aryl group represent an organic group that may contain an ether bond, a ketone bond, or an ester bond,

[0040] n1, n2, and n3 are each greater than 0 and are less than or equal to R 6 , R 7 and R 8 The maximum integer that can be substituted. ],

[0041] As a fourth aspect, the resist underlayer film forming composition according to the second aspect, wherein R 1 It is a divalent organic group obtained by removing two hydrogen atoms from the aromatic ring of N,N'-diphenyl-1,4-phenylenediamine.

[0042] As a fifth aspect, the resist underlayer film forming composition according to any one of the second aspect to the fourth aspect, wherein R 3 is a hydrogen atom,

[0043] R 2 is an aryl group selected from phenyl, naphthyl, anthracenyl, and pyrenyl, which may have a halogen atom, a nitro group, an amino group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, a formyl group, a carboxyl group, or a hydroxyl group as a substituent,

[0044] As a sixth aspect, the resist underlayer film forming composition according to any one of the second aspect to the fourth aspect, wherein R 3 is a hydrogen atom,

[0045] R 2 is a phenyl group which may have a halogen atom, a nitro group, an amino group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, a formyl group, a carboxyl group, or a hydroxyl group as a substituent,

[0046] According to a seventh aspect, the resist underlayer film forming composition according to any one of the second aspect to the sixth aspect, wherein T 1 is phenylene,

[0047] According to an eighth aspect, in the resist underlayer film forming composition according to the second aspect, the structural group (C) is the following formula (1-1):

[0048]

[0049] [In formula (1-1),

[0050] R 2 and R 3are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, a heterocyclic group, or a combination thereof, and the alkyl group, the aryl group, and the heterocyclic group are organic groups which may have a halogen atom, a nitro group, an amino group, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, a formyl group, a carboxyl group, an alkoxy group, or a hydroxyl group as a substituent, and R 2 With R 3 Together with the carbon atoms to which they are attached, they can form a ring.

[0051] T 2 represents a hydrogen atom, a methyl group, or a phenyl group,

[0052] m1 is an integer from 2 to 3600. ],

[0053] According to a ninth aspect, the resist underlayer film-forming composition according to any one of the first aspect to the eighth aspect further comprises a crosslinking agent.

[0054] According to a tenth aspect, the resist underlayer film-forming composition according to any one of the first aspect to the ninth aspect further comprises an acid and / or an acid generator.

[0055] As an eleventh aspect, a resist underlayer film is obtained by applying the resist underlayer film-forming composition according to any one of the first aspect to the tenth aspect onto a semiconductor substrate and firing the coating.

[0056] As a twelfth aspect, a method for manufacturing a semiconductor device comprises the following steps: a step of forming a resist underlayer film on a semiconductor substrate using the resist underlayer film-forming composition according to any one of the first aspect to the tenth aspect; a step of forming a resist film on the resist underlayer film; a step of forming a resist pattern by irradiating and developing with light or electron beams; a step of etching the resist underlayer film using the formed resist pattern; and a step of processing the semiconductor substrate using the patterned resist underlayer film.

[0057] As the 13th aspect, a method for manufacturing a semiconductor device comprises the following steps: a step of forming a resist underlayer film on a semiconductor substrate using a resist underlayer film forming composition described in any one of the 1st aspect to the 10th aspect; a step of forming a hard mask on the above-mentioned resist underlayer film; a step of further forming a resist film on the above-mentioned hard mask; a step of forming a resist pattern by irradiating and developing with light or electron beams; a step of etching the hard mask through the formed resist pattern; a step of etching the resist underlayer film through the patterned hard mask; and a step of processing the semiconductor substrate through the patterned resist underlayer film.

[0058] Effects of the Invention

[0059] The resist underlayer film-forming composition of the present invention improves heat reflowability during firing, for example, by introducing an alkyl group, which generally lowers the glass transition temperature (Tg) of a polymer, into the main resin backbone of the resist underlayer film-forming composition. Therefore, when the resist underlayer film-forming composition of the present invention is applied on a substrate and fired, the high heat reflowability of the polymer can improve the filling property of the pattern formed on the substrate.

[0060] Moreover, the resist underlayer film forming composition of the present invention can form a flat film on the substrate regardless of the open area (non-pattern area), DENSE (dense) and ISO (sparse) pattern areas on the substrate. Therefore, the resist underlayer film forming composition of the present invention can simultaneously satisfy the filling properties of the pattern and the flattening properties after filling, thereby forming an excellent flattened film.

[0061] Furthermore, the novolac resin in the resist underlayer film-forming composition of the present invention can exhibit crosslinking properties when heated by introducing a crosslinkable functional group at its terminal, thereby preventing mixing of the resist underlayer film formed from the resist underlayer film-forming composition of the present invention with the upper layer.

[0062] The present invention can provide a resist underlayer film-forming composition capable of forming a resist underlayer film having well-balanced properties, particularly heat resistance, planarization property, and etching resistance. DETAILED DESCRIPTION

[0063] The present invention is a composition for forming a resist underlayer film, comprising a novolac resin containing a structural group (C), wherein the structural group (C) is formed by reacting an aromatic ring of an aromatic compound (A) containing at least two amino groups and at least three aromatic rings having 6 to 40 carbon atoms with a vinyl group of an aromatic vinyl compound (B).

[0064] In the present invention, the resist underlayer film-forming composition contains the novolac resin and may contain a solvent, a crosslinking agent, an acid, an acid generator, a surfactant, and the like as necessary.

[0065] The solid content of the resist underlayer film-forming composition of the present invention is 0.1 to 70% by mass, or 0.1 to 60% by mass. The solid content is the content ratio of all components after removing the solvent from the resist underlayer film-forming composition. The above-mentioned novolac resin can be contained in the solid content at a ratio of 1 to 100% by mass, or 1 to 99.9% by mass, or 50 to 99.9% by mass, or 50 to 95% by mass, or 50 to 90% by mass.

[0066] The weight average molecular weight of the novolac resin used in the present invention is 600 to 1,000,000, or 600 to 200,000.

[0067] The novolac resin used in the present invention contains a structural group (C) at the terminal of the novolac resin, preferably a structural group represented by formula (1).

[0068] The novolac resin containing the structural group (C) represented by formula (1) comprises: a novolac resin obtained by reacting an organic compound containing at least two amino groups and at least three aromatic rings having 6 to 40 carbon atoms with an aldehyde or a ketone as an aromatic compound (A), and a structural group (C) formed by reacting the aromatic ring of the aromatic compound (A) with the vinyl group of an aromatic vinyl compound (B).

[0069] In formula (1), R 1 is a divalent group containing at least two amino groups and at least three aromatic rings having 6 to 40 carbon atoms,

[0070] R 2 and R 3 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, a heterocyclic group, or a combination thereof, and the alkyl group, the aryl group, and the heterocyclic group are organic groups which may have a halogen atom, a nitro group, an amino group, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, a formyl group, a carboxyl group, an alkoxy group, or a hydroxyl group as a substituent, and R 2 With R 3 can form rings with the carbon atoms to which they are attached,

[0071] T 1 It is an arylene group having 6 to 40 carbon atoms.

[0072] T 3 represents 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, a hydroxyl group, a cyano group, a nitro group, an amino group, a carboxyl group, an acetyl group, a hydroxymethyl group, a halomethyl group, a -YZ group, a halogen atom, or a combination thereof. Y represents an oxygen atom, a sulfur atom, a carbonyl group, or an ester group, and Z represents an alkyl group having 1 to 10 carbon atoms.

[0073] T 2 represents a hydrogen atom, a methyl group, or a phenyl group.

[0074] m is an integer from 0 to (5+2n),

[0075] n represents the structure as T 1 The degree of fusion of the aromatic rings of the arylene group is defined.

[0076] T2 Preferred is methyl.

[0077] m1 is an integer of 2 to 3600, or an integer of 2 to 3000, or an integer of 2 to 2000, or an integer of 2 to 735, or an integer of 3 to 3600, or an integer of 3 to 3000, or an integer of 3 to 2000, or an integer of 3 to 735, or an integer of 5 to 3600, or an integer of 5 to 3000, or an integer of 5 to 2000, or an integer of 5 to 735.

[0078] Examples of the amino group include a primary amino group, a secondary amino group and a tertiary amino group.

[0079] In addition, examples of the aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring, and a pyrene ring.

[0080] R in formula (1) 1 It is a divalent group containing at least two amino groups and at least three aromatic rings having 6 to 40 carbon atoms, which forms the main chain of the novolac resin. The divalent group containing the above amino groups and aromatic rings can be used. In particular, R 1 It is preferably a divalent group containing two amino groups and three aromatic rings having 6 to 40 carbon atoms.

[0081] R in formula (1) 1 It may be a divalent organic group obtained by removing two hydrogen atoms from the aromatic ring of the compound represented by formula (2). The aromatic ring in the compound represented by formula (2) forms a novolac resin with an aldehyde or a ketone.

[0082] The compound represented by formula (2) is derived into a divalent organic group, so that a bond for forming a novolac resin with an aldehyde or a ketone is generated at any two positions of the aromatic ring in (2). 1 with Ar 3 ,Ar 1 with Ar 2 ,Ar 1 with Ar 1 ,Ar 2 with Ar 2 , R 4 ~R 8 Aryl, or Ar 1 ~Ar 3 With R 4 ~R 8 The aromatic group of the aldehyde or ketone can form a bond with the aldehyde or ketone. In addition, when the aldehyde or ketone has an aromatic ring as a substituent, the aromatic ring can form a bond with the aldehyde or ketone.

[0083] In formula (2), Ar 1 ,Ar 2 and Ar 3 each independently represents a benzene ring or a naphthalene ring,

[0084] R 6 、R 7 and R 8 are each independently a substituent on these rings, and they are selected from a halogen atom, a nitro group, an amino group, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, and a combination thereof. Moreover, the alkyl group, the alkenyl group, and the aryl group represent an organic group that may contain an ether bond, a ketone bond, or an ester bond.

[0085] R 4 and R 5 are each independently selected from a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, and a combination thereof. Moreover, the alkyl group, the alkenyl group, and the aryl group represent an organic group that may contain an ether bond, a ketone bond, or an ester bond.

[0086] n1, n2, and n3 are each 0 or more, and they are integers less than or equal to the maximum number that can be substituted by R 6 、R 7 and R 8 . n1, n2, and n3 are usually each an integer of 0 to 4, or 0 to 3, or 0 to 2, or 0 to 1.

[0087] As the aromatic vinyl compound (B), a vinyl group-containing compound having a structure represented by formula (B-1) can be exemplified.

[0088]

[0089] In formula (B-1),

[0090] T 1 represents an arylene group having 6 to 40 carbon atoms (original Japanese: アルール基),

[0091] T 3 represents 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, a hydroxyl group, a cyano group, a nitro group, an amino group, a carboxyl group, an acetyl group, a hydroxymethyl group, a halomethyl group, a -Y-Z group, a halogen atom, or a combination thereof. Y represents an oxygen atom, a sulfur atom, a carbonyl group, or an ester group, and Z represents an alkyl group having 1 to 10 carbon atoms.

[0092] T 2 represents a hydrogen atom, a methyl group, or a phenyl group. Preferably, T 2 is a hydrogen atom.

[0093] m is an integer of 0 to (5 + 2n),

[0094] n represents the number of 1The degree of fusion of the aromatic rings of the arylene group is defined.

[0095] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

[0096] Examples of the alkyl group having 1 to 10 carbon atoms include methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, 1-methyl-cyclopropyl, 2-methyl-cyclopropyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl, 1,2-dimethyl-n-propyl, 2,2-dimethyl-n-propyl, 1-ethyl-n-propyl, cyclopentyl, 1-methyl-cyclobutyl, 2-methyl-cyclobutyl 1-ethyl-cyclopropyl, 2-ethyl-cyclopropyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n-pentyl, 4-methyl-n-pentyl, 1,1-dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1,3-dimethyl-n-butyl, 2,2-dimethyl-n-butyl, 2,3-dimethyl-n-butyl, 3,3-dimethyl-n-butyl, 1-ethyl- -n-butyl, 2-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl, 1,2,2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl, 1-ethyl-2-methyl-n-propyl, cyclohexyl, 1-methyl-cyclopentyl, 2-methyl-cyclopentyl, 3-methyl-cyclopentyl, 1-ethyl-cyclobutyl, 2-ethyl-cyclobutyl, 3-ethyl-cyclobutyl, 1,2-dimethyl-cyclobutyl, 1,3-dimethyl-cyclobutyl, 2,2-dimethyl-cyclobutyl, 2,3-dimethyl-cyclobutyl Methyl-cyclobutyl, 2,4-dimethyl-cyclobutyl, 3,3-dimethyl-cyclobutyl, 1-n-propyl-cyclopropyl, 2-n-propyl-cyclopropyl, 1-isopropyl-cyclopropyl, 2-isopropyl-cyclopropyl, 1,2,2-trimethyl-cyclopropyl, 1,2,3-trimethyl-cyclopropyl, 2,2,3-trimethyl-cyclopropyl, 1-ethyl-2-methyl-cyclopropyl, 2-ethyl-1-methyl-cyclopropyl, 2-ethyl-2-methyl-cyclopropyl and 2-ethyl-3-methyl-cyclopropyl, etc.

[0097] Examples of the alkenyl group having 2 to 10 carbon atoms include vinyl, 1-propenyl, 2-propenyl, 1-methyl-1-vinyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl, 1-ethylvinyl, 1-methyl-1-propenyl, 1-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-n-propylvinyl, 1-methyl-1-butenyl, 1-methyl-2-butenyl, 1-methyl-3-butenyl, 2-ethyl-2-propenyl, 2-methyl-1-butenyl, 2-methyl-2-butenyl, 2-methyl-3-butenyl. 1-butylene, 1-methyl-1-pentenyl, 1-methyl-2-pentenyl, 1-methyl-3-pentenyl, 1-methyl-4-pentenyl, 1-butylene, 2-methyl-1-pentenyl, 2-methyl-2-pentenyl, 2-methyl-3-pentenyl, 1-methyl-2-pentenyl, 1-methyl-3-pentenyl, 1-methyl-4-pentenyl, 1-butylene, 2-methyl-1-pentenyl, 2-methyl-2-pentenyl, 2-methyl-3-pentenyl , 2-methyl-4-pentenyl, 2-n-propyl-2-propenyl, 3-methyl-1-pentenyl, 3-methyl-2-pentenyl, 3-methyl-3-pentenyl, 3-methyl-4-pentenyl, 3-ethyl-3-butenyl, 4-methyl-1-pentenyl, 4-methyl-2-pentenyl, 4-methyl-3-pentenyl, 4-methyl-4-pentenyl, 1,1-dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl, 1,2-dimethyl-1-butenyl, 1,2-dimethyl-2-butenyl, 1,2-dimethyl-3-butenyl, 1-methyl-2-ethyl-2-propenyl, 1-sec-butylvinyl, 1,3- dimethyl-1-butenyl, 1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl, 1-isobutylvinyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 2-isopropyl-2-propenyl, 3,3-dimethyl-1-butenyl, 1-ethyl-1-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 1-n-propyl-1-propenyl, 1-n-propyl-2-propenyl, 2-ethyl-1-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1,1,2-Trimethyl-2-propenyl, 1-tert-butylvinyl, 1-methyl-1-ethyl-2-propenyl, 1-ethyl-2-methyl-1-propenyl, 1-ethyl-2-methyl-2-propenyl, 1-isopropyl-1-propenyl, 1-isopropyl-2-propenyl, 1-methyl-2-cyclopentenyl, 1-methyl-3-cyclopentenyl, 2-methyl-1-cyclopentenyl, 2-methyl-2-cyclopentenyl cyclopentenyl, 2-methyl-3-cyclopentenyl, 2-methyl-4-cyclopentenyl, 2-methyl-5-cyclopentenyl, 2-methylene-cyclopentyl, 3-methyl-1-cyclopentenyl, 3-methyl-2-cyclopentenyl, 3-methyl-3-cyclopentenyl, 3-methyl-4-cyclopentenyl, 3-methyl-5-cyclopentenyl, 3-methylene-cyclopentyl, 1-cyclohexenyl, 2-cyclohexenyl and 3-cyclohexenyl, etc.

[0098] Examples of the alkynyl group having 2 to 10 carbon atoms include ethynyl and propargyl.

[0099] The alkoxy group having 1 to 20 carbon atoms or 1 to 10 carbon atoms includes, for example, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, 1-methyl-n-butoxy, 2-methyl-n-butoxy, 3-methyl-n-butoxy, 1,1-dimethyl-n-propoxy, 1,2-dimethyl-n-propoxy, 2,2-dimethyl-n-propoxy, 1-ethyl-n-propoxy, n-hexyloxy, 1-methyl-n-pentoxy, 2-methyl-n-pentoxy, 3-methyl-n-butoxy, -methyl-n-pentoxy, 4-methyl-n-pentoxy, 1,1-dimethyl-n-butoxy, 1,2-dimethyl-n-butoxy, 1,3-dimethyl-n-butoxy, 2,2-dimethyl-n-butoxy, 2,3-dimethyl-n-butoxy, 3,3-dimethyl-n-butoxy, 1-ethyl-n-butoxy, 2-ethyl-n-butoxy, 1,1,2-trimethyl-n-propoxy, 1,2,2-trimethyl-n-propoxy, 1-ethyl-1-methyl-n-propoxy, and 1-ethyl-2-methyl-n-propoxy, etc.

[0100] Examples of the aryl group having 6 to 40 carbon atoms include phenyl, o-methylphenyl, m-methylphenyl, p-methylphenyl, o-chlorophenyl, m-chlorophenyl, p-chlorophenyl, o-fluorophenyl, p-fluorophenyl, o-methoxyphenyl, p-methoxyphenyl, p-nitrophenyl, p-cyanophenyl, α-naphthyl, β-naphthyl, o-biphenyl, m-biphenyl, p-biphenyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl, 9-phenanthryl and pyrene.

[0101] The heterocyclic group is preferably an organic group consisting of a 5- to 6-membered heterocyclic ring containing a nitrogen atom, a sulfur atom, or an oxygen atom, and examples thereof include pyrrolyl, furyl, thienyl, imidazolyl, Azolyl, thiazolyl, pyrazolyl, iso Azolyl, isothiazolyl, pyridyl, etc.

[0102] Among them, a heterocyclic group containing a sulfur atom is preferred for use in a high refractive index material.

[0103] Examples of the arylene group having 6 to 40 carbon atoms include phenylene, o-methylphenylene, m-methylphenylene, p-methylphenylene, o-chlorophenylene, m-chlorophenylene, p-chlorophenylene, o-fluorophenylene, p-fluorophenylene, o-methoxyphenylene, p-methoxyphenylene, p-nitrophenylene, p-cyanophenylene, α-naphthylene, β-naphthylene, o-biphenylene, m-biphenylene, p-biphenylene, 1-anthrylene, 2-anthrylene, 9-anthrylene, 1-phenanthrylene, 2-phenanthrylene, 3-phenanthrylene, 4-phenanthrylene and 9-phenanthrylene.

[0104] In the above formula (1), R 3 is a hydrogen atom, R 2 It is an aryl group selected from phenyl, naphthyl, anthracenyl, and pyrene, and the aryl group may be a group having a halogen atom, a nitro group, an amino group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, a formyl group, a carboxyl group, or a hydroxyl group as a substituent.

[0105] Moreover, R 3 is a hydrogen atom, R 2 The phenyl group may be a phenyl group which may have a halogen atom, a nitro group, an amino group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, a formyl group, a carboxyl group, or a hydroxyl group as a substituent.

[0106] Examples of the aldehydes used for producing the novolac resin of the present invention include saturated aliphatic aldehydes such as formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, valeraldehyde, hexanal, 2-methylbutyraldehyde, hexanal, undecanal, 7-methoxy-3,7-dimethyloctylaldehyde, cyclohexanal, 3-methyl-2-butyraldehyde, glyoxal, malondialdehyde, succinaldehyde, glutaraldehyde, glutaraldehyde, and adipaldehyde; unsaturated aliphatic aldehydes such as acrolein and methacrolein; Heterocyclic aldehydes such as furfural, pyridinealdehyde, and thiophenealdehyde, benzaldehyde, naphthaldehyde, anthracenealdehyde, phenylbenzaldehyde, anisaldehyde, ethoxybenzaldehyde, n-pentyloxybenzaldehyde, n-octyloxybenzaldehyde, trimethoxybenzaldehyde, ethylbenzaldehyde, n-butylbenzaldehyde, tert-butylbenzaldehyde, isopropylbenzaldehyde, isobutylbenzaldehyde, terephthalaldehyde, pyrenecarboxaldehyde, phenanthrenaldehyde, salicylaldehyde, phenylacetaldehyde, 3-phenylpropanaldehyde, toluylaldehyde, (N,N-dimethylamino)benzaldehyde, and aromatic aldehydes such as acetoxybenzaldehyde, etc. Aromatic aldehydes can be particularly preferably used.

[0107] The ketones used for producing the novolac resin of the present invention are diaryl ketones, and examples thereof include diphenyl ketone, phenyl naphthyl ketone, dinaphthyl ketone, phenyl tolyl ketone, xylyl ketone, and 9-fluorenone.

[0108] The novolac reaction (condensation reaction) of an organic compound containing at least 2 amino groups and at least 3 aromatic groups having 6 to 40 carbon atoms, preferably an aromatic compound represented by formula (2), with an aldehyde or a ketone is preferably carried out in a molar ratio of the aromatic compound to the aldehyde or the ketone of 1:0.1 to 10, 1:0.5 to 2.0, or 1:1.

[0109] In the reaction between the aromatic ring of the aromatic compound (A) and the vinyl group of the aromatic vinyl compound (B), it is preferred that (A) and (B) be reacted at a molar ratio of 1:0.1 to 8.0 or 1:0.1 to 4.0.

[0110] The above-mentioned condensation reaction and the addition reaction with the vinyl group of the aromatic vinyl compound (B) can be carried out simultaneously. As the acid catalyst used in these reactions, inorganic acids such as sulfuric acid, phosphoric acid, and perchloric acid, organic sulfonic acids such as p-toluenesulfonic acid, p-toluenesulfonic acid monohydrate, methanesulfonic acid, and trifluoromethanesulfonic acid, and carboxylic acids such as formic acid and oxalic acid are used.

[0111] The amount of the acid catalyst used is variously selected depending on the type of acid used, and is usually 0.001 to 10,000 parts by mass, preferably 0.01 to 1,000 parts by mass, and more preferably 0.1 to 100 parts by mass, based on 100 parts by mass of the aromatic compound.

[0112] The above-mentioned condensation reaction and addition reaction can be carried out without a solvent, but are usually carried out using a solvent. As a solvent, any solvent that does not hinder the reaction can be used. Examples thereof include 1,2-dimethoxyethane, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, butyl cellosolve, tetrahydrofuran, dimethoxyethane ... In addition, if the acid catalyst used is a liquid acid catalyst such as formic acid, it can also function as a solvent.

[0113] The reaction temperature during condensation is usually 40° C. to 200° C. The reaction time is variously selected depending on the reaction temperature, but is usually about 30 minutes to 50 hours.

[0114] The weight average molecular weight Mw of the polymer obtained as described above is usually 500 to 1,000,000, or 600 to 200,000.

[0115] Examples of the novolac resin obtained by the reaction of an aromatic compound with an aldehyde or a ketone include novolac resins having the following unit structures.

[0116] Moreover, R in formula (1) 1 It may be a divalent organic group obtained by removing two hydrogen atoms from the aromatic ring of N,N'-diphenyl-1,4-phenylenediamine. This compound may have three benzene rings and further have a benzene ring as a substituent, but similarly to the above, a bond with an aldehyde or a ketone to form a novolac resin is generated at any two of these benzene rings.

[0117] The novolac resin of the present invention is a polymer having a structural group (C) added to its terminal. For example, the novolac resin of the present invention is a polymer having structural groups represented by formulas (C-1) to (C-22) at the terminal of a novolac resin having a unit structure represented by the following formulas (3-1) to (3-22).

[0118] As the polymer containing the structural group represented by formula (1), a polymer containing the structural group represented by formula (1-1) is typically preferred.

[0119] In formula (1), at T 3 In the case of an alkoxy group such as tert-butoxy, T in the formula (1-1) is hydrolyzed to 3 Converted to hydroxyl.

[0120] Preferred T 1 is phenylene, T 2 It is methyl.

[0121] In formula (1-1), R 2 and R 3 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, a heterocyclic group, or a combination thereof, and the alkyl group, the aryl group, and the heterocyclic group are organic groups which may have a halogen atom, a nitro group, an amino group, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, a formyl group, a carboxyl group, an alkoxy group, or a hydroxyl group as a substituent, and R 2 With R 3 Together with the carbon atoms to which they are attached, they can form a ring.

[0122] T 2 represents a hydrogen atom, a methyl group, or a phenyl group.

[0123] m1 is an integer of 2 to 3600, or an integer of 2 to 3000, or an integer of 2 to 2000, or an integer of 2 to 735, or an integer of 3 to 3600, or an integer of 3 to 3000, or an integer of 3 to 2000, or an integer of 3 to 735, or an integer of 5 to 3600, or an integer of 5 to 3000, or an integer of 5 to 2000, or an integer of 5 to 735.

[0124] R 2 is a hydrogen atom, R 3 Examples include a phenyl group having an alkoxy group having 1 to 10 carbon atoms as a substituent.

[0125] The novolac resin used in the present invention may have the following unit structure.

[0126]

[0127]

[0128] Examples of the structural group (C) present at the terminal of the novolac resin are shown below.

[0129]

[0130]

[0131] The resist underlayer film forming composition of the present invention may include a crosslinking agent component. As the crosslinking agent, melamine system, substituted urea system, or polymer system thereof, etc. may be cited. Preferably, the crosslinking agent has at least two crosslinking substituents, such as methoxymethylated glycoluril, butoxymethylated glycoluril, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzoguanamine, butoxymethylated benzoguanamine, methoxymethylated urea, butoxymethylated urea, methoxymethylated thiourea, or methoxymethylated thiourea. In addition, condensates of these compounds may also be used.

[0132] As the crosslinking agent, a crosslinking agent with high heat resistance can be used. As the crosslinking agent with high heat resistance, a compound containing a crosslinking-forming substituent having an aromatic ring (for example, a benzene ring or a naphthalene ring) in the molecule can be preferably used.

[0133] Examples of the compound include a compound having a partial structure represented by the following formula (4) and a polymer or oligomer having a repeating unit represented by the following formula (5).

[0134]

[0135] In the above formula, R 15 , R 16 , R 17 , and R18 Each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and the alkyl groups exemplified above can be used as these alkyl groups.

[0136] In the above formula, n15 represents an integer of 1 to 2, n16 represents an integer of 1 to (6-n15), n17 represents an integer of 1 to 2, and n18 represents an integer of 0 to (4-n17).

[0137] Examples of the compounds, polymers and oligomers represented by formula (4) and formula (5) are shown below.

[0138]

[0139]

[0140] The above compounds can be obtained as products of Asahi Organic Materials Industries, Ltd. and Honshu Chemical Industries, Ltd. For example, the compound of formula (4-24) among the above crosslinking agents can be obtained as TM-BIP-A from Asahi Organic Materials Industries, Ltd.

[0141] The amount of the crosslinking agent added varies depending on the coating solvent used, the base substrate used, the required solution viscosity, the required film shape, etc., but is 0.001 to 80% by mass, preferably 0.01 to 50% by mass, and more preferably 0.05 to 40% by mass relative to the total solid content. These crosslinking agents sometimes undergo crosslinking reactions by self-condensation, but when there are crosslinking substituents in the above-mentioned polymer of the present invention, they can undergo crosslinking reactions with these crosslinking substituents.

[0142] In the present invention, as a catalyst for promoting the crosslinking reaction, an acid and / or an acid generator may be added, and p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridine p-Toluenesulfonate, salicylic acid, 5-sulfosalicylic acid, 4-phenolsulfonic acid, pyridine Acidic compounds such as 4-phenolsulfonate, camphorsulfonic acid, 4-chlorobenzenesulfonic acid, benzene disulfonic acid, 1-naphthalenesulfonic acid, citric acid, benzoic acid, hydroxybenzoic acid, naphthoic acid, and / or thermal acid generators such as 2,4,4,6-tetrabromocyclohexadienone, benzoin toluenesulfonate, 2-nitrobenzyl toluenesulfonate, and other organic sulfonic acid alkyl esters.

[0143] The amount of the compounding agent is 0.0001 to 20% by mass, preferably 0.0005 to 10% by mass, and more preferably 0.01 to 3% by mass, based on the total solid content.

[0144] The resist underlayer film-forming composition for lithography of the present invention may contain a photoacid generator in order to make the acidity of the composition match that of the photoresist to be coated as an upper layer in the photolithography step.

[0145] Preferred photoacid generators include, for example, bis(4-tert-butylphenyl)iodide. Trifluoromethanesulfonate, triphenylsulfonium trifluoromethanesulfonate, etc. Salt-based photoacid generators, halogen-containing compound-based photoacid generators such as phenyl-bis(trichloromethyl)-s-triazine, and sulfonic acid-based photoacid generators such as benzoin tosylate and N-hydroxysuccinimide trifluoromethanesulfonate.

[0146] The photoacid generator is contained in an amount of 0.2 to 10% by mass, preferably 0.4 to 5% by mass, based on the total solid content.

[0147] The resist underlayer film composition for lithography of the present invention may further contain a light absorber, a rheology regulator, an adhesion aid, a surfactant, etc. in addition to the above-mentioned components as necessary.

[0148] As further light absorbers, commercially available light absorbers described in, for example, "Technology and Market of Industrial Pigments" (Technology and Market of Industrial Pigments, published by CMC) and "Dye Handbook" (Dye Handbook, edited by the Society of Synthetic Organic Chemistry) can be preferably used, for example, CI Disperse Yellow 1, 3, 4, 5, 7, 8, 13, 23, 31, 49, 50, 51, 54, 60, 64, 66, 68, 79, 82, 88, 90, 93, 102, 114 and 124; CI Disperse Orange 1, 5, 13 , 25, 29, 30, 31, 44, 57, 72 and 73; CI Disperse Red 1, 5, 7, 13, 17, 19, 43, 50, 54, 58, 65, 72, 73, 88, 117, 137, 143, 199 and 210; CI Disperse Violet 43; CI Disperse Blue 96; CI Fluorescent Brightener 112, 135 and 163; CI Solvent Orange 2 and 45; CI Solvent Red 1, 3, 8, 23, 24, 25, 27 and 49; CI Pigment Green 10; CI Pigment Brown 2, etc.

[0149] The light absorber is usually blended in a ratio of 10% by mass or less, preferably 5% by mass or less, based on the total solid content of the resist underlayer film composition for lithography.

[0150] The rheology control agent is mainly added to improve the fluidity of the resist underlayer film forming composition, particularly to improve the uniformity of the film thickness of the resist underlayer film and to improve the filling property of the resist underlayer film forming composition into the inside of the pores during the baking step.

[0151] 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.

[0152] These rheology control agents are usually blended in a ratio of less than 30 mass % based on the total solid content of the resist underlayer film composition for lithography.

[0153] The adhesion aid is mainly added for the purpose of improving the adhesion between the substrate or the resist and the resist underlayer film-forming composition, and particularly for the purpose of preventing the resist from peeling off during development.

[0154] Specific examples include chlorosilanes such as trimethylchlorosilane, dimethylvinylchlorosilane, methyldiphenylchlorosilane, and chloromethyldimethylchlorosilane; alkoxysilanes such as trimethylmethoxysilane, dimethyldiethoxysilane, methyldimethoxysilane, dimethylvinylethoxysilane, diphenyldimethoxysilane, and phenyltriethoxysilane; silazanes such as hexamethyldisilazane, N,N'-bis(trimethylsilyl)urea, dimethyltrimethylsilylamine, and trimethylsilylimidazole; silanes such as vinyltrichlorosilane, γ-chloropropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and γ-glycidoxypropyltrimethoxysilane; benzotriazole, benzimidazole, indazole, imidazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, and 2-mercaptobenzothiazole. Heterocyclic compounds such as azole, urea, thiouracil, mercaptoimidazole, and mercaptopyrimidine, ureas such as 1,1-dimethylurea and 1,3-dimethylurea, or thiourea compounds.

[0155] These adhesion aids are usually blended in a ratio of less than 5 mass %, preferably less than 2 mass %, based on the total solid content of the resist underlayer film composition for lithography.

[0156] The resist underlayer film composition for lithography of the present invention may contain a surfactant in order to prevent the generation of pinholes, streaks, etc. and to further improve coating properties to surface unevenness.

[0157] Examples of the surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether, polyoxyethylene alkyl aryl ethers such as polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, and sorbitan tristearate, and sorbitan fatty acid esters such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate. Nonionic surfactants such as alcohol tristearate and other polyoxyethylene sorbitan fatty acid esters, Etotron EF301, EF303, and EF352 (Todo Co., Ltd. Made by ロダクツ, trade name), メガファック F171, F173, R-30, R-30N (made by Dainippon Co., Ltd., trade name), フロラード FC430, Fluorine-based surfactants such as FC431 (trade name, manufactured by Sumitomo Slide Group Co., Ltd.), Asahigard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, and SC106 (trade names, manufactured by Asahi Glass Co., Ltd.), and organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0158] The amount of these surfactants added is usually 2.0% by mass or less, preferably 1.0% by mass or less, based on the total solid content of the resist underlayer film composition for lithography of the present invention. These surfactants may be added alone or in combination of two or more.

[0159] In the present invention, as a solvent for dissolving the above-mentioned polymer, crosslinking agent component, crosslinking catalyst, etc., ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol propyl 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-methylbutyrate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, etc. These organic solvents can be used alone or in combination of two or more.

[0160] Furthermore, a high boiling point solvent such as propylene glycol monobutyl ether and propylene glycol monobutyl ether acetate may be mixed and used. Among these solvents, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, butyl lactate, and cyclohexanone are preferred for improving leveling properties.

[0161] The resist used in the present invention is a photoresist or an electron beam resist.

[0162] As the photoresist coated on the upper part of the photolithography resist underlayer film in the present invention, both negative and positive types can be used, including: a positive photoresist composed of a novolac resin and 1,2-naphthoquinonediazosulfonate, a chemically amplified photoresist composed of a binder having a group whose alkali dissolution rate increases when decomposed by an acid and a photoacid generator, a chemically amplified photoresist composed of an alkali-soluble binder, a low molecular compound whose alkali dissolution rate increases when decomposed by an acid, and a photoacid generator, a chemically amplified photoresist composed of a binder having a group whose alkali dissolution rate increases when decomposed by an acid, a low molecular compound whose alkali dissolution rate increases when decomposed by an acid, and a photoacid generator, a photoresist having a Si atom in the skeleton, and the like, for example, the product name APEX-E manufactured by Lombard Haus Co., Ltd.

[0163] In addition, as the electron beam resist applied to the upper part of the photolithography resist underlayer film in the present invention, for example, a composition composed of a resin containing Si-Si bonds in the main chain and aromatic rings at the ends and an acid generator that generates acid by electron beam irradiation, or a composition composed of poly(p-hydroxystyrene) in which a hydroxyl group is substituted with an organic group containing N-carboxyamine and an acid generator that generates acid by electron beam irradiation, etc. With respect to the latter electron beam resist composition, the acid generated by the acid generator by electron beam irradiation reacts with the N-carboxyaminooxy group of the polymer side chain, and the polymer side chain is decomposed into a hydroxyl group, exhibits alkali solubility, and is dissolved in an alkaline developer, thereby forming a resist pattern. Examples of the acid generator that generates an acid by electron beam irradiation include halogenated organic compounds such as 1,1-bis[p-chlorophenyl]-2,2,2-trichloroethane, 1,1-bis[p-methoxyphenyl]-2,2,2-trichloroethane, 1,1-bis[p-chlorophenyl]-2,2-dichloroethane, and 2-chloro-6-(trichloromethyl)pyridine, triphenylsulfonium salts, and diphenyliodonium. Salt, etc. salts, sulfonates such as nitrobenzyl tosylate and dinitrobenzyl tosylate.

[0164] As a developer for a resist having a resist underlayer film formed using the resist underlayer film composition for lithography of the present invention, aqueous solutions of alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and inorganic bases such as aqueous ammonia, primary amines such as ethylamine and n-propylamine, secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, quaternary ammonium salts such as choline, and cyclic amines such as pyrrole and piperidine can be used.

[0165] Furthermore, an appropriate amount of alcohols such as isopropyl alcohol and nonionic surfactants may be added to the above-mentioned aqueous alkali solution for use. Among them, a preferred developer is a quaternary ammonium salt, and tetramethylammonium hydroxide and choline are more preferred.

[0166] Next, the resist pattern forming method of the present invention is described. After applying the resist lower film forming composition on the substrate (e.g., silicon / silicon dioxide coating, glass substrate, ITO substrate and other transparent substrates) used in the manufacture of precision integrated circuit elements by a spin coater, coater or other appropriate coating method, it is baked to solidify and make a coating type lower film. Here, the film thickness of the resist lower film is preferably 0.01 to 3.0 μm. In addition, the conditions for baking after coating are 80 to 400°C and 0.5 to 120 minutes. Then, the resist is directly applied on the resist lower film, or after forming a film of one to several layers of coating material on the coating type lower film as needed, the resist is applied, and light or electron beams are irradiated through a specified mask, and development, rinsing and drying are performed, so that a good resist pattern can be obtained. Post-irradiation heating (PEB: Post Exposure Bake) of light or electron beams can also be performed as needed. Furthermore, the resist underlayer film in the portion where the resist has been removed by development in the above-mentioned step can be removed by dry etching, thereby forming a desired pattern on the substrate.

[0167] The exposure light in the case of the above-mentioned photoresist is a chemical radiation such as near-ultraviolet, far-ultraviolet, or extreme ultraviolet (e.g., EUV, wavelength 13.5nm), and light with a wavelength of, for example, 248nm (KrF laser), 193nm (ArF laser), 157nm (F2 laser) is used. In the light irradiation, any method that can generate acid by a photoacid generator can be used without particular limitation, and the exposure amount is 1 to 2000mJ / cm 2 , or 10~1500mJ / cm 2 , or 50~1000mJ / cm 2 .

[0168] The electron beam resist can be irradiated with electron beams using, for example, an electron beam irradiation device.

[0169] In the present invention, a semiconductor device can be manufactured through the following steps: a step of forming a resist underlayer film on a semiconductor substrate using a resist underlayer film-forming composition; a step of forming a resist film on the resist underlayer film; a step of forming a resist pattern by irradiating with light or electron beams and developing; a step of etching the resist underlayer film using the formed resist pattern; and a step of processing a semiconductor substrate using the patterned resist underlayer film.

[0170] In the future, if the miniaturization of the resist pattern is carried out, the problem of resolution and the problem that the resist pattern collapses after development will occur, and the thin film of the resist is expected. Therefore, it is difficult to obtain a sufficient resist pattern film thickness for substrate processing, and it is necessary to make not only the resist pattern, but also the resist lower film made between the resist and the semiconductor substrate to be processed also have a process that functions as a mask during substrate processing. As the resist lower film used in such a process, different from the conventional high-etching rate resist lower film, it is required to have a photolithography resist lower film with a selectivity of dry etching speed close to the resist, a photolithography resist lower film with a selectivity of dry etching speed smaller than the resist, and a photolithography resist lower film with a selectivity of dry etching speed smaller than the semiconductor substrate. In addition, such a resist lower film can also be given anti-reflection ability, and can have the function of the conventional anti-reflection film.

[0171] On the other hand, in order to obtain a fine resist pattern, a process has begun to be used in which the resist pattern and the resist underlayer film are made thinner than the pattern width during resist development when the resist underlayer film is dry-etched. As a resist underlayer film used in such a process, unlike the conventional high-etching rate anti-reflection film, a resist underlayer film having a dry-etching rate selectivity close to that of the resist is required. In addition, such a resist underlayer film can also be given an anti-reflection capability, and can have the function of the conventional anti-reflection film.

[0172] In the present invention, after forming the resist underlayer film of the present invention on the substrate, the resist can be directly coated on the resist underlayer film, or one to several layers of coating material can be formed on the resist underlayer film as needed and then the resist can be coated. Thus, even if the resist pattern width is narrowed and the resist is thinly coated to prevent pattern collapse, the substrate can be processed by selecting an appropriate etching gas.

[0173] That is, a semiconductor device can be manufactured through the following steps: a step of forming a resist underlayer film on a semiconductor substrate using a resist underlayer film-forming composition; a step of forming a hard mask on the resist underlayer film by a coating material containing a silicon component or the like or by vapor deposition (for example, silicon nitride oxide); a step of further forming a resist film on the hard mask; a step of forming a resist pattern by irradiation and development with light or electron beams; a step of etching the hard mask with a halogen-based gas through the formed resist pattern; a step of etching the resist underlayer film with an oxygen-based gas or a hydrogen-based gas through the patterned hard mask; and a step of processing the semiconductor substrate with a halogen-based gas through the patterned resist underlayer film.

[0174] The composition for forming a resist underlayer film for lithography of the present invention, taking into account the effect as an anti-reflective film, has a light absorbing portion introduced into the skeleton, so there is no diffusion into the photoresist during heating and drying. In addition, the light absorbing portion has a sufficiently large light absorption performance, so the reflected light prevention effect is good.

[0175] The resist underlayer film-forming composition for lithography of the present invention has high thermal stability, can prevent contamination of the upper layer film by decomposition products during firing, and can provide a temperature margin for the firing step.

[0176] Furthermore, the resist underlayer film composition for lithography of the present invention can be used as a film having the function of preventing reflection of light, and further preventing interaction between the substrate and the photoresist or preventing the adverse effects of materials used in the photoresist or substances generated when the photoresist is exposed on the substrate, depending on the process conditions.

[0177] Example

[0178] Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples.

[0179] (Example 1)

[0180] In a 300 mL four-necked flask, N,N'-diphenyl-1,4-phenylenediamine (41.98 g, 0.161 mol, manufactured by Tokyo Chemical Industry Co., Ltd.), 4-pentyloxybenzaldehyde (31.02 g, 0.161 mol, manufactured by Tokyo Chemical Industry Co., Ltd.), 4-(tert-butoxy)styrene (94.75 g, 0.537 mol, manufactured by Wako Pure Chemical Industries, Ltd.), propylene glycol monomethyl ether (172.37 g, manufactured by Kanto Chemical Co., Ltd.) was added, and methanesulfonic acid (4.65 g, 0.048 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) was added and stirred, and the mixture was heated to 135°C to dissolve the mixture and initiate polymerization. After 18 hours, the mixture was cooled to room temperature, and then reprecipitated using a mixed solvent of methanol (1000 g, manufactured by Kanto Chemical Co., Ltd.), 1000 g of ultrapure water, and 30% ammonia water (100 g, manufactured by Kanto Chemical Co., Ltd.). The obtained precipitate was filtered and dried at 80°C for 24 hours using a vacuum dryer to obtain 136.68 g of the target polymer (having a repeating unit structure of formula (3-15) and a structural group of formula (C-15) at the end). This polymer is hereinafter referred to as pDPPDA-AOBA-TBOS.

[0181] The weight average molecular weight Mw of pDPPDA-AOBA-TBOS measured by GPC in terms of polystyrene was 1400, and the polydispersity Mw / Mn was 1.29.

[0182] Next, 1.00 g of the obtained novolac resin (pDPPDA-AOBA-TBOS), 0.20 g of tetramethoxymethyl glycoluril (product name: POWDERLINK [registered trademark] 1174, manufactured by Nippon Science Instruments Co., Ltd.) as a crosslinking agent, 0.030 g of K-PURE TAG-2689 (manufactured by Key Instruments Co., Ltd.) as a crosslinking catalyst, and 0.001 g of a surfactant (manufactured by DIC Corporation, product name: Megafac [trade name] R-30N, a fluorine-based surfactant) were dissolved in 7.00 g of propylene glycol monomethyl ether and 16.36 g of propylene glycol monomethyl ether acetate to prepare a composition for forming a resist underlayer film.

[0183] (Example 2)

[0184] 1.00 g of pDPPDA-AOBA-TBOS as a polymer, 0.20 g of 2,2-bis[3,5-bis[(2-methoxy-1-methylethoxy)methyl]-4-hydroxyphenyl]propane (a compound obtained by dehydration condensation of the four hydroxymethyl groups of formula (4-20) with propylene glycol monomethyl ether, abbreviated as PGME-BIP-A, represented by formula (5-1)) as a crosslinking agent, and 0.020 g of pyridine as a crosslinking catalyst (acid catalyst) were added. -Phenolsulfonate and 0.001 g of a surfactant (manufactured by DIC Corporation, product name: Megafac R-30N, a fluorine-based surfactant) were dissolved in 7.00 g of propylene glycol monomethyl ether and 16.36 g of propylene glycol monomethyl ether acetate to prepare a composition for forming a resist underlayer film.

[0185]

[0186] (Comparative Example 1)

[0187] Diphenylamine (15.94 g, 0.094 mol, manufactured by Tokyo Chemical Industry Co., Ltd.), benzaldehyde (10.00 g, 0.094 mol, manufactured by Tokyo Chemical Industry Co., Ltd.), propylene glycol monomethyl ether (62 g, manufactured by Kanto Chemical Industry Co., Ltd.) were added to a 100 mL four-necked flask, and methanesulfonic acid (0.45 g, 0.005 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) was added and stirred, and the mixture was heated to 135°C to dissolve the mixture and initiate polymerization. After 1 hour, the mixture was cooled to room temperature and reprecipitated using methanol (800 g, manufactured by Kanto Chemical Industry Co., Ltd.). The obtained precipitate was filtered and dried at 80°C for 24 hours in a reduced pressure dryer to obtain 15.07 g of the target polymer (corresponding to formula (6-1). The addition reaction of the aromatic vinyl compound (B) to the terminal is not carried out.), hereinafter abbreviated as pDPA-BA).

[0188] The weight average molecular weight Mw of pDPA-BA measured by GPC in terms of polystyrene was 4100, and the polydispersity Mw / Mn was 2.22.

[0189] Next, 1.00 g of the obtained novolac resin, 0.20 g of 3,3',5,5'-tetramethoxymethyl-4,4'-bisphenol (trade name: TMOM-BP, manufactured by Honshu Chemical Industry Co., Ltd., formula (4-23)) as a cross-linking agent, 0.030 g of pyridinium p-phenolsulfonate as a cross-linking catalyst, and 0.001 g of a surfactant (manufactured by DIC Corporation, product name: Megafac [trade name] R-30N, a fluorine-based surfactant) were dissolved in 2.63 g of propylene glycol monomethyl ether and 6.14 g of propylene glycol monomethyl ether acetate to prepare a composition for forming an anti-etching agent underlayer film.

[0190]

[0191] (Comparative Example 2)

[0192] In a 100 mL four-necked flask, N-phenyl-1-naphthylamine (17.53 g, 0.080 mol, manufactured by Tokyo Chemical Industry Co., Ltd.), benzaldehyde (8.49 g, 0.080 mol, manufactured by Tokyo Chemical Industry Co., Ltd.), propylene glycol monomethyl ether acetate (62 g, manufactured by Kanto Chemical Industry Co., Ltd.) was added, and methanesulfonic acid (0.77 g, 0.008 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) was added and stirred, and the mixture was heated to 135° C. to dissolve and initiate polymerization. After 30 minutes, the mixture was cooled to room temperature, and tetrahydrofuran (THF) (18 g, manufactured by Kanto Chemical Industry Co., Ltd.) was added for dilution, and methanol (800 g, manufactured by Kanto Chemical Industry Co., Ltd.) was used for reprecipitation. The obtained precipitate was filtered and dried in a reduced pressure dryer at 80°C for 24 hours to obtain 21.04 g of the target polymer (corresponding to formula (7-1). No addition reaction of the aromatic vinyl compound (B) was performed at the terminal.), hereinafter abbreviated as pNP1NA-BA).

[0193] The weight average molecular weight Mw of pNP1NA-BA measured by GPC in terms of polystyrene was 3700, and the polydispersity Mw / Mn was 2.14.

[0194] Next, 1.00 g of the obtained novolac resin, 0.20 g of 3,3',5,5'-tetramethoxymethyl-4,4'-bisphenol (trade name: TMOM-BP, manufactured by Honshu Chemical Industry Co., Ltd., formula (4-23)) as a crosslinking agent, 0.030 g of pyridinium p-phenolsulfonate as a crosslinking catalyst, and 0.001 g of a surfactant (manufactured by DIC Corporation, product name: Megafac [trade name] R-30N, a fluorine-based surfactant) were dissolved in 2.63 g of propylene glycol monomethyl ether and 6.14 g of propylene glycol monomethyl ether acetate to prepare a composition for forming an anti-etching agent underlayer film.

[0195]

[0196] (Comparative Example 3)

[0197] 1,4-dihydropyridine was added to 10.00 g of phenyl-1-naphthylamine, 10.50 g of 1-pyrenecarboxaldehyde, 8.04 g of 4-tert-butoxystyrene, and 0.88 g of methanesulfonic acid. The mixture was stirred under reflux for 17 hours in a nitrogen atmosphere with 22.06 g of alkane and 22.06 g of toluene. The reaction solution was added dropwise to methanol, and the precipitated resin was filtered, washed, and dried under reduced pressure at 70° C. to obtain 11.44 g of a resin having a structure represented by formula (8-1).

[0198] The weight average molecular weight of the resin measured by GPC was 1,400 in terms of standard polystyrene.

[0199] Next, 1.00 g of the obtained resin, 0.20 g of tetramethoxymethyl glycoluril (product name: POWDERLINK [registered trademark] 1174, manufactured by Japan Science Instruments Co., Ltd.) as a cross-linking agent, 0.030 g of K-PURE TAG-2689 (manufactured by Key Instruments Co., Ltd.) as a cross-linking catalyst, and 0.002 g of a surfactant (manufactured by DIC Corporation, product name: Megafac, trade name R-40, a fluorine-based surfactant) were dissolved in 13.30 g of propylene glycol monomethyl ether and 5.70 g of propylene glycol monomethyl ether acetate to prepare a composition for forming an anti-etching agent underlayer film.

[0200]

[0201] 〔Optical constants, etching rate selectivity〕

[0202] The resist underlayer film-forming compositions prepared in Examples 1 to 2 and Comparative Examples 1 to 3 were applied onto silicon wafers, respectively, and heated on a hot plate at 400° C. for 90 seconds to form resist underlayer films. The refractive index and attenuation coefficient of the resist underlayer films at 193 nm were measured.

[0203] The refractive index and the attenuation coefficient were measured using an ellipsometer (VUV-VASE) manufactured by Ulam Japan Co., Ltd.

[0204] The compositions for forming an anti-etching underlayer film prepared in Examples 1 to 2 and Comparative Examples 1 to 3 were respectively coated on silicon wafers and heated on a hot plate at 400°C for 90 seconds to form an anti-etching underlayer film. The dry etching rates of the anti-etching underlayer film and the anti-etching film obtained by using an anti-etching solution manufactured by Sumitomo Chemical Co., Ltd. (product name: Sumirejist PAR855) were compared.

[0205] The dry etching rate was measured using a dry etching apparatus (RIE-10NR) manufactured by Samco Corporation, and the dry etching rate with respect to CF 4 gas was measured.

[0206] Table 1 shows the refractive index (n value), the attenuation coefficient (k value), and the ratio of dry etching rates (selectivity of dry etching rates) of the resist underlayer film.

[0207] Dry etching rate selectivity = (dry etching rate of each resist underlayer film) / (dry etching rate of the resist film)

[0208] [Table 1]

[0209] Table 1

[0210]

[0211] According to the results in Table 1, the resist underlayer film obtained using the resist underlayer film-forming composition of the present invention has an appropriate antireflection effect. Furthermore, after a resist film is formed on the upper layer of the resist underlayer film obtained using the resist underlayer film-forming composition of the present invention, and a resist pattern is formed by exposure and development, dry etching is performed using an etching gas or the like according to the resist pattern to process the substrate, the resist underlayer film of the present invention has a large dry etching rate relative to the resist film, so that the substrate can be processed.

[0212] [Coating test on high-low substrate]

[0213] As an evaluation of the high-low coverage, a SiO2 substrate with a film thickness of 200nm was used to compare the coating thickness of the dense pattern area (DENSE) with a groove width of 50nm and a spacing of 100nm and the open area (OPEN) without a pattern. After the compositions for forming the resist underlayer film of Examples 1 to 2 and Comparative Examples 1 to 2 were coated on the above-mentioned substrates, they were fired at 400°C for 90 seconds and adjusted to form a film thickness of 150nm. The high-low coverage of the substrate was observed using a scanning electron microscope (S-4800) manufactured by Hitachi HiTech Nologis Co., Ltd., and the film thickness difference (the coating height difference between the dense area and the open area, called Bias) of the high-low substrate was measured to evaluate the flattening property. The film thickness and the coating height difference of each area are shown in Table 2. In the evaluation of the planarization property, the smaller the Bias value is, the higher the planarization property is.

[0214] [Table 2]

[0215] Table 2

[0216]

[0217] If the coverage on uneven substrates is compared, the results of Examples 1 to 2 show that the coating height difference between the pattern area and the open area is smaller than that of Comparative Examples 1 and 3. Therefore, the resist underlayer film obtained from the resist underlayer film forming composition of Examples 1 to 2 can be said to have good planarization properties.

[0218] In the method for forming a resist underlayer film obtained by coating the resist underlayer film forming composition of the present invention on a semiconductor substrate and firing it, the coating height difference between the portion with the height difference and the portion without the height difference of the substrate can be 10 to 60 nm, or 10 to 50 nm, or 10 to 30 nm.

[0219] The present invention can provide a resist underlayer film-forming composition capable of forming a resist underlayer film having well-balanced properties, particularly heat resistance, planarization property, and etching resistance.

[0220] Industrial Availability

[0221] The present invention can provide a composition for forming a resist underlayer film which is not easily mixed when a photoresist composition and different resist underlayer films are stacked, and improves the filling property of a pattern during firing by increasing the thermal reflowability of a polymer.

Claims

1. A resist underlayer film-forming composition comprising a novolac resin containing a structural group (C) formed by reacting an aromatic ring of an aromatic compound (A) containing at least two amino groups and at least three aromatic rings having 6 to 40 carbon atoms with a vinyl group of an aromatic vinyl compound (B), The aromatic compound (A) is a novolac resin obtained by reacting an organic compound containing at least two amino groups and at least three aromatic rings having 6 to 40 carbon atoms with an aldehyde or a ketone.

2. The resist underlayer film-forming composition according to claim 1, wherein the structural group (C) is the following formula (1): In formula (1), R 1 is a divalent group containing at least two amino groups and at least three aromatic rings having 6 to 40 carbon atoms, R 2 and R 3 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, a heterocyclic group, or a combination thereof, and the alkyl group, the aryl group, and the heterocyclic group are organic groups which may have a halogen atom, a nitro group, an amino group, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, a formyl group, a carboxyl group, an alkoxy group, or a hydroxyl group as a substituent, and R 2 With R 3 can form rings with the carbon atoms to which they are attached, T 1 is an arylene group having 6 to 40 carbon atoms, T 3 represents 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, a hydroxyl group, a cyano group, a nitro group, an amino group, a carboxyl group, an acetyl group, a hydroxymethyl group, a halomethyl group, a -YZ group, a halogen atom, or a combination thereof; Y represents an oxygen atom, a sulfur atom, a carbonyl group, or an ester group, and Z represents an alkyl group having 1 to 10 carbon atoms; T 2 represents a hydrogen atom, a methyl group, or a phenyl group, m is an integer from 0 to (5+2n), n represents the structure as T 1 The degree of fusion of the aromatic rings of the arylene group is defined as, m1 is an integer from 2 to 3600.

3. The resist underlayer film-forming composition according to claim 2, wherein R 1 is a divalent organic group obtained by removing two hydrogen atoms from the aromatic ring of the compound represented by the following formula (2), In formula (2), Ar 1 ,Ar 2 and Ar 3 each independently represents a benzene ring or a naphthalene ring, R 6 , R 7 and R 8 are each independently a substituent on these rings, and R 6 , R 7 and R 8 are each independently selected from a halogen atom, a nitro group, an amino group, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, and a combination thereof, and the alkyl group, the alkenyl group and the aryl group represent an organic group that may contain an ether bond, a ketone bond, or an ester bond, R 4 and R 5 are each independently selected from a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, and a combination thereof, and the alkyl group, the alkenyl group, and the aryl group represent an organic group that may contain an ether bond, a ketone bond, or an ester bond, n1, n2, and n3 are each greater than 0 and are less than or equal to R 6 , R 7 and R 8 The largest integer that can be substituted.

4. The resist underlayer film forming composition according to claim 2, wherein R 1 It is a divalent organic group obtained by removing two hydrogen atoms from the aromatic ring of N,N'-diphenyl-1,4-phenylenediamine.

5. The resist underlayer film forming composition according to any one of claims 2 to 4, wherein R 3 is a hydrogen atom, R 2 It is an aryl group selected from phenyl, naphthyl, anthracenyl, and pyrene, and the aryl group may have a halogen atom, a nitro group, an amino group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, a formyl group, a carboxyl group, or a hydroxyl group as a substituent.

6. The resist underlayer film forming composition according to any one of claims 2 to 4, wherein R 3 is a hydrogen atom, R 2 The phenyl group may have a halogen atom, a nitro group, an amino group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, a formyl group, a carboxyl group, or a hydroxyl group as a substituent.

7. The resist underlayer film forming composition according to claim 2, wherein 1 It is phenylene.

8. The resist underlayer film-forming composition according to claim 2, wherein the structural group (C) is the following formula (1-1): In formula (1-1), R 2 and R 3 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, a heterocyclic group, or a combination thereof, and the alkyl group, the aryl group, and the heterocyclic group are organic groups which may have a halogen atom, a nitro group, an amino group, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, a formyl group, a carboxyl group, an alkoxy group, or a hydroxyl group as a substituent, and R 2 With R 3 can form rings with the carbon atoms to which they are attached; T 2 represents a hydrogen atom, a methyl group, or a phenyl group, m1 is an integer from 2 to 3600. 9 . The resist underlayer film-forming composition according to claim 1 , further comprising a cross-linking agent. 10 . The resist underlayer film forming composition according to claim 1 , further comprising an acid and / or an acid generator. 11 . A resist underlayer film obtained by applying the resist underlayer film-forming composition according to claim 1 onto a semiconductor substrate and firing the resulting composition.

12. A method for manufacturing a semiconductor device, comprising the following steps: a step of forming a resist underlayer film on a semiconductor substrate using the resist underlayer film-forming composition described in any one of claims 1 to 10; a step of forming a resist film on the resist underlayer film; a step of forming a resist pattern by irradiating and developing with light or electron beams; a step of etching the resist underlayer film using the formed resist pattern; and a step of processing a semiconductor substrate using the patterned resist underlayer film.

13. A method for manufacturing a semiconductor device, comprising the following steps: a step of forming a resist underlayer film on a semiconductor substrate using the resist underlayer film-forming composition described in any one of claims 1 to 10; a step of forming a hard mask on the resist underlayer film; a step of further forming a resist film on the hard mask; a step of forming a resist pattern by irradiating and developing with light or electron beams; a step of etching the hard mask using the formed resist pattern; a step of etching the resist underlayer film using the patterned hard mask; and a step of processing a semiconductor substrate using the patterned resist underlayer film.

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