Organic resin composition for forming metal oxide resist pattern

Abstract

A composition for forming an organic film, which is used for forming an organic film, forming the organic film between resist patterns formed from a metal-containing resist film, and then removing the organic film, and which contains an organic film constituent component and a solvent.

Description

Technical Field

[0001] The present invention relates to an organic film-forming composition for forming an organic film, which is used for forming the organic film between resist patterns formed of a metal-containing resist and thereafter removing the organic film. Background Art

[0002] In the past, microfabrication was performed by photolithography using photoresist in the manufacture of semiconductor devices. The microfabrication is a processing method in which a thin film of photoresist is formed on a semiconductor substrate such as a silicon wafer, active light such as ultraviolet rays is irradiated on the thin film through a mask pattern on which a pattern of a semiconductor device is drawn, and then developed, and the substrate is etched using the obtained photoresist pattern as a protective film, thereby forming microscopic irregularities corresponding to the pattern on the substrate surface.

[0003] As semiconductor devices become more and more highly integrated, the active light used is also tending to be shorter in wavelength from KrF excimer laser (248nm) to ArF excimer laser (193nm), and exposure technology using EUV (Extreme Ultra violet) and electron beam has been studied.

[0004] Towards further fine patterning of resists, in recent years, the development of lithography technology using metal oxide resists (also referred to as MOR, metal-containing resists) with excellent etching resistance compared to conventional chemically amplified resists has been actively carried out (for example, Patent Document 1, etc.). In the future, further miniaturization will require thinner resist films, but the present metal oxide resist (MOR) (hereinafter also referred to as "metal-containing resist") has sufficient etching resistance for fine patterning even in thin films, and therefore has been expected as a material used in the next generation EUV lithography technology in recent years.

[0005] Prior art literature

[0006] Patent Literature

[0007] Patent Document 1: Japanese Patent Application Publication No. 2011-253185 Summary of the invention

[0008] Technical problem to be solved by the invention

[0009] As the resist pattern formed of a metal-containing resist becomes finer, resist pattern collapse becomes a problem.

[0010] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide an organic film-forming composition capable of preventing pattern collapse in fine patterning using a metal-containing resist film, and a method for manufacturing a semiconductor device using the organic film-forming composition.

[0011] Technical solutions for solving technical problems

[0012] The present inventors have conducted intensive studies to solve the above-mentioned technical problems, and as a result, have found that the above-mentioned technical problems can be solved, and have completed the present invention having the following gist.

[0013] That is, the present invention includes the following contents.

[0014] [1] A composition for forming an organic film, which is used for forming an organic film, wherein the organic film is formed between resist patterns formed of a metal-containing resist film and then the organic film is removed,

[0015] The organic film-forming composition contains organic film-constituting components and a solvent.

[0016] [2] The composition for forming an organic film according to [1], wherein the metal-containing resist film contains at least one element of Si, Ge, Sn, Ti, Zr, Hf, Al, and Co.

[0017] [3] The composition for forming an organic film according to [1], wherein the organic film-constituting component contains a polymer (A).

[0018] [4] The composition for forming an organic film according to [3], wherein the polymer (A) is not water-soluble.

[0019] [5] The composition for forming an organic film according to [4], wherein the polymer (A) is a polymer (A1) having a ring structure.

[0020] [6] The composition for forming an organic film according to [5], wherein the polymer (A1) is a polymer (A1-1) having a ring structure in its main chain.

[0021] [7] The composition for forming an organic film according to [5], wherein the polymer (A1) is a polymer (A1-2) having a ring structure in a side chain.

[0022] [8] The composition for forming an organic film according to [6], wherein at least one of the main chain ring structures in the polymer (A1-1) is a monocyclic aliphatic ring.

[0023] [9] The composition for forming an organic film according to [8], wherein the polymer (A1-1) is a polymer (X) having a repeating unit represented by the following formula (X).

[0024] [Chemistry 1]

[0025]

[0026] (In the formula (X), T represents a group having a monocyclic aliphatic ring constituting the main chain of the polymer (X).

[0027] Q represents a divalent linking group.

[0028] Ar represents an aromatic group which may have a substituent. )

[0029]

[10] The composition for forming an organic film according to [6], wherein at least one of the main chain ring structures in the polymer (A1-1) is a heterocyclic ring.

[0030]

[11] The composition for forming an organic film according to

[10] , wherein the polymer (A1-1) is a polymer (Y) having a repeating unit represented by the following formula (Y).

[0031] [Chemistry 2]

[0032]

[0033] (In formula (Y), A 1 , A 2 , A 3 , A 4 , A 5 and A 6 They represent a hydrogen atom, a methyl group or an ethyl group respectively.

[0034] X 1 It represents the following formula (Y2), the following formula (Y3), the following formula (Y4), or the following formula (Y0).

[0035] Q represents the following formula (Y5) or the following formula (Y6).

[0036] [Chemistry 3]

[0037]

[0038] (In formula (Y2), formula (Y3), formula (Y4) and formula (Y0), R 1 and R 2Each of them represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 3 to 6 carbon atoms, a benzyl group or a phenyl group, and the alkyl group having 1 to 6 carbon atoms, the alkenyl group having 3 to 6 carbon atoms, the benzyl group and the phenyl group may be substituted by a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a cyano group, a hydroxyl group, a carboxyl group and an alkylthio group having 1 to 6 carbon atoms. 1 and R 2 They may be bonded to each other to form a ring having 3 to 6 carbon atoms.

[0039] R 3 represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 3 to 6 carbon atoms, a benzyl group or a phenyl group, and the phenyl group may be substituted by a group selected from an alkyl group having 1 to 6 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a cyano group, a hydroxyl group and an alkylthio group having 1 to 6 carbon atoms.

[0040] Indicates a bond. 1 represents a bond to a carbon atom. 2 represents the bond to the nitrogen atom. )

[0041] [Chemistry 4]

[0042]

[0043] (In formula (Y5) and formula (Y6), Q 1 represents an alkylene group having 1 to 10 carbon atoms, a phenylene group, a naphthylene group, or anthrylene group, and the alkylene group, the phenylene group, the naphthylene group, and the anthrylene group may be substituted by an alkyl group having 1 to 6 carbon atoms, a carbonyloxyalkyl group having 2 to 7 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a phenyl group, a nitro group, a cyano group, a hydroxyl group, an alkylthio group having 1 to 6 carbon atoms, a group having a disulfide group, a carboxyl group, or a group containing a combination thereof.

[0044] n 1 and n 2 Represents 0 or 1 respectively.

[0045] X 2 It represents the above-mentioned formula (Y2), the above-mentioned formula (Y3), or the above-mentioned formula (Y0).

[0046] Indicates a bond. )

[0047]

[12] The composition for forming an organic film according to [7], wherein at least one of the ring structures of the side chains in the polymer (A1-2) is a heterocyclic ring.

[0048]

[13] The composition for forming an organic film according to [7], wherein at least one of the ring structures of the side chains in the polymer (A1-2) is a lactone ring.

[0049]

[14] The composition for forming an organic film according to

[13] , wherein the polymer (A1-2) is a polymer (Z) having a repeating unit represented by the following formula (Z).

[0050] [Chemistry 5]

[0051]

[0052] (In formula (Z), Q represents a divalent linking group.

[0053] R 1 It represents a substituted or unsubstituted trivalent hydrocarbon group having 3 or 4 carbon atoms.

[0054] P represents a bonding group constituting the main chain.

[0055] R 2 represents a hydrogen atom, a methyl group, or a halogen atom. )

[0056]

[15] The composition for forming an organic film according to [4], wherein the polymer (A) is a polymer (A2) having a repeating unit represented by the following formula (Q).

[0057] [Chemistry 6]

[0058]

[0059] (In formula (Q), R 11 It represents an alkyl group having 1 to 4 carbon atoms.

[0060] R 12 represents a hydrogen atom, a methyl group, or a halogen atom. )

[0061]

[16] The organic film-forming composition according to any one of [1] to

[15] , which is used to prevent the resist pattern from collapsing.

[0062]

[17] The organic film-forming composition according to any one of [1] to

[16] , which also serves as a developer when forming the resist pattern.

[0063]

[18] A method for manufacturing a semiconductor element, comprising: irradiating a metal-containing resist film with light or an electron beam;

[0064] A step of bringing a developer into contact with the metal-containing resist film irradiated with the light or electron beam to obtain a resist pattern;

[0065] A step of applying the organic film-forming composition described in any one of [1] to

[16] on the resist pattern without drying the resist pattern in contact with the developer to form an organic film between the resist patterns; and

[0066] A step of removing the organic film.

[0067]

[19] The method for manufacturing a semiconductor element according to

[18] , wherein, in the step of forming the organic film, the organic film is also formed on the resist pattern.

[0068]

[20] A method for manufacturing a semiconductor element according to

[18] or

[19] , wherein the step of removing the organic film is selected from dry etching, wet etching, radiation etching, high temperature sintering, dissolution removal using a solvent, and ozone treatment.

[0069]

[21] A substrate having a metal-containing resist pattern, wherein the organic film-forming composition described in any one of [1] to

[16] is applied onto the metal-containing resist pattern, and an organic film is embedded between the metal-containing resist patterns.

[0070]

[22] A method for manufacturing a substrate with a metal-containing resist pattern, comprising: coating the organic film-forming composition described in any one of [1] to

[16] on the metal-containing resist pattern, and embedding an organic film between the metal-containing resist patterns.

[0071] Effects of the Invention

[0072] According to the present invention, it is possible to provide an organic film-forming composition capable of preventing pattern collapse in fine patterning using a metal-containing resist film, and a method for manufacturing a semiconductor device using the organic film-forming composition. BRIEF DESCRIPTION OF THE DRAWINGS

[0073] Figure 1A This is a schematic cross-sectional view for explaining one embodiment of a method for manufacturing a semiconductor element (part 1).

[0074] Figure 1B This is a schematic cross-sectional view for explaining one embodiment of a method for manufacturing a semiconductor element (part 2).

[0075] Figure 1C This is a schematic cross-sectional view for explaining one embodiment of a method for manufacturing a semiconductor element (part 3).

[0076] Figure 1D This is a schematic cross-sectional view for explaining one embodiment of a method for manufacturing a semiconductor element (Part 4).

[0077] Figure 1EThis is a schematic cross-sectional view for explaining one embodiment of a method for manufacturing a semiconductor element (part 5).

[0078] Figure 2 It is a schematic cross-sectional view showing one embodiment of an organic film between resist patterns.

[0079] Figure 3A This is a schematic cross-sectional view for explaining another embodiment of the method for manufacturing a semiconductor element (Part 1).

[0080] Figure 3B This is a schematic cross-sectional view for explaining another embodiment of the method for manufacturing a semiconductor element (part 2).

[0081] Figure 3C This is a schematic cross-sectional view for explaining another embodiment of the method for manufacturing a semiconductor element (Part 3).

[0082] Figure 3D This is a schematic cross-sectional view for explaining another embodiment of the method for manufacturing a semiconductor element (Part 4). DETAILED DESCRIPTION

[0083] (Organic film-forming composition)

[0084] The organic film-forming composition of the present invention is an organic film-forming composition for forming an organic film which is formed between resist patterns formed of a metal-containing resist film and is subsequently removed.

[0085] The organic film-forming composition contains organic film-constituting components and a solvent.

[0086] The present inventors have found that when a resist pattern is formed from a resist film containing a metal, resist pattern collapse is likely to occur after development.

[0087] Generally, in forming a resist pattern, after development, drying is performed to remove a developing solution.

[0088] The present inventors have made repeated studies and found that the collapse of the resist pattern can be prevented by forming an organic film between the resist patterns after development and removing the organic film instead of drying and removing the developer after development, thereby completing the present invention.

[0089] It should be noted that the present inventors believe that during drying for removing the developer, the capillary force of the developer may have an influence and cause the resist pattern to collapse.

[0090] It should be noted that International Publication No. 2012 / 128251 discloses a developer for use in a photolithography process, the developer comprising a polymer for forming a dry etching mask and an organic solvent (for example, see claim 1). However, the developer is used to form a reverse pattern by the polymer contained therein, and in this respect, the invention described in International Publication No. 2012 / 128251 is clearly different from the technical concept of the present invention.

[0091] In addition, Japanese Patent Publication No. 2011-33842 discloses a treatment liquid containing a resin soluble in an organic solvent and an organic solvent, which is used to form a pattern using a chemically amplified resist composition (for example, refer to claim 1). Here, according to paragraph

[0013] of Japanese Patent Publication No. 2011-33842, it is inferred that in this technology, the resin soluble in an organic solvent promotes the penetration of a developer or a rinse liquid into the resist composition, which helps to increase the dissolution rate. In contrast, in the present invention, a metal-containing resist film is used as the resist film. Generally, resins are incompatible with metal-containing resist films, so when the resist film is a metal-containing resist film, it is not expected that the resin soluble in an organic solvent promotes the penetration of a developer or a rinse liquid into the resist composition. In this regard, the invention recorded in Japanese Patent Publication No. 2011-33842 is significantly different from the technical concept of the present invention.

[0092] The metal-containing resist film is not particularly limited, but preferably contains at least one element of Si, Ge, Sn, Ti, Zr, Hf, Al, and Co.

[0093] The organic film-forming composition is preferably used to prevent the resist pattern from collapsing.

[0094] The organic film-forming composition also serves as a developer when forming a resist pattern, for example.

[0095] The method for removing the organic film is not particularly limited, and examples thereof include a method for removing the organic film used in a semiconductor photolithography process.

[0096] Examples of methods for removing the organic film include dry etching, wet etching (e.g., removal by decomposition with an acidic solution), radiation etching, high temperature calcination, removal by dissolution using a solvent, and ozone treatment, etc. These methods may be performed alone or in combination of two or more.

[0097] <Organic film constituent components>

[0098] The organic film constituent components are not particularly limited, and examples thereof include low molecular weight compounds, polymers, crosslinking agents, surfactants, curing catalysts, fillers, and other additives.

[0099] The organic film constituent components refer to components that exist in the organic film directly or by reacting with other components when the organic film is formed from the organic film-forming composition, and can be said to be components other than the solvent in the organic film-forming composition.

[0100] The organic film constituent components are not particularly limited as long as they contain organic components, and do not need to be composed entirely of organic components, and may contain, for example, inorganic components.

[0101] The organic film constituent component preferably contains a polymer (A).

[0102] <<Polymer (A)>>

[0103] The polymer (A) is not particularly limited.

[0104] Examples of the polymer (A) include addition polymers and condensation polymers such as polyester, polystyrene, polyimide, acrylic polymer, methacrylic polymer, polyvinyl ether, phenol novolac, naphthol novolac, polyether, polyamide, and polycarbonate.

[0105] Examples of the polymer (A) include the polymer (A1) and the polymer (A2) described below.

[0106] The polymer (A) is not polysiloxane, for example.

[0107] The polymer (A) may be a homopolymer or a copolymer.

[0108] The weight average molecular weight of the polymer (A) is not particularly limited, but is preferably 1,000 to 200,000, more preferably 1,500 to 150,000, and particularly preferably 2,000 to 100,000.

[0109] In this specification, the weight average molecular weight is a molecular weight obtained by polystyrene conversion based on GPC (Gel Permeation Chromatography) analysis.

[0110] The polymer (A) is preferably not water-soluble. In this specification, water-soluble means that at 25°C, in 100g of water, 5g or more of the object (e.g., polymer) is dissolved. That is, the so-called non-water-soluble means that at 25°C, in 100g of water, the amount of the object (e.g., polymer) dissolved is less than 5g. The above-mentioned dissolution means that after the solution after the object is dissolved is placed for 1 hour at a temperature of 20 to 30°C and in the atmosphere, no precipitate can be observed by visual observation. It should be noted that the polymers synthesized in Synthesis Examples 1 to 4 in the Examples of this specification are not water-soluble.

[0111] The polymer (A) is, for example, a polymer (A1) having a ring structure.

[0112] The polymer (A1) is, for example, a polymer (A1-1) having a ring structure in its main chain.

[0113] The polymer (A1) is, for example, a polymer (A1-2) having a ring structure in a side chain.

[0114] The polymer (A1-1) having a ring structure in the main chain may have the ring structure only in the main chain or in a side chain.

[0115] The polymer (A1-2) having a ring structure in a side chain may have a ring structure only in a side chain or may have a ring structure in a main chain.

[0116] The main chain refers to, for example, a portion including the longest atomic chain in a polymer.

[0117] At least one type of the main chain ring structure in the polymer (A1-1) is, for example, a monocyclic aliphatic ring.

[0118] At least one of the main chain ring structures in the polymer (A1-1) is, for example, a heterocyclic ring. Examples of heteroatoms constituting the heterocyclic ring include oxygen atoms and nitrogen atoms. Examples of the heterocyclic ring include an isocyanurate ring and a barbituric acid ring.

[0119] At least one type of the ring structure of the side chain in the polymer (A1-2) is, for example, a heterocycle. Examples of heteroatoms constituting the heterocycle include oxygen atoms and nitrogen atoms. Examples of the heterocycle include 5- to 7-membered rings.

[0120] At least one type of the ring structure of the side chain in the polymer (A1-2) is, for example, a lactone ring.

[0121] <<<Polymer (X)>>>

[0122] The polymer (A1-1) is preferably a polymer (X) having a repeating unit represented by the following formula (X).

[0123] [Chemistry 7]

[0124]

[0125] (In the formula (X), T represents a group having a monocyclic aliphatic ring constituting the main chain of the polymer (X).

[0126] Q represents a divalent linking group.

[0127] Ar represents an aromatic group which may have a substituent. )

[0128] The polymer (X) may have two or more repeating units represented by the formula (X) in which Ar in the formula (X) is different.

[0129] Examples of the monocyclic aliphatic ring include cycloalkane rings having 4 to 10 carbon atoms, among which a cyclohexane ring is preferred.

[0130] The monocyclic aliphatic ring may have a substituent other than -Q-Ar in formula (X). Examples of the substituent include an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, a halogen atom, a nitro group, and an amino group.

[0131] Examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a cyclopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a cyclobutyl group, a 1-methyl-cyclopropyl group, a 2-methyl-cyclopropyl 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, a cyclopentyl group, a 1-methyl-cyclobutyl group, a 2-methyl-cyclo Butyl, 3-methyl-cyclobutyl, 1,2-dimethyl-cyclopropyl, 2,3-dimethyl-cyclopropyl, 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.

[0132] Examples of the aryl group having 6 to 20 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 and 9-phenanthryl.

[0133] In the present invention, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

[0134] As the repeating unit represented by the formula (X), a repeating unit represented by the following formula (Xa) is preferred.

[0135] [Chemistry 8]

[0136]

[0137] (In formula (Xa), R 1 It represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, a halogen atom, a nitro group, or an amino group.

[0138] Q represents a divalent linking group.

[0139] Ar represents an aromatic group which may have a substituent. )

[0140] The aromatic ring in the aromatic group of Ar in Formula (X) and Formula (Xa) may be an aromatic hydrogen ring or an aromatic hetero ring. The aromatic ring may be a monocyclic ring or a condensed ring.

[0141] Examples of the aromatic hydrocarbon ring include a benzene ring, a naphthalene ring, and an anthracene ring.

[0142] Examples of the substituent that Ar has in formula (X) and formula (Xa) include an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a hydroxyl group, a halogen atom, a nitro group, and an amino group.

[0143] Examples of the number of atoms in the divalent linking group constituting Q in the formula (X) and the formula (Xa) include 1 to 20 atoms.

[0144] Examples of Q include the following linking groups (Qa).

[0145] [Chemistry 9]

[0146]

[0147] (In formula (Qa), 1 represents a bond to the monocyclic aliphatic ring. 2 represents a bond to the aromatic ring. )

[0148] The polymer (X) is, for example, a reaction product of a polymer (X1) having a repeating unit represented by the following formula (X1) and an aromatic carboxylic acid (X2).

[0149] [Chemistry 10]

[0150]

[0151] (In formula (Xa), R 1 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, a halogen atom, a nitro group, or an amino group.

[0152] A commercially available polymer having a repeating unit represented by formula (X1) may be used, and examples of the commercially available polymer include EHPE3150 (manufactured by Daicel Chemical Industries, Ltd.).

[0153] Examples of the aromatic carboxylic acid (X2) include monocyclic aromatic carboxylic acids and condensed-ring aromatic carboxylic acids.

[0154] Examples of the monocyclic aromatic carboxylic acid include benzoic acid and the like.

[0155] Examples of the fused ring aromatic carboxylic acid include naphthalenecarboxylic acid and anthracenecarboxylic acid.

[0156] Examples of the polymer (X) include the following polymers (X-1) to (X-12). The following polymers have two or three types of repeating units.

[0157] [Chemistry 11]

[0158]

[0159] [Chemistry 12]

[0160]

[0161] [Chemistry 13]

[0162]

[0163] [Chemistry 14]

[0164]

[0165] [Chemistry 15]

[0166]

[0167] [Chemistry 16]

[0168]

[0169] [Chemistry 17]

[0170]

[0171] [Chemistry 18]

[0172]

[0173] [Chemistry 19]

[0174]

[0175] [Chemistry 20]

[0176]

[0177] [Chemistry 21]

[0178]

[0179] [Chemistry 22]

[0180]

[0181] Examples of the polymer (X) include polymers described in International Publication No. 2011 / 021555. The contents of International Publication No. 2011 / 021555 are incorporated herein by reference to the same extent as if all were expressly stated.

[0182] The weight average molecular weight of the polymer (X) is not particularly limited, but is preferably 1,000 to 15,000, more preferably 1,500 to 10,000, and particularly preferably 2,000 to 7,000.

[0183] <<<Polymer (Y)>>>

[0184] The polymer (A1-1) is preferably a polymer (Y) having a repeating unit represented by the following formula (Y).

[0185] [Chemistry 23]

[0186]

[0187] (In formula (Y), A 1 , A 2 , A 3 , A 4 , A 5 and A 6 They represent a hydrogen atom, a methyl group or an ethyl group respectively.

[0188] X 1It represents the following formula (Y2), the following formula (Y3), the following formula (Y4), or the following formula (Y0).

[0189] Q represents the following formula (Y5) or the following formula (Y6).

[0190] [Chemistry 24]

[0191]

[0192] (In formula (Y2), formula (Y3), formula (Y4) and formula (Y0), R 1 and R 2 Each of them represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 3 to 6 carbon atoms, a benzyl group or a phenyl group, and the alkyl group having 1 to 6 carbon atoms, the alkenyl group having 3 to 6 carbon atoms, the benzyl group and the phenyl group may be substituted by a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a cyano group, a hydroxyl group, a carboxyl group and an alkylthio group having 1 to 6 carbon atoms. 1 and R 2 They may be bonded to each other to form a ring having 3 to 6 carbon atoms.

[0193] R 3 represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 3 to 6 carbon atoms, a benzyl group or a phenyl group, and the phenyl group may be substituted by a group selected from an alkyl group having 1 to 6 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a cyano group, a hydroxyl group and an alkylthio group having 1 to 6 carbon atoms.

[0194] Indicates a bond. 1 represents a bond to a carbon atom. 2 represents the bond to the nitrogen atom. )

[0195] [Chemistry 25]

[0196]

[0197] (In formula (Y5) and formula (Y6), Q 1 represents an alkylene group having 1 to 10 carbon atoms, a phenylene group, a naphthylene group, or anthrylene group, and the alkylene group, the phenylene group, the naphthylene group, and the anthrylene group may be substituted by an alkyl group having 1 to 6 carbon atoms, a carbonyloxyalkyl group having 2 to 7 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a phenyl group, a nitro group, a cyano group, a hydroxyl group, an alkylthio group having 1 to 6 carbon atoms, a group having a disulfide group, a carboxyl group, or a group containing a combination thereof.

[0198] n 1 and n 2Represents 0 or 1 respectively.

[0199] X 2 It represents the above-mentioned formula (Y2), the above-mentioned formula (Y3), or the above-mentioned formula (Y0).

[0200] Indicates a bond. )

[0201] Examples of the repeating unit represented by the formula (Y) include repeating units represented by the following formulae (Y-1) to (Y-20).

[0202] [Chemistry 26]

[0203]

[0204] [Chemistry 27]

[0205]

[0206] [Chemistry 28]

[0207]

[0208] [Chemistry 29]

[0209]

[0210] [Chemistry 30]

[0211]

[0212] In formula (Y-20), R is an alcohol residue (an organic group other than a hydroxyl group of an alcohol), and this R represents an alkyl group, an ether group, or a combination thereof. Examples of the above R include an alkyl group and an alkoxyalkyl group.

[0213] Examples of the polymer (Y) include polymers described in International Publication No. 2013 / 018802. The contents of International Publication No. 2013 / 018802 are incorporated herein by reference to the same extent as if all were expressly stated.

[0214] The weight average molecular weight of the polymer (Y) is not particularly limited, but is preferably 1,000 to 30,000, more preferably 2,000 to 20,000, and particularly preferably 3,000 to 15,000.

[0215] <<<Polymer (Z)>>>

[0216] The polymer (A1-2) is preferably a polymer (Z) having a repeating unit represented by the following formula (Z).

[0217] [Chemistry 31]

[0218]

[0219] (In formula (Z), Q represents a divalent linking group.

[0220] R 1 It represents a substituted or unsubstituted trivalent hydrocarbon group having 3 or 4 carbon atoms.

[0221] P represents a bonding group constituting the main chain.

[0222] R 2 represents a hydrogen atom, a methyl group, or a halogen atom. )

[0223] As the repeating unit represented by the formula (Z), a repeating unit represented by the following formula (Za) is preferred.

[0224] [Chemistry 32]

[0225]

[0226] (In formula (Za), R 2 represents a hydrogen atom, a methyl group or a halogen atom.

[0227] L represents the following formula (L-1) or formula (L-2).

[0228] [Chemistry 33]

[0229]

[0230] (In formula (L-1) and formula (L-2), Indicates a bond. )

[0231] The polymer (Z) may have a repeating unit represented by the following formula (Z-2).

[0232] [Chemistry 34]

[0233]

[0234] (In formula (Z-2), R 3 represents a hydrogen atom, a methyl group or a halogen atom.

[0235] R 4 represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted carbocyclic aromatic group, or a substituted or unsubstituted heterocyclic aromatic group.

[0236] Examples of the repeating unit represented by the formula (Z-2) include a repeating unit represented by the following formula (Z-2-1) and a repeating unit represented by the formula (Z-2-2).

[0237] [Chemistry 35]

[0238]

[0239] (In formula (Z-2-1) and formula (Z-2-2), R 3 represents a hydrogen atom, a methyl group or a halogen atom.

[0240] R 4a It represents an alkyl group having 1 to 4 carbon atoms substituted with a hydroxy group.

[0241] R 4b represents a substituted or unsubstituted carbocyclic aromatic group. )

[0242] As R in formula (Z-2) 4 Examples of the substituted or unsubstituted alkyl group having 1 to 10 carbon atoms include alkyl groups having 1 to 10 carbon atoms and alkyl groups having 1 to 4 carbon atoms substituted with a hydroxy group.

[0243] R in formula (Z-2) 4 R in formula (Z-2-2) 4b Examples of the substituted or unsubstituted carbocyclic aromatic group in include phenyl, benzyl, naphthyl, anthracenyl, anthracenylmethyl and the like.

[0244] Examples of the alkyl group having 1 to 4 carbon atoms substituted with a hydroxy group include a 2-hydroxyethyl group and a 2-hydroxypropyl group.

[0245] The polymer (Z) may have other repeating units. Examples of monomers from which other repeating units are derived include acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, styrenes, and crotonates.

[0246] Examples of the acrylamides include acrylamide, N-alkyl acrylamide, N-aryl acrylamide, N,N-dialkyl acrylamide, N,N-diaryl acrylamide, N-methyl-N-phenyl acrylamide, and N-2-acetamidoethyl-N-acetylacrylamide.

[0247] Examples of the methacrylamides include methacrylamide, N-alkyl methacrylamide, N-aryl methacrylamide, N,N-dialkyl methacrylamide, N,N-diaryl methacrylamide, N-methyl-N-phenyl methacrylamide, and N-ethyl-N-phenyl methacrylamide.

[0248] Examples of the vinyl ethers include alkyl vinyl ethers and vinyl aryl ethers.

[0249] Examples of the vinyl esters include vinyl butyrate, vinyl isobutyrate, and trimethylvinyl acetate.

[0250] Examples of the styrenes include styrene, alkylstyrene, alkoxystyrene, halogenated styrene, and carboxystyrene.

[0251] Examples of the crotonic acid esters include crotonic acid alkyl esters such as butyl crotonate, hexyl crotonate, and glycerol monocrotonate.

[0252] In addition, itaconate dialkyl esters, dialkyl esters or monoalkyl esters of maleic acid or fumaric acid, crotonic acid, itaconic acid, maleic anhydride, acrylonitrile, methacrylonitrile, maleonitrile, and the like can be mentioned.

[0253] Examples of the polymer (Z) include polymers described in International Publication No. 03 / 017002. The contents of International Publication No. 03 / 017002 are incorporated herein by reference to the same extent as if all were expressly stated.

[0254] The weight average molecular weight of the polymer (Z) is not particularly limited, but is preferably 10,000 to 200,000, more preferably 30,000 to 150,000, and particularly preferably 50,000 to 100,000.

[0255] <<<Polymer (Q)>>>

[0256] The polymer (A) is preferably a polymer (A2) having a repeating unit represented by the following formula (Q).

[0257] [Chemistry 36]

[0258]

[0259] (In formula (Q), R 11 It represents an alkyl group having 1 to 4 carbon atoms.

[0260] R 12 represents a hydrogen atom, a methyl group, or a halogen atom. )

[0261] The polymer (A2) may be a homopolymer or a copolymer.

[0262] When the polymer (A2) is a homopolymer, the polymer (A2) is preferably polymethyl methacrylate, for example.

[0263] When the polymer (A2) is a copolymer, the polymer (A2) may have a repeating unit represented by the formula (Z-2) as a repeating unit other than the repeating unit represented by the formula (Q).

[0264] When the polymer (A2) is a copolymer, the polymer (A2) may have repeating units derived from acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, styrenes, crotonates, and the like.

[0265] The weight average molecular weight of the polymer (Q) is not particularly limited, but is preferably 1,000 to 30,000, more preferably 2,000 to 20,000, and particularly preferably 3,000 to 15,000.

[0266] The content of the polymer (A) in the organic film-forming composition is not particularly limited, but is preferably 30 to 100% by mass, more preferably 50 to 100% by mass, and particularly preferably 70 to 100% by mass, based on the organic film constituent components.

[0267] <<Crosslinking agent>>

[0268] The cross-linking agent is not particularly limited.

[0269] The cross-linking agent has a structure different from that of the polymer (A).

[0270] As the crosslinking agent, an aminoplast crosslinking agent or a phenoplast crosslinking agent is preferred.

[0271] Aminoplast crosslinking agents are addition condensation products of compounds having amino groups such as melamine and guanamine with formaldehyde.

[0272] Phenolic plastic crosslinking agent refers to the addition condensation product of a compound having a phenolic hydroxyl group and formaldehyde.

[0273] Examples of the cross-linking agent include compounds having two or more of the following structures.

[0274] [Chemistry 37]

[0275]

[0276] (In the structure, R 101 represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxyalkyl group having 2 to 6 carbon atoms, Indicates a bond. )

[0277] The bonding bond is, for example, bonding to a nitrogen atom or a carbon atom constituting an aromatic hydrocarbon ring.

[0278] As R 101 , preferably a hydrogen atom, a methyl group, an ethyl group or a group represented by the following structure.

[0279] [Chemistry 38]

[0280]

[0281] (In the structure, R 102 represents a hydrogen atom, a methyl group, or an ethyl group, and * represents a bond. )

[0282] As the crosslinking agent, melamine compounds, guanamine compounds, glycoluril compounds, urea compounds, and compounds having a phenolic hydroxyl group are preferred, and these can be used alone or in combination of two or more.

[0283] Examples of the melamine compound include hexamethylolmelamine, hexamethoxymethylmelamine, a compound obtained by methoxymethylating one to six hydroxymethyl groups of hexamethylolmelamine, or a mixture thereof, hexamethoxyethylmelamine, hexaacyloxymethylmelamine, a compound obtained by acyloxymethylating one to six hydroxymethyl groups of hexamethylolmelamine, or a mixture thereof, and the like.

[0284] Examples of the guanamine compound include tetramethylolguanamine, tetramethoxymethylguanamine, compounds obtained by methoxymethylating 1 to 4 hydroxymethyl groups of tetramethylolguanamine, or mixtures thereof, tetramethoxyethylguanamine, tetraacyloxyguanamine, compounds obtained by acyloxymethylating 1 to 4 hydroxymethyl groups of tetramethylolguanamine, or mixtures thereof.

[0285] Examples of the glycoluril compound include tetrakishydroxymethyl glycoluril, tetramethoxy glycoluril, tetramethoxymethyl glycoluril, a compound in which 1 to 4 hydroxymethyl groups of tetrakishydroxymethyl glycoluril are methoxymethylated, or a mixture thereof, and a compound in which 1 to 4 hydroxymethyl groups of tetrakishydroxymethyl glycoluril are acyloxymethylated, or a mixture thereof.

[0286] In addition, the glycoluril compound may be, for example, a glycoluril derivative represented by the following formula (1E).

[0287] [Chemistry 39]

[0288]

[0289] (In formula (1E), the four R 1 Each independently represents a methyl group or an ethyl group, R 2 and R 3 Each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group.

[0290] Examples of the glycoluril derivative represented by the above formula (1E) include compounds represented by the following formulas (1E-1) to (1E-6).

[0291] [Chemistry 40]

[0292]

[0293] The glycoluril derivative represented by the formula (1E) can be obtained, for example, by reacting a glycoluril derivative represented by the following formula (2E) with at least one compound represented by the following formula (3d).

[0294] [Chemistry 41]

[0295]

[0296] (In formula (2E), R 2 and R 3 Each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group, and R 4 Each independently represents an alkyl group having 1 to 4 carbon atoms.

[0297] [Chemistry 42]

[0298]

[0299] (In formula (3d), R 1 represents a methyl or ethyl group. )

[0300] Examples of the glycoluril derivatives represented by the above formula (2E) include compounds represented by the following formulas (2E-1) to (2E-4). Furthermore, examples of the compounds represented by the above formula (3d) include compounds represented by the following formulas (3d-1) and (3d-2).

[0301] [Chemistry 43]

[0302]

[0303] [Chemistry 44]

[0304]

[0305] Examples of the urea compound include tetramethylol urea, tetramethoxymethyl urea, a compound in which 1 to 4 methylol groups of tetramethylol urea are methoxymethylated, or a mixture thereof, and tetramethoxyethyl urea.

[0306] Examples of the compound having a phenolic hydroxyl group include compounds represented by the following formula (G-1) or formula (G-2).

[0307] [Chemistry 45]

[0308]

[0309] (In formula (G-1) and formula (G-2), Q 1 It represents a single bond or an m1-valent organic group.

[0310] R 1 and R 4Each of them represents an alkyl group having 2 to 10 carbon atoms or an alkyl group having 2 to 10 carbon atoms having an alkoxy group having 1 to 10 carbon atoms.

[0311] R 2 and R 5 represent a hydrogen atom or a methyl group, respectively.

[0312] R 3 and R 6 Each of them represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 40 carbon atoms.

[0313] n 1 Indicates 1≤n 1 An integer ≤3, n 2 It means 2≤n 2 An integer ≤5, n 3 Indicates 0≤n 3 An integer ≤3, n 4 Indicates 0≤n 4 An integer ≤3, 3≤(n 1 +n 2 +n 3 +n 4 )≤6.

[0314] n 5 Indicates 1≤n 5 An integer ≤3, n 6 Indicates 1≤n 6 An integer ≤ 4, n 7 Indicates 0≤n 7 An integer ≤3, n 8 Indicates 0≤n 8 Integer ≤3, 2≤(n 5 +n 6 +n 7 +n 8 )≤5.

[0315] m1 represents an integer from 2 to 10. )

[0316] Moreover, as a compound which has a phenolic hydroxyl group, the compound represented by the following formula (G-3) or formula (G-4) is mentioned, for example.

[0317] The compound represented by formula (G-1) or formula (G-2) can be obtained by reacting a compound represented by the following formula (G-3) or formula (G-4) with a hydroxyl group-containing ether compound or an alcohol having 2 to 10 carbon atoms.

[0318] [Chemistry 46]

[0319]

[0320] (In formula (G-3) and formula (G-4), Q 2 It represents a single bond or an m2-valent organic group.

[0321] R 8 , R 9 , R 11 and R 12 represent a hydrogen atom or a methyl group, respectively.

[0322] R 7 and R 10 Each of them represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 40 carbon atoms.

[0323] n 9 Indicates 1≤n 9 An integer ≤3, n 10 It means 2≤n 10 An integer ≤5, n 11 Indicates 0≤n 11 An integer ≤3, n 12 Indicates 0≤n 12 An integer ≤3, 3≤(n 9 +n 10 +n 11 +n 12 )≤6.

[0324] n 13 Indicates 1≤n 13 An integer ≤3, n 14 Indicates 1≤n 14 An integer ≤ 4, n 15 Indicates 0≤n 15 An integer ≤3, n 16 Indicates 0≤n 16 Integer ≤3, 2≤(n 13 +n 14 +n 15 +n 16 )≤5.

[0325] m2 represents an integer from 2 to 10. )

[0326] As Q 2 The m2-valent organic group in the formula (a) includes, for example, an m2-valent organic group having 1 to 4 carbon atoms.

[0327] Examples of the compound represented by formula (G-1) or formula (G-2) include the following compounds.

[0328] [Chemistry 47]

[0329]

[0330] [Chemistry 48]

[0331]

[0332] [Chemistry 49]

[0333]

[0334] [Chemistry 50]

[0335]

[0336] [Chemistry 51]

[0337]

[0338] Examples of the compound represented by formula (G-3) or formula (G-4) include the following compounds.

[0339] [Chemistry 52]

[0340]

[0341] [Chemistry 53]

[0342]

[0343] The above compounds can be obtained as products of Asahi Organic Materials Industries, Ltd. and Honshu Chemical Industries, Ltd. As a product, for example, TMOM-BP, a trade name of Asahi Organic Materials Industries, Ltd., can be mentioned.

[0344] Among them, glycoluril compounds are preferred, specifically, tetrakishydroxymethyl glycoluril, tetramethoxy glycoluril, tetramethoxymethyl glycoluril, compounds obtained by methoxymethylating 1 to 4 hydroxymethyl groups of tetrakishydroxymethyl glycoluril or mixtures thereof, compounds obtained by acyloxymethylating 1 to 4 hydroxymethyl groups of tetrakishydroxymethyl glycoluril or mixtures thereof, and tetramethoxymethyl glycoluril is more preferred.

[0345] The molecular weight of the cross-linking agent is not particularly limited, but is preferably 500 or less.

[0346] When the organic film-forming composition contains a crosslinking agent, the content of the crosslinking agent in the organic film-forming composition is not particularly limited, but is, for example, 1 to 70 mass %, preferably 5 to 60 mass % based on the polymer (A).

[0347] <<Curing catalyst>>

[0348] As the curing catalyst as an organic film constituent component contained as an optional component in the organic film-forming composition, any of a thermal acid generator and a photoacid generator can be used, and a thermal acid generator is preferably used.

[0349] Examples of the thermal acid generator include sulfonic acid compounds and carboxylic acid compounds such as p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium-p-toluenesulfonate (pyridinium-p-toluenesulfonic acid), pyridinium phenolsulfonic acid, pyridinium-p-hydroxybenzenesulfonic acid (pyridinium p-phenolsulfonic acid), pyridinium-trifluoromethanesulfonic acid, salicylic acid, camphorsulfonic acid, 5-sulfosalicylic acid, 4-chlorobenzenesulfonic acid, 4-hydroxybenzenesulfonic acid, benzenedisulfonic acid, 1-naphthalenesulfonic acid, citric acid, benzoic acid, hydroxybenzoic acid, N-methylmorpholine-p-toluenesulfonic acid, N-methylmorpholine-p-hydroxybenzenesulfonic acid, and N-methylmorpholine-5-sulfosalicylic acid.

[0350] Examples of the photoacid generator include onium salt compounds, sulfonyl imide compounds, and disulfonyldiazomethane compounds.

[0351] Examples of the onium salt compound include iodonium salt compounds such as diphenyliodonium hexafluorophosphate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, diphenyliodonium perfluoro-n-octanesulfonate, diphenyliodonium camphorsulfonate, bis(4-tert-butylphenyl)iodonium camphorsulfonate, and bis(4-tert-butylphenyl)iodonium trifluoromethanesulfonate; and sulfonium salt compounds such as triphenylsulfonium hexafluoroantimonate, triphenylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium camphorsulfonate, and triphenylsulfonium trifluoromethanesulfonate.

[0352] Examples of the sulfonyl imide compound include N-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluoro-n-butanesulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, and N-(trifluoromethanesulfonyloxy)naphthalimide.

[0353] Examples of the disulfonyldiazomethane compound include bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(2,4-dimethylbenzenesulfonyl)diazomethane, and methylsulfonyl-p-toluenesulfonyldiazomethane.

[0354] The curing catalyst may be used alone or in combination of two or more.

[0355] When a curing catalyst is used, the content ratio of the curing catalyst is, for example, 0.1 mass % to 50 mass %, and preferably 1 mass % to 30 mass % based on the cross-linking agent.

[0356] <<Other ingredients>>

[0357] To the organic film-forming composition, a surfactant may be further added as an organic film-constituting component in order to prevent pinholes, striations, and the like from being generated and to further improve coating properties on surface unevenness.

[0358] 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 fatty acid esters such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, and sorbitan tristearate; and nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate. Fluorine-based surfactants such as EF301, EF303, EF352 (manufactured by Tochem Products Co., Ltd., trade names), Megafac F171, F173, R-30 (manufactured by DIC Corporation, trade names), Fluorad FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd., trade names), AsahiGuard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGC Corporation, trade names), and organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0359] 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 organic film-forming composition.

[0360] These surfactants may be added alone or in combination of two or more.

[0361] <Solvent>

[0362] The solvent used in the composition for forming an organic film is not particularly limited, but preferably an organic solvent commonly used in a chemical solution for a semiconductor photolithography process. Specifically, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, cycloheptanone, 4-methyl-2-pentanol, methyl 2-hydroxyisobutyrate, 2-hydroxy Ethyl isobutyrate, ethyl ethoxylate, 2-hydroxyethyl acetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, 2-heptanone, methoxycyclopentane, anisole, γ-butyrolactone, N-methylpyrrolidone, N,N-dimethylformamide and N,N-dimethylacetamide. These solvents can be used alone or in combination of two or more.

[0363] Among these solvents, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, butyl lactate, and cyclohexanone are preferred, and propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate are particularly preferred.

[0364] The solvent preferably does not contain water. In other words, the composition for forming an organic film preferably does not contain water.

[0365] The water content in the organic film-forming composition is not particularly limited, but is preferably 0% by mass to 10% by mass, more preferably 0% by mass to 5% by mass, and particularly preferably 0% by mass to 3% by mass.

[0366] The content of the solvent in the organic film-forming composition is not particularly limited, but is preferably 80% by mass to 99.99% by mass, more preferably 85% by mass to 99.9% by mass, and particularly preferably 90% by mass to 99% by mass.

[0367] In other words, the content of the organic film-forming component in the organic film-forming composition is not particularly limited, but is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, and particularly preferably 1 to 10% by mass.

[0368] (Method for manufacturing semiconductor element)

[0369] An example of a method for manufacturing a semiconductor element of the present invention includes an irradiation step, a resist pattern formation step, an organic film formation step, and an organic film removal step.

[0370] An example of a method for manufacturing a semiconductor element may include other steps.

[0371] <Irradiation process>

[0372] The irradiation step is a step of irradiating the metal-containing resist film with light or electron beams.

[0373] The metal-containing resist film is not particularly limited, but preferably contains at least one element of Si, Ge, Sn, Ti, Zr, Hf, Al, and Co.

[0374] The metal-containing resist film is formed of, for example, a metal-containing resist.

[0375] A metal-containing resist is also called a metal oxide resist (Metal Oxide Resist (MOR)), and a representative example thereof is a tin oxide-based resist.

[0376] As a metal oxide resist material, for example, there can be mentioned a coating composition described in Japanese Patent Application Laid-Open No. 2019-113855, which contains a metal oxo-hydroxo network having an organic ligand via a metal-carbon bond and / or a metal carboxylate bond.

[0377] An example of a metal-containing resist uses a peroxidized ligand as a radiation sensitivity stabilizing ligand. For example, the details of the metal oxygen-hydroxy compound of the peroxide are described in the patent document recorded in paragraph

[0011] of the Japanese Public Table 2019-532489 Gazette. As the patent document, for example, U.S. Patent No. 9176377B2 Specification, U.S. Patent Application Publication No. 2013 / 0224652A1 Specification, U.S. Patent No. 9310684B2 Specification, U.S. Patent Application Publication No. 2016 / 0116839A1 Specification, U.S. Patent Application Publication No. 15 / 291738 Specification can be cited.

[0378] Another example of a metal-containing resist includes compositions described in Japanese Unexamined Patent Application Publication No. 2011-253185, WO2015 / 026482, WO2016 / 065120, WO2017 / 066319, WO2017 / 156388, WO2018 / 031896, Japanese Unexamined Patent Application Publication No. 2020-122959, Japanese Unexamined Patent Application Publication No. 2020-122960, WO2019 / 099981, WO2019 / 199467, WO2019 / 195522, WO2019 / 195522, WO2020 / 210660, WO2021 / 011367, and WO2021 / 016229.

[0379] These contents are incorporated into this specification to the same extent as if they were all expressly stated.

[0380] The method of forming a metal-containing resist film from a metal-containing resist is not particularly limited, and examples thereof include a method of applying a coating type resist material (metal-containing resist film-forming composition) as a metal-containing resist and then firing.

[0381] In addition, the metal-containing resist film can also be formed by evaporation. As a method for forming a metal-containing resist film using evaporation, for example, the method described in Japanese Patent Publication No. 2017-116923 can be cited. The content of Japanese Patent Publication No. 2017-116923 is introduced into this specification to the same extent as all explicit indications. It should be noted that in Japanese Patent Publication No. 2017-116923, the metal-containing resist film in the present invention is referred to as a film containing metal oxide.

[0382] The film thickness of the metal-containing resist film is, for example, 5 nm to 10000 nm, or 5 nm to 1000 nm, or 5 nm to 40 nm.

[0383] The metal-containing resist film is formed on, for example, a substrate, a resist underlayer film, or the like.

[0384] Examples of the substrate include substrates used in the manufacture of precision integrated circuit elements. Examples of such substrates include semiconductor substrates such as silicon wafers coated with silicon oxide films, silicon nitride films, or silicon nitride oxide films, silicon nitride substrates, quartz substrates, glass substrates (including alkali-free glass, low-alkali glass, and crystallized glass), glass substrates formed with ITO (indium tin oxide) films and IZO (indium zinc oxide) films, plastic (polyimide, PET, etc.) substrates, substrates coated with low dielectric constant materials (low-k materials), and flexible substrates.

[0385] The resist underlayer film is not particularly limited, and for example, a known resist underlayer film can be used. Examples of the resist underlayer film include an organic underlayer film and a silicon-containing resist underlayer film.

[0386] The resist film may be formed directly on the substrate, or may be formed on the resist underlayer film of the substrate on which the resist underlayer film is formed. The resist underlayer film may be a single layer or may be a multilayer. For example, a two-layer resist underlayer film may be present between the substrate and the resist film. As the two-layer resist underlayer film, for example, a two-layer resist underlayer film of an organic underlayer film and a silicon-containing resist underlayer film may be cited.

[0387] The film thickness of the resist underlayer film is, for example, 10 nm to 1000 nm, 20 nm to 500 nm, 50 nm to 300 nm, 100 nm to 200 nm, or 10 to 150 nm.

[0388] Examples of light or electron beams that are irradiated to the metal-containing resist film include KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), F 2 Excimer laser (wavelength 157nm), EUV (wavelength 13.5nm), electron beam.

[0389] The irradiation amount of the light or electron beam to be irradiated to the metal-containing resist film is not particularly limited.

[0390] After irradiation, post-exposure baking may be performed as needed. The post-exposure baking is performed under conditions appropriately selected from, for example, a heating temperature of 70° C. to 250° C. and a heating time of 0.3 minutes to 10 minutes.

[0391] <Resist pattern forming step>

[0392] The resist pattern forming step is a step of bringing a developer into contact with the metal-containing resist film irradiated with light or electron beams to obtain a resist pattern.

[0393] As a developer, an organic solvent can be used, and after irradiation with light or electron beams, development is performed using a developer (solvent). Thus, for example, when a negative metal-containing resist film is used, the metal-containing resist film in the unexposed portion is removed to form a pattern of the metal-containing resist film.

[0394] Examples of the developer (organic solvent) include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, methoxyethyl acetate, ethoxyethyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monophenyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl acetate. butyl acetate, 4-propoxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate, 3-methyl-3-methoxypentyl acetate, 3-methyl-4-methoxypentyl acetate, 4-methyl-4-methoxypentyl acetate, propylene glycol diacetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate , butyl lactate, propyl lactate, ethyl carbonate, propyl carbonate, butyl carbonate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, butyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, propyl 3-methoxypropionate, etc. are exemplified. Furthermore, surfactants etc. can also be added to these developers. As the conditions for development, it can be appropriately selected from a temperature of 5° C. to 50° C. and a time of 10 seconds to 600 seconds.

[0395] As a developing method using a developer, for example, spin development using spin coating can be cited. The rotation speed during spin development is not particularly limited, and for example, 500 rpm (revolutions per minute) to 1500 rpm can be cited. The time for spin development is not particularly limited, and for example, 30 seconds to 120 seconds can be cited.

[0396] In the resist pattern forming step, development is performed so that the resist pattern in contact with the developer is not dried.

[0397] Generally, in the formation of a resist pattern, drying is performed to remove a developing solution after development, but in the present invention, drying of the developing solution is not performed because drying of the developing solution would cause collapse of the resist pattern.

[0398] For example, when development is performed by spin development, spin drying is usually performed after spin development, but spin drying is not performed in the present invention. After spin development, the organic film forming step is performed without spin drying.

[0399] In general, the rotation speed during spin drying is not particularly limited, and examples thereof include 2000 rpm to 3000 rpm. The spin drying time is not particularly limited, and examples thereof include 10 seconds to 90 seconds.

[0400] <Organic film formation process>

[0401] The organic film forming step is a step of applying the organic film forming composition of the present invention on the resist pattern without drying the resist pattern in contact with the developer to form an organic film between the resist patterns.

[0402] The method for forming the organic film is not particularly limited, and an example thereof is spin coating. The rotation speed during spin coating is not particularly limited, and an example thereof is 500 rpm to 1500 rpm. The time for spin coating is not particularly limited, and an example thereof is 30 seconds to 120 seconds.

[0403] The organic film formed by the organic film forming step may be formed only between the resist patterns. In addition, the organic film may be formed on the resist patterns in addition to being formed between the resist patterns.

[0404] The thickness of the formed organic film is not particularly limited, and is set to an appropriate thickness according to the thickness of the metal-containing resist film, for example. The thickness of the organic film is, for example, 0.5 to 1.5 times the thickness of the metal-containing resist film.

[0405] <Organic film removal process>

[0406] The organic film removing step is not particularly limited as long as the organic film can be removed.

[0407] Examples of methods for removing the organic film include dry etching, wet etching (e.g., removal by decomposition with an acidic solution), radiation etching, high temperature calcination, removal by dissolution using a solvent, and ozone treatment, etc. These methods may be performed alone or in combination of two or more.

[0408] The temperature in the high temperature calcination is, for example, 200° C. to 300° C. The calcination time in the high temperature calcination is, for example, 1 minute or longer. The atmosphere in the high temperature calcination is, for example, an air atmosphere.

[0409] Examples of the solvent used in the dissolving and removing using a solvent include the organic solvents mentioned in the description of the developer (organic solvent) used in the resist pattern forming step.

[0410] Examples of the gas used for dry etching include tetrafluoromethane (CF 4 ), perfluorocyclobutane (C 4 F 8 ), perfluoropropane (C 3 F 8 ), trifluoromethane, carbon monoxide, argon, oxygen, nitrogen, sulfur hexafluoride, difluoromethane, nitrogen trifluoride, chlorine trifluoride, chlorine, trichloroborane, dichloroborane, etc. These can be used alone or in combination of two or more.

[0411] Radiation etching is performed by irradiating ultraviolet rays in the presence of oxygen (for example, in the air) or in the presence of an inert gas (for example, nitrogen).

[0412] In radiation etching, the organic film is decomposed and removed by ultraviolet rays.

[0413] Alternatively, in radiation etching, ozone is generated by irradiation with ultraviolet rays (e.g., ultraviolet rays of 100nm to 400nm, 185nm). Furthermore, ultraviolet rays (e.g., 254nm) are absorbed by ozone, generating active oxygen. Furthermore, the organic film is decomposed by the active oxygen. As a result, the organic film is removed.

[0414] In the organic film removal process, the organic film is preferably selectively removed. In this regard, the etching speed (etching rate) of the organic film when removing the organic film is preferably more than twice the etching speed of the metal-containing resist film, more preferably more than 10 times, and particularly preferably more than 20 times. There is no particular restriction on the upper limit of the etching speed, for example, the etching speed of the organic film when removing the organic film is less than 100 times the etching speed of the metal-containing resist film.

[0415] In one example of a method for manufacturing a semiconductor element, the resist lower layer film (middle layer) is removed using the resist pattern of the metal-containing resist film (upper layer) formed in this way as a protective film, and then the organic lower layer film (lower layer) is removed using a film including the patterned metal-containing resist film and the patterned resist lower layer film (middle layer) as a protective film. Finally, the substrate is processed using the patterned resist lower layer film (middle layer) and the patterned organic lower layer film (lower layer) as protective films.

[0416] The removal (patterning) of the resist lower layer film (intermediate layer) using the pattern of the metal-containing resist film (upper layer) as a protective film is performed by dry etching, and tetrafluoromethane (CF 4), perfluorocyclobutane (C 4 F 8 ), perfluoropropane (C 3 F 8 ), trifluoromethane, carbon monoxide, argon, oxygen, nitrogen, sulfur hexafluoride, difluoromethane, nitrogen trifluoride, chlorine trifluoride, chlorine, trichloroborane and dichloroborane and other gases.

[0417] It should be noted that, in the dry etching of the resist underlayer film, it is preferred to use a halogen-based gas. In the dry etching using a halogen-based gas, it is basically difficult to remove the metal-containing resist film. In contrast, the resist underlayer film containing a large amount of silicon atoms is quickly removed by the halogen-based gas. Therefore, it is possible to suppress the reduction in the film thickness of the metal-containing resist film accompanying the dry etching of the resist underlayer film. Then, as a result, the metal-containing resist film can be used in the form of a thin film. Therefore, the dry etching of the resist underlayer film is preferably performed using a fluorine-based gas, and as the fluorine-based gas, for example, tetrafluoromethane (CF 4 ), perfluorocyclobutane (C 4 F 8 ), perfluoropropane (C 3 F 8 ), trifluoromethane, difluoromethane (CH 2 F 2 ), etc., but are not limited to these.

[0418] In the case where there is an organic underlayer film between the substrate and the resist underlayer film, the removal (patterning) of the organic underlayer film (lower layer) is preferably performed by dry etching using an oxygen-based gas (oxygen gas, oxygen / carbonyl sulfide (COS) mixed gas, etc.) with the film containing the patterned metal-containing resist underlayer film (upper layer) (if remaining) as a protective film. This is because the resist underlayer film of the present invention containing a large amount of silicon atoms is difficult to remove by dry etching using an oxygen-based gas.

[0419] Thereafter, processing (patterning) of the (semiconductor) substrate using the patterned resist underlayer film (intermediate layer) and, if desired, the patterned organic underlayer film (underlayer) as a protective film is preferably performed by dry etching using a fluorine-based gas.

[0420] Examples of fluorine-based gases include tetrafluoromethane (CF 4 ), perfluorocyclobutane (C 4 F 8 ), perfluoropropane (C 3 F 8 ), trifluoromethane and difluoromethane (CH 2 F 2 )wait.

[0421] After the organic underlayer film is removed (patterned) or after the substrate is processed (patterned), the resist underlayer film can be removed. The resist underlayer film can be removed by dry etching or wet etching (wet method).

[0422] The dry etching of the resist underlayer film is preferably carried out using a fluorine-based gas, such as tetrafluoromethane (CF 4 ), perfluorocyclobutane (C 4 F 8 ), perfluoropropane (C 3 F 8 ), trifluoromethane, difluoromethane (CH 2 F 2 ), etc., but are not limited to these.

[0423] Examples of chemical solutions used in wet etching of resist underlayer films include dilute hydrofluoric acid (HF), buffered hydrofluoric acid (HF and NH 4 F mixed solution), aqueous solution containing hydrochloric acid and hydrogen peroxide (SC-2 solution), aqueous solution containing sulfuric acid and hydrogen peroxide (SPM solution), aqueous solution containing hydrofluoric acid and hydrogen peroxide (FPM solution), aqueous solution containing ammonia and hydrogen peroxide (SC-1 solution) and other alkaline solutions. In addition, as the alkaline solution, in addition to the ammonia hydrogen peroxide mixture (SC-1 solution) obtained by mixing the above-mentioned ammonia, hydrogen peroxide water and water, there can be mentioned aqueous solutions containing 1 to 99% by mass of ammonia, tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, choline hydroxide, benzyltrimethylammonium hydroxide, benzyltriethylammonium hydroxide, DBU (diazabicycloundecene), DBN (diazabicyclononene), hydroxylamine, 1-butyl-1-methylpyrrolidinium hydroxide, 1-propyl-1-methylpyrrolidinium hydroxide, 1-butyl-1-methylpiperidinium hydroxide, 1-propyl-1-methylpiperidinium hydroxide, mepiquatium hydroxide, trimethylsulfonium hydroxide, hydrazines, ethylenediamines, or guanidine. These solutions can also be used in combination.

[0424] In addition, an organic anti-reflection film can be formed on the upper layer of the resist underlayer film before forming the metal-containing resist film. There is no particular limitation on the anti-reflection film composition used here, and for example, any anti-reflection film composition conventionally used in photolithography can be selected and used. In addition, the anti-reflection film can be formed by conventional methods, such as coating and firing using a spin coater or a coating machine.

[0425] In addition, the substrate coated with the silicon-containing resist underlayer film-forming composition for forming a silicon-containing resist underlayer film may have an organic or inorganic antireflection film formed by a CVD method or the like on its surface, and the resist underlayer film may be formed thereon. In the case where the silicon-containing resist underlayer film is formed thereon after the organic underlayer film is formed on the substrate, the substrate used may have an organic or inorganic antireflection film formed by a CVD method or the like on its surface.

[0426] The resist underlayer film formed by the resist underlayer film-forming composition containing silicon may also absorb the light at the wavelength of the light used in the photolithography process, and in such a case, it can function as an antireflection film having the effect of preventing reflected light from the substrate.

[0427] Furthermore, the resist underlayer film can also be used as a layer for preventing interaction between the substrate and the metal-containing resist film, a layer having the function of preventing the adverse effects of materials used in the metal-containing resist film or substances generated when the metal-containing resist film is exposed on the substrate, a layer having the function of preventing substances generated from the substrate from diffusing into the metal-containing resist film during heating and firing, and a barrier layer for reducing the poisoning effect of the metal-containing resist film caused by the dielectric layer of the semiconductor substrate, etc.

[0428] <Other embodiments>

[0429] In another example of the method for producing a semiconductor device of the present invention, the organic film-forming composition may also serve as a developer. In this case, another example of the method for producing a semiconductor device includes an irradiation step, a resist pattern and an organic film forming step, and an organic film removing step.

[0430] As the irradiation step, the above-mentioned irradiation step can be mentioned.

[0431] As the organic film removing step, the above-mentioned organic film removing step can be mentioned.

[0432] The resist pattern and organic film forming step is a step that replaces the above-mentioned resist pattern forming step and organic film forming step.

[0433] In the resist pattern and organic film forming step, the organic film forming composition of the present invention is applied on a metal-containing resist film irradiated with light or electron beams, the metal-containing resist film is developed to obtain a resist pattern, and an organic film is formed between the resist patterns.

[0434] Therefore, in this example, no developer is used.

[0435] The organic film-forming composition contains, for example, a solvent capable of dissolving the unexposed metal-containing resist film.

[0436] The organic film-forming composition is applied by, for example, spin coating. The rotation speed during spin coating is not particularly limited, and for example, 500 rpm to 1500 rpm can be cited. The spin coating time is not particularly limited, and for example, 30 seconds to 120 seconds can be cited.

[0437] (Substrate with metal-containing resist pattern, method for manufacturing substrate with metal-containing resist pattern)

[0438] The substrate with a metal-containing resist pattern of the present invention is a substrate with a metal-containing resist pattern in which the organic film-forming composition of the present invention is applied on the metal-containing resist pattern to embed an organic film between the metal-containing resist patterns.

[0439] The method for producing a substrate with a metal-containing resist pattern of the present invention comprises the step of applying the organic film-forming composition of the present invention on the metal-containing resist pattern to embed an organic film between the metal-containing resist patterns.

[0440] The metal-containing resist pattern is a resist pattern formed of a metal-containing resist film.

[0441] The metal-containing resist pattern can be formed, for example, through the above-mentioned <irradiation step> and <resist pattern forming step>.

[0442] As a method for forming an organic film, for example, the coating method mentioned in the above-mentioned <Organic film forming step> etc. are mentioned.

[0443] The metal-containing resist pattern can be formed, for example, on a substrate, on a resist underlayer film, or the like.

[0444] Hereinafter, one embodiment of a method for manufacturing a semiconductor element will be described with reference to the drawings.

[0445] Figure 1A to Figure 1E This is a schematic cross-sectional view for explaining an embodiment of a method for manufacturing a semiconductor element. This embodiment includes an irradiation step, a resist pattern forming step, an organic film forming step, and an organic film removing step.

[0446] First, prepare a substrate 1 ( Figure 1A ). An organic underlayer film 2, a resist underlayer film 3 containing silicon, and a resist film 4 containing metal are sequentially stacked on a substrate 1.

[0447] Next, the metal-containing resist film 4 is irradiated with light L ( Figure 1B ). The light L is, for example, EUV light. Alternatively, an electron beam may be irradiated instead of the light L.

[0448] Next, a developer is brought into contact with the metal-containing resist film irradiated with the light L to obtain a resist pattern 4A ( Figure 1C ). Development is performed by spin development. Spin drying is not performed at this time.

[0449] Next, without spin drying, the organic film-forming composition of the present invention is applied on the resist pattern 4A to form an organic film 5 ( Figure 1D ). It should be noted that if Figure 1D As shown, the organic film 5 may also be formed on the resist pattern 4A.

[0450] Next, the organic film 5 ( Figure 1E ).

[0451] Thereby, a resist pattern in which pattern collapse is suppressed can be obtained.

[0452] It should be noted that if Figure 2 As shown, the organic film 5 between the resist patterns 4A may exist only between the resist patterns 4A, and not exist on the resist patterns 4A.

[0453] Hereinafter, another embodiment of the method for manufacturing a semiconductor element will be described with reference to the drawings.

[0454] Figure 3A to Figure 3D This is a schematic cross-sectional view for explaining an embodiment of a method for manufacturing a semiconductor element. This embodiment includes an irradiation step, a resist pattern and an organic film forming step, and an organic film removing step. In addition, the organic film forming composition also serves as a developer.

[0455] First, prepare a substrate 1 ( Figure 3A ). An organic underlayer film 2, a resist underlayer film 3 containing silicon, and a resist film 4 containing metal are sequentially stacked on a substrate 1.

[0456] Next, the metal-containing resist film 4 is irradiated with light L ( Figure 3B ). The light L is, for example, EUV light. Alternatively, an electron beam may be irradiated instead of the light L.

[0457] Next, the organic film-forming composition of the present invention is applied to the metal-containing resist film 4 irradiated with the light L, the metal-containing resist film 4 is developed to obtain a resist pattern 4A, and an organic film 5 ( Figure 3C ). The coating was performed by spin coating.

[0458] Next, the organic film 5 ( Figure 3D ).

[0459] Thereby, a resist pattern in which pattern collapse is suppressed can be obtained.

[0460] Example

[0461] Hereinafter, the present invention will be described in more detail with reference to synthesis examples and examples, but the present invention is not limited only to the following examples.

[0462] In addition, in the examples, the apparatus and conditions used for analyzing the physical properties of the samples are as follows.

[0463] (1) Molecular weight determination

[0464] The molecular weight used in the present invention is a molecular weight obtained by polystyrene conversion based on GPC analysis. The measurement conditions of GPC are as follows.

[0465] ·GPC device: Trade name HLC-8220GPC (manufactured by Tosoh Corporation)

[0466] ·GPC column: Trade name Shodex (registered trademark) KF803L, KF802, KF801 (manufactured by Showa Denko K.K.)

[0467] Column temperature: 40°C

[0468] ·Eluent (elution solvent): tetrahydrofuran

[0469] Flow rate: 1.0mL / min

[0470] · Standard sample: Polystyrene (manufactured by Showa Denko K.K.)

[0471] [1] Synthesis of polymers

[0472] (Synthesis example 1)

[0473] In a two-necked flask, 40.0 g of EHPE3150 (manufactured by Daicel Chemical Industry Co., Ltd.), 20.3 g of 9-anthracenecarboxylic acid and 13.7 g of benzoic acid were dissolved in 302.0 g of propylene glycol monomethyl ether, and 1.5 g of benzyltriethylammonium was added, and the mixture was refluxed for 24 hours to react. 11 g of anion exchange resin and 11 g of cation exchange resin were added to the obtained solution, and ion exchange treatment was performed at room temperature for 4 hours. The ion exchange resin was separated to obtain a solution of a polymer of formula (E-1). The weight average molecular weight Mw of the obtained resin measured by polystyrene conversion based on GPC was 4100.

[0474] [Chemistry 54]

[0475]

[0476] (Synthesis example 2)

[0477] After dissolving 6.6 g (0.039 mol) of butyrolactone methacrylate, 6.6 g (0.046 mol) of 2-hydroxypropyl methacrylate, and 6.8 g (0.039 mol) of benzyl methacrylate in 64.4 g of tetrahydrofuran in a flask, the flask was replaced with nitrogen and the temperature was raised to reflux temperature. After the reflux started, 0.2 g of azobisisobutyronitrile (AIBN) dissolved in 10 g of tetrahydrofuran was added under nitrogen pressure, and the reaction was carried out for 24 hours. After the reaction solution was cooled, diethyl ether was added to reprecipitate the polymer, and the polymer was heated and dried to obtain a polymer of formula (E-2). The obtained polymer had a degree of polymerization of 490, a weight average molecular weight of Mw80000 (polystyrene conversion), and a yield of 90%.

[0478] 1.5 g of the obtained polymer was dissolved in 48.5 g of propylene glycol monomethyl ether to obtain a polymer solution.

[0479] [Chemistry 55]

[0480]

[0481] (Synthesis example 3)

[0482] 100 g of monoallyl diglycidyl isocyanuric acid (manufactured by Shikoku Chemical Industry Co., Ltd.), 66.4 g of 5,5-diethylbarbituric acid, and 4.1 g of benzyltriethylammonium chloride were dissolved in 682 g of propylene glycol monomethyl ether, and then reacted at 130° C. for 24 hours to obtain a solution of a polymer having a unit structure of formula (E-3) as a repeating structure. The obtained polymer was subjected to GPC analysis, and the weight average molecular weight was 6800 in terms of standard polystyrene.

[0483] [Chemistry 56]

[0484]

[0485] (Synthesis example 4)

[0486] 30.00 g of propylene glycol monomethyl ether acetate was placed in a reaction container equipped with a thermometer, a cooling tube, a dropping device, and a stirring device, and the temperature was raised to 80° C. in a nitrogen atmosphere. In another container, 15.46 g of methyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) and 2.53 g of azobis(isobutyric acid) dimethyl ester (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were dissolved in 42.00 g of propylene glycol monomethyl ether acetate, placed in a dropping container, and dropped into the above reaction container over 30 minutes in a nitrogen atmosphere.

[0487] After stirring at 80° C. for 24 hours under a nitrogen atmosphere, a polymer solution containing methyl methacrylate was obtained. The obtained polymer was subjected to GPC analysis, and the weight average molecular weight Mw was 6300. The obtained polymer can be represented by the following formula (E-4).

[0488] [Chemistry 57]

[0489]

[0490] [2-1] O 2 Determination of etching rate

[0491] For O 2 The following etcher and etching gas were used for measuring the etching rate.

[0492] Etcher: RIE-10NR (Samco)

[0493] Etching gas: O 2 gas

[0494] The polymer solutions obtained in Synthesis Examples 1 to 4 were applied onto a silicon wafer using a spin coater, respectively, and heated on a hot plate at 250° C. for 1 minute to form a coating film having a film thickness of 50 nm.

[0495] Similarly, a tin oxide-based resist composition was applied to form a resist film (film thickness 22 nm) on a silicon wafer using a spin coater.

[0496] For the coating film obtained from the polymer solution and the resist film obtained from the tin oxide resist composition, O 2 The dry etching rate of the coating film prepared from the polymer solution obtained in Synthesis Examples 1 to 4 was compared with the dry etching rate of the resist film obtained from the tin oxide-based resist composition.

[0497] The obtained results are shown in Table 1. In addition, the etching rate in Table 1 is an etching rate when the etching rate of the resist film obtained from the tin oxide-based resist composition is set to 1.

[0498] [Table 1]

[0499]

[0500] [2-2] UV / O 3 Determination of etching rate

[0501] For UV / O 3 The following etcher was used as the etcher for measuring the etching rate.

[0502] Etcher: SUS867 (manufactured by Ushio Electric)

[0503] The polymer solutions obtained in Synthesis Examples 1 to 4 were applied onto a silicon wafer using a spin coater, respectively, and heated on a hot plate at 250° C. for 1 minute to form a coating film having a film thickness of 50 nm.

[0504] Similarly, a tin oxide-based resist composition was applied to form a resist film (film thickness 22 nm) on a silicon wafer using a spin coater.

[0505] The coating film obtained from the polymer solution and the resist film obtained from the tin oxide resist composition were irradiated with 172 nm light in the presence of air, and UV / O 3 Etching Rate. The dry etching rate of the coating films prepared from the polymer solutions obtained in Synthesis Examples 1 to 4 was compared with the dry etching rate of the resist film obtained from the tin oxide-based resist composition.

[0506] The obtained results are shown in Table 2. In addition, the etching rate in Table 2 is an etching rate when the etching rate of the resist film obtained from the tin oxide-based resist composition is set to 1.

[0507] [Table 2]

[0508]

[0509] [3] Preparation of organic underlayer film-forming composition

[0510] Under nitrogen, carbazole (6.69 g), 9-fluorenone (7.28 g), and p-toluenesulfonic acid monohydrate (0.76 g) were added to a 100 ml four-necked flask, 1,4-dioxane (6.69 g) was added and stirred, and the temperature was raised to 100°C to dissolve to initiate polymerization. After 24 hours, the mixture was cooled to 60°C.

[0511] Chloroform (34 g) was added to the cooled reaction mixture to dilute it, and the diluted mixture was added to methanol (168 g) to precipitate it. The obtained precipitate was filtered and recovered, and the recovered solid was dried at 80° C. for 24 hours using a reduced pressure dryer to obtain 9.37 g of the target polymer represented by formula (T) (hereinafter referred to as PCzFL).

[0512] The weight average molecular weight Mw of PCzFL was 2800 as determined by polystyrene conversion using GPC, and the polydispersity Mw / Mn was 1.77.

[0513] [Chemistry 58]

[0514]

[0515] 20 g of PCzFL, 3.0 g of tetramethoxymethyl glycoluril (manufactured by Cytec Industries, Japan (formerly Cytec Co., Ltd., Mitsui) as a crosslinking agent, trade name Powder Link 1174), 0.30 g of pyridinium p-toluenesulfonate as a catalyst, and 0.06 g of Megafac R-30 (manufactured by DIC Corporation, trade name) as a surfactant were mixed, and the obtained mixture was dissolved in 88 g of propylene glycol monomethyl ether acetate to prepare a solution. Then, the obtained solution was filtered using a polyethylene microfilter with a pore size of 0.10 μm, and further filtered using a polyethylene microfilter with a pore size of 0.05 μm to prepare a composition for forming an organic underlayer film.

[0516] [4] Preparation of a composition for forming a resist underlayer film

[0517] 20.8 g of tetraethoxysilane, 7.6 g of methyltriethoxysilane, and 62.1 g of propylene glycol monoethyl ether were added to a 300-ml flask, and 8.4 g of a 0.2 M nitric acid aqueous solution was added dropwise while the resulting mixed solution was stirred with a magnetic stirrer.

[0518] After the dropwise addition, the flask was transferred to an oil bath adjusted to 60° C. and refluxed for 20 hours. Then, ethanol and water as reaction by-products were distilled off under reduced pressure and concentrated to obtain an aqueous solution of a hydrolysis condensate (polymer).

[0519] Propylene glycol monoethyl ether was further added, and the concentration was adjusted to 10% by mass in terms of solid residue at 150° C. as a solvent ratio of 100% of propylene glycol monoethyl ether, and filtered using a nylon filter (pore size 0.1 μm). The obtained polysiloxane polymer had a structure represented by the following formula (U), and its weight average molecular weight was Mw2400 as measured by polystyrene conversion based on GPC.

[0520] [Chemistry 59]

[0521]

[0522] The obtained polysiloxane polymer solution (solid content 10 mass %) (4.9 g), maleic acid (0.005 g), triphenylsulfonium nitrate (0.005 g), and propylene glycol monoethyl ether (195 g) were mixed and filtered through a 0.1 μm fluororesin filter to prepare a resist underlayer film-forming composition.

[0523] [5-1] Example 1

[0524] <Formation of resist pattern>

[0525] The organic underlayer film-forming composition was spin-coated on a silicon wafer and heated on a hot plate at 215° C. for 1 minute to form an organic underlayer film (layer A) (film thickness: 90 nm).

[0526] The resist underlayer film-forming composition was spin-coated thereon, and the mixture was heated on a hot plate at 215° C. for 1 minute to form a resist underlayer film (layer B) (film thickness: 10 nm).

[0527] A resist solution (tin oxide resist) was further spin-coated thereon, and heated at 130° C. for 1 minute to form an EUV resist layer (C layer), and then exposed using an EB exposure device (ELS-G130) manufactured by ELIONIX. It should be noted that during exposure, exposure was performed so that the line width of the resist became 16 nm and the width between the lines (space width) became 28 nm after the development described below.

[0528] After exposure, post-exposure heating (PEB, 180°C for 1 minute) was performed, and the substrate was cooled to room temperature on a cooling plate, and a developer (propylene glycol monomethyl ether acetate) was used to perform spin development at 1000 rpm for 60 seconds. Then, without spin drying, the polymer solution prepared in Synthesis Example 1 was applied, and the propylene glycol monomethyl ether acetate used in the development was replaced with the solution. Then, the silicon substrate was rotated at 1500 rpm for 60 seconds to dry the solvent in the solution, and then heated at 250°C for 60 seconds to form a coating film, and the resist pattern was embedded. By using O 2 (flow rate 10sccm) and N 2 The formed coating film was removed by dry etching using a mixed gas (flow rate: 20 sccm) to obtain a resist pattern.

[0529] [5-2] Example 2

[0530] <Formation of resist pattern>

[0531] In Example 1, a resist pattern was obtained in the same manner as in Example 1, except that the polymer solution prepared in Synthesis Example 1 was changed to the polymer solution prepared in Synthesis Example 2.

[0532] [5-3] Example 3

[0533] <Formation of resist pattern>

[0534] In Example 1, a resist pattern was obtained in the same manner as in Example 1, except that the polymer solution prepared in Synthesis Example 1 was changed to the polymer solution prepared in Synthesis Example 3.

[0535] [5-4] Example 4

[0536] <Formation of resist pattern>

[0537] In Example 1, a resist pattern was obtained in the same manner as in Example 1, except that the polymer solution prepared in Synthesis Example 1 was changed to the polymer solution prepared in Synthesis Example 4.

[0538] [5-5] Example 5

[0539] <Formation of resist pattern>

[0540] The organic underlayer film-forming composition was spin-coated on a silicon wafer and heated on a hot plate at 215° C. for 1 minute to form an organic underlayer film (layer A) (film thickness: 90 nm).

[0541] The resist underlayer film-forming composition was spin-coated thereon, and the mixture was heated on a hot plate at 215° C. for 1 minute to form a resist underlayer film (layer B) (film thickness: 10 nm).

[0542] A resist solution (tin oxide resist) was further spin-coated thereon, and heated at 130° C. for 1 minute to form an EUV resist layer (C layer), and then exposed using an EB exposure device (ELS-G130) manufactured by ELIONIX. It should be noted that during exposure, exposure was performed so that the line width of the resist became 16 nm and the width between the lines (space width) became 28 nm after the development described below.

[0543] After exposure, post-exposure heating (PEB, 180°C for 1 minute) was performed, and the surface was cooled to room temperature on a cooling plate, and a spin development was performed at 1000 rpm for 60 seconds using an organic solvent (propylene glycol monomethyl ether acetate) as a developer. Then, without spin drying, the polymer solution prepared in Synthesis Example 4 was applied, and the propylene glycol monomethyl ether acetate used in the development was replaced with this solution. Then, the above-mentioned silicon substrate was rotated at 1500 rpm for 60 seconds to dry the solvent in the solution, and then heated at 250°C for 60 seconds to form a coating film, and the above-mentioned resist pattern was embedded. Using SUS867 (manufactured by Ushio Electric), 172 nm light was irradiated in the presence of air, and UV / O 3 The formed coating film is removed by etching to obtain a resist pattern.

[0544] [6] Comparative Example 1

[0545] <Formation of resist pattern>

[0546] The organic underlayer film-forming composition was spin-coated on a silicon wafer and heated on a hot plate at 215° C. for 1 minute to form an organic underlayer film (layer A) (film thickness: 90 nm).

[0547] The resist underlayer film-forming composition was spin-coated thereon, and the mixture was heated on a hot plate at 215° C. for 1 minute to form a resist underlayer film (layer B) (film thickness: 10 nm).

[0548] A resist solution (tin oxide resist) was further spin-coated thereon, and heated at 130° C. for 1 minute to form an EUV resist layer (C layer), and then exposed using an EB exposure device (ELS-G130) manufactured by ELIONIX. It should be noted that during exposure, exposure was performed so that the line width of the resist became 16 nm and the width between the lines (space width) became 28 nm after the development described below.

[0549] After exposure, post-exposure heating (PEB, 180°C for 1 minute) was performed, cooled to room temperature on a cooling plate, and spin developed at 1000 rpm for 60 seconds using an organic solvent (propylene glycol monomethyl ether acetate) as a developer. Then, spin drying was performed at 2500 rpm for 30 seconds to remove the developer to obtain a resist pattern.

[0550] The resist patterns obtained in Examples 1 to 4 and Comparative Example 1 were measured for pattern size using a length measurement SEM (CG4100) manufactured by Hitachi High-Technologies Corporation. The obtained results are shown in Table 3. In Table 3, "good" means that a pattern with a size of 16 nm was formed without peeling or warping.

[0551] [Table 3]

[0552]

[0553] As shown in Table 3, when a pattern is formed by embedding a pattern using a polymer solution after development and then removing the resin by dry etching, peeling of the pattern during development can be suppressed, and a good fine pattern can be formed.

[0554] Description of Reference Numerals

[0555] 1 substrate

[0556] 2 Organic lower membrane

[0557] 3 Silicon-containing resist underlayer film

[0558] 4 Metal-containing resist film

[0559] 4A Resist pattern

[0560] 5 Organic film

[0561] 10 Mask

[0562] L light.

Claims

1. A composition for forming an organic film, characterized in that for forming an organic film, forming the organic film between resist patterns formed of a metal-containing resist film and thereafter removing the organic film, The organic film-forming composition contains organic film-constituting components and a solvent.

2. The composition for forming an organic film according to claim 1, wherein The metal-containing resist film contains at least any one element of Si, Ge, Sn, Ti, Zr, Hf, Al, and Co.

3. The composition for forming an organic film according to claim 1, wherein The organic film constituent component contains a polymer (A).

4. The composition for forming an organic film according to claim 3, wherein The polymer (A) is not water-soluble.

5. The composition for forming an organic film according to claim 4, wherein The polymer (A) is a polymer (A1) having a ring structure.

6. The composition for forming an organic film according to claim 5, wherein The polymer (A1) is a polymer (A1-1) having a ring structure in its main chain.

7. The composition for forming an organic film according to claim 5, wherein The polymer (A1) is a polymer (A1-2) having a ring structure in the side chain.

8. The composition for forming an organic film according to claim 6, wherein In the polymer (A1-1), at least one of the ring structures in the main chain is a monocyclic aliphatic ring.

9. The composition for forming an organic film according to claim 8, wherein The polymer (A1-1) is a polymer (X) having a repeating unit represented by the following formula (X), In the formula (X), T represents a group having a monocyclic aliphatic ring constituting the main chain of the polymer (X), Q represents a divalent linking group, Ar represents an aromatic group which may be substituted.

10. The composition for forming an organic film according to claim 6, wherein In the polymer (A1-1), at least one of the ring structures in the main chain is a heterocyclic ring.

11. The composition for forming an organic film according to claim 1, wherein The polymer (A1-1) is a polymer (Y) having a repeating unit represented by the following formula (Y), In formula (Y), A1, A2, A3, A4, A5 and A6 represent a hydrogen atom, a methyl group or an ethyl group, respectively. X1 represents the following formula (Y2), the following formula (Y3), the following formula (Y4), or the following formula (Y0), Q represents the following formula (Y5), or the following formula (Y6); In formula (Y2), formula (Y3), formula (Y4) and formula (Y0), R1 and R2 each represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 3 to 6 carbon atoms, a benzyl group or a phenyl group, and the alkyl group having 1 to 6 carbon atoms, the alkenyl group having 3 to 6 carbon atoms, the benzyl group and the phenyl group may or may not be selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a cyano group, a hydroxyl group, a carboxyl group and a Alkylthio In addition, R1 and R2 are not bonded to each other or bonded to each other to form a ring having 3 to 6 carbon atoms, R3 represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 3 to 6 carbon atoms, a benzyl group or a phenyl group, and the phenyl group may be substituted with a group selected from an alkyl group having 1 to 6 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a cyano group, a hydroxyl group and an alkylthio group having 1 to 6 carbon atoms, Indicates a bond, 1 represents the bond to the carbon atom, 2 represents a bond to the nitrogen atom; In formula (Y5) and formula (Y6), Q1 represents an alkylene group having 1 to 10 carbon atoms, a phenylene group, a naphthylene group, or an anthrylene group, and the alkylene group, the phenylene group, the naphthylene group, and the anthrylene group are each substituted or not substituted by an alkyl group having 1 to 6 carbon atoms, a carbonyloxyalkyl group having 2 to 7 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a phenyl group, a nitro group, a cyano group, a hydroxyl group, an alkylthio group having 1 to 6 carbon atoms, a group having a disulfide group, a carboxyl group, or a group containing a combination thereof, n1 and n2 represent 0 or 1 respectively. X2 represents the above formula (Y2), the above formula (Y3), or the above formula (Y0), Indicates a bond.

12. The composition for forming an organic film according to claim 7, wherein In the polymer (A1-2), at least one of the ring structures of the side chains is a heterocyclic ring.

13. The composition for forming an organic film according to claim 7, wherein At least one of the ring structures of the side chains in the polymer (A1-2) is a lactone ring.

14. The composition for forming an organic film according to claim 13, wherein The polymer (A1-2) is a polymer (Z) having a repeating unit represented by the following formula (Z), In formula (Z), Q represents a divalent linking group, R 1 represents a substituted or unsubstituted trivalent hydrocarbon group having 3 or 4 carbon atoms, P represents a bonding group constituting the main chain, R 2 represents a hydrogen atom, a methyl group or a halogen atom.

15. The composition for forming an organic film according to claim 4, wherein The polymer (A) is a polymer (A2) having a repeating unit represented by the following formula (Q), In formula (Q), R 11 represents an alkyl group having 1 to 4 carbon atoms, R 12 represents a hydrogen atom, a methyl group or a halogen atom.

16. The composition for forming an organic film according to claim 1, wherein The organic film-forming composition is used to prevent the resist pattern from collapsing.

17. The composition for forming an organic film according to claim 1, wherein The organic film-forming composition also serves as a developer when forming the resist pattern.

18. A method for manufacturing a semiconductor element, characterized in that: Including the following processes: A step of irradiating a metal-containing resist film with light or an electron beam; A step of bringing a developer into contact with the metal-containing resist film irradiated with the light or electron beam to obtain a resist pattern; A step of applying the organic film-forming composition according to any one of claims 1 to 16 onto the resist pattern without drying the resist pattern in contact with the developer to form an organic film between the resist patterns; and A step of removing the organic film.

19. The method for manufacturing a semiconductor element according to claim 18, wherein: In the step of forming the organic film, the organic film is also formed on the resist pattern.

20. The method for manufacturing a semiconductor element according to claim 18, wherein: The step of removing the organic film is selected from dry etching, wet etching, radiation etching, high temperature firing, dissolution removal using a solvent, and ozone treatment.

21. A substrate with a metal-containing resist pattern, characterized in that: The organic film-forming composition according to any one of claims 1 to 16 is applied onto a metal-containing resist pattern to embed an organic film between the metal-containing resist patterns.

Images