Methods for manufacturing compositions containing organic acid compounds, methods for manufacturing photolithography compositions containing organic acid compounds, and methods for manufacturing photoresist patterns.

Abstract

The objective of this invention is to provide a method for reducing standing waves during the lithography process. To reduce standing waves during the lithography process, the present invention provides a method using a composition containing an organic acid compound (AA) having a specific structure.

Description

[Technical Field]

[0001] This invention relates to a method of using a composition containing an organic acid compound to reduce standing waves in a photolithography step. Furthermore, this invention relates to a photolithography composition containing an organic acid compound, and a method for manufacturing photoresist patterns and devices using the same. [Previous Technology]

[0002] In recent years, the demand for high integration in LSIs has been increasing, requiring finer patterns. To meet this demand, lithography processes using short-wavelength KrF excimer lasers (248nm), ArF excimer lasers (193nm), extreme ultraviolet (EUV; 13nm), X-rays, and electron beams are becoming practical. To meet this demand for finer photoresist patterns, high-resolution photosensitive resin compositions used as photoresists in fine processing are also required. Fine patterns can be formed by exposure using short-wavelength light, but high dimensional accuracy is required.

[0003] In the photolithography process, a photoresist pattern is formed by exposing and developing the photoresist. It is known that during exposure, the incident light hitting the photoresist and the reflected light from the substrate-air interface will interfere multiple times, resulting in a standing wave phenomenon. The generation of standing waves will reduce the dimensional accuracy of the pattern. In order to reduce standing waves, an anti-reflective film is formed on the upper and / or lower layers of the photoresist.

[0004] There is an attempt to improve exposure margin by using a chemically amplified photoresist composition containing a salt formed from a specific sulfonic acid and an organic amine on top of an antireflective film to perform a buffering function (e.g., Patent Document 1). [Prior Art Documents] [Patent Documents]

[0005] Patent Document 1 Japanese Patent Application Publication No. 2005-17409 [Summary of the Invention]

[0006] [The problem the invention aims to solve]

[0007] The inventor focused on controlling the activity of acids in chemical processes performing fine processing. For example, even if an anti-reflective film is formed on the substrate during the microfilm process, a photoresist film is formed on it and exposure is performed, the standing wave will remain, and further techniques are required. Also, the lower anti-reflective film needs to be removed after the photoresist pattern is formed, so there are situations where the process cannot be used, or other means need to be sought. The inventor believes that there are still one or plural topics seeking improvement. These can be enumerated as follows: reducing standing waves in the microshaping step; reducing standing waves of photoresist patterns; suppressing inhomogeneity of photoresist pattern width; suppressing pattern collapse of photoresist patterns; obtaining well-shaped photoresist patterns; obtaining photoresist films with good sensitivity; obtaining photoresistors with good resolution film;obtains more subtle patterns;controls acid activity in chemical processes;inhibits acid movement speed in chemical processes;enlarges exposure margin;increases focus depth;enlarges process latitude;obtains photoresist patterns that can be removed cleanly;improves yield of microshaping step. [Means used to solve problems]

[0008] The invention is a method of using a composition containing an organic acid compound (AA), which is used to reduce the standing wave in a microshaping step; na2 is 0, 1 or 2).

[0009] The microshape composition of the present invention is made up containing an organic acid compound (AA) and a solvent (B), herein, the organic acid compound (AA) is represented by the formula (aa): (Here, Ra is a C1-40 alkyl group, at least one of the methylene contained in the preceding alkyl group can be replaced by a carbonyl group, Xa is SO3H or COOH, and na2 is 10, 1, or na2).

[0010] The method of fabricating the membrane of the present invention contains the steps described below. (1) application of the above-mentioned microshadow composition over the substrate;(2) formation of a film from the microshadow composition by resorting to decompression and or heating.

[0011] The method of fabrication of the device of the present invention contains the above method. [Effect of the invention]

[0012] According to the present invention, one or more of the following effects are expected: Reduction of standing waves in the lithography process; reduction of standing waves in the photoresist pattern; suppression of unevenness in the width of the photoresist pattern; suppression of pattern collapse of the photoresist pattern; obtaining a photoresist pattern with a good shape; obtaining a photoresist film with good sensitivity; obtaining a photoresist film with good resolution; obtaining a finer pattern; controlling the activity of acid in the chemical process; suppressing the migration speed of acid in the chemical process; obtaining a photoresist film with a large exposure margin; enabling an increase in depth of focus; enabling an increase in process latitude; enabling the obtaining of a photoresist pattern that can be cleanly removed; and increasing the yield of the lithography process.

Implementation Method

[0014] The following is a detailed description of the embodiments of the present invention.

[0015] [Definitions] In this specification, unless otherwise specified or mentioned, the definitions and examples set forth in this paragraph shall apply. The singular form includes the plural form, and "a" and "the" mean "at least one". The elements of a concept can be expressed in a plural form, and when a quantity is stated (e.g., mass%, mol%), the quantity means the sum of such plural forms. "And / or" includes all combinations of elements, and also includes the use of elements. When "~" or "-" is used to indicate a numerical range, these include both endpoints and the units are common. For example, 5~25 mol% means more than 5 mol% and less than 25 mol%. The notations "Cx-y", "Cx~Cy", and "Cx" refer to the number of carbons in a molecule or substituent. For example, C1-6 alkyl refers to an alkane chain having more than 1 and less than 6 carbons (methyl, ethyl, propyl, butyl, pentyl, hexyl, etc.). When a polymer has a plurality of repeating units, these repeating units are copolymerized. Such copolymerization can be any of alternating copolymerization, random copolymerization, block copolymerization, graft copolymerization, or a mixture thereof. When representing polymers or resins using structural formulas, the n, m, etc., enclosed in parentheses indicate the number of repeating units. The unit of temperature is Celsius. For example, 20 degrees Celsius means 20 degrees Celsius. Additives refer to the compound itself that has the function (e.g., if it is a base-generating agent, it is the compound that generates the base). The compound can also be dissolved or dispersed in a solvent and added to the composition. As one aspect of the invention, such a solvent is preferably contained in the composition of the invention as solvent (B) or other components.

[0016] [Method using a composition containing an organic acid compound (AA)] This invention relates to a method for using a composition containing an organic acid compound (AA) represented by formula (aa) (hereinafter sometimes referred to as "the composition used in this invention") to reduce standing waves in a photolithography step. Preferably, the composition used in this invention is applied above a substrate to form a film. According to this invention, since standing waves can be reduced, a lower anti-reflective film (BARC) may not be formed on the lower layer of the composition used in this invention. Therefore, applying the composition used in this invention without forming a BARC is also a suitable form of this invention. Furthermore, since a further standing wave reduction effect can be achieved when a BARC is formed, this invention can also be used when forming a BARC. The composition of the method of using this invention is preferably the photolithography composition described later.

[0017] Organic Acid Compound (AA) The organic acid compound (AA) (hereinafter sometimes referred to as (AA) component; the same applies to (B) and thereafter) is represented by formula (aa). Here, Ra is a C1-40 (preferably C1-20; more preferably C5-10) hydrocarbon group. The aforementioned hydrocarbon group may form a ring. The aforementioned ring may be an unsaturated ring or a saturated ring. At least one of the methylene groups contained in the aforementioned hydrocarbon group may be substituted with a carbonyl group. As a suitable form of the present invention, one of the methylene groups contained in the aforementioned hydrocarbon group is substituted with a carbonyl group. Xa is SO3H or COOH (preferably SO3H). na1 is 1 or 2 (preferably 1). na2 is 0, 1 or 2 (preferably 0).

[0018] The organic acid compound (AA) is preferably represented by the formula (aa-1), (aa-2), (aa-3) or (aa-4).

[0019] Formula (aa-1) is as follows. Here, AL refers to a C5-20 (preferably C6-8) alicyclic ring. At least one of the methylene groups in the aforementioned alicyclic ring may be substituted with a carbonyl group. As a suitable form of the present invention, one of the methylene groups contained in the aforementioned alicyclic ring is substituted with a carbonyl group. The alicyclic ring may contain intercarbon double bonds, but is preferably a saturated alicyclic ring. Xa1 refers to SO3H or COOH (preferably SO3H). Ra1 refers to alkyl groups, each independently of C1-5 (preferably methyl or ethyl; more preferably methyl). n11 refers to 1 or 2 (preferably 1). n12 refers to 0, 1 or 2 (preferably 1). n13 refers to 0, 1 or 2 (preferably 2). n14 refers to 0, 1 or 2 (preferably 0).

[0020] For a specific example of an organic acid compound (AA) represented by formula (aa-1), 10-camphor sulfonic acid can be cited.

[0021] Formula (aa-2) is as follows. Here, Xa2 is SO3H or COOH (preferably SO3H). Ra2 is each independently a C1-15 alkyl group (preferably a C1-12 alkyl group; more preferably methyl or dodecyl). n21 is 1 or 2 (preferably 1). n22 is 0, 1 or 2 (preferably 0 or 1; more preferably 1). n23 is 0, 1 or 2 (preferably 0 or 1; more preferably 0).

[0022] Specific examples of organic acid compounds (AA) represented by formula (aa-2) include: p-toluenesulfonic acid, dodecylbenzenesulfonic acid, benzoic acid, 2-hydroxybenzoic acid (salicylic acid), 3-hydroxybenzoic acid, 4-hydroxybenzoic acid, etc.

[0023] Formula (aa-3) is as follows. Here, Xa3 refers to SO3H or COOH (preferably SO3H). Ra3 refers to a C1-10 alkyl group, a C1-10 fluorinated alkyl group, or a C2-10 alkenyl group (preferably a C1-4 alkyl group). In this specification, fluorinated alkyl group means that some or all of the H atoms in the alkyl group are replaced with F atoms, and complete replacement is also a preferred form. In this specification, alkenyl group means a straight-chain or branched hydrocarbon having a carbon-carbon double bond and having a hydrogen group removed from any carbon atom.

[0024] Specific examples of organic acid compounds (AA) represented by formula (aa-3) include: methanesulfonic acid, 1-propanesulfonic acid, 1-butanesulfonic acid, trifluoromethanesulfonic acid, heptafluoro-1-propanesulfonic acid, nonafluoro-1-butanesulfonic acid, etc.

[0025] Formula (aa-4) is as follows. Here, Xa4 is SO3H or COOH (preferably COOH). Ra3 is a C1-10 alkyl group or a C2-10 alkenyl group (preferably a C1-4 alkyl group or a C2-4 alkenyl group; more preferably a methylene group or a C2 alkenyl group). In this specification, alkenyl group means a divalent hydrocarbon group having a carbon-carbon double bond.

[0026] Specific examples of organic acid compounds (AA) represented by formula (aa-4) include malonic acid, maleic acid, etc.

[0027] The organic acid compound (AA) is more preferably represented by formula (aa-1) or (aa-2); more preferably by formula (aa-1).

[0028] While not bound by theory, it is believed that the reduction of standing waves by containing organic acid compounds (AA) is due to their contribution to suppressing the movement speed of substances generated in the film during the lithography process (e.g., acids generated by acid generating agent (D)). For clarity, in the composition of the present invention containing solvent (B), the components contained in the composition may be in an ionic state, may be in a salt state, or may be both. For example, it may be a state in which organic acid compounds (AA) and basic compounds (AB) are dissolved in solvent (B), and ions and salts coexist in the composition.

[0029] Basic Compound (AB) The composition used in this invention is preferably further comprising a basic compound (AB). The basic compound (AB) is selected from the group consisting of primary amines, secondary amines, and tertiary amines. The preferred basic compound (AB) and its content are the same as those described in the following description of the photolithography composition.

[0030] Solvent (B) The composition used in this invention is preferably composed of solvent (B). The preferred solvent (B) and its content are the same as those described in the following description of photolithography compositions.

[0031] Film-forming component (C) The composition used in this invention is preferably composed of a film-forming component (C). The preferred film-forming component (C) and its content are the same as those described in the following description of photolithography compositions.

[0032] [Photolithography Composition] The photolithography composition of the present invention is composed of an organic acid compound (AA) represented by formula (aa) and a solvent (B). In the present invention, the term "photolithography composition" refers to a composition used in photolithography processes, such as those used for cleaning and film formation. Specifically, examples include: photoresist composition, planarization film forming composition, lower antireflective film forming composition, upper antireflective film forming composition, rinsing solution, photoresist removal agent, etc. The photolithography composition may or may not be removed after the process, but removal is preferable. The residue formed by the photolithography composition may or may not remain in the final device, but non-residue is preferable. The photolithography composition of the present invention is a photolithography film forming composition, more preferably a photoresist composition. Both positive and negative photoresist compositions can be used, but negative photoresist compositions are preferred. Furthermore, the photolithography composition of the present invention is preferably a chemically amplified photoresist composition, and more preferably a chemically amplified negative photoresist composition. In this case, it is more preferably composed of, in addition to components (A) and (B), the polymer, acid generator and crosslinking agent described later.

[0033] Organic Acid Compound (AA) The organic acid compound (AA) used in the photolithography composition of the present invention is as described above, and its preferred form is also the same as described above. The organic acid compound (AA) can be used alone or in combination of two or more. The content of the organic acid compound (AA), based on the solvent (B), is preferably 0.001 to 10% by mass (more preferably 0.050 to 1% by mass; further preferably 0.075 to 0.2% by mass). The content of the organic acid compound (AA), based on the film-forming component (C), is preferably 0.05 to 30% by mass (more preferably 0.1 to 2% by mass; further preferably 0.2 to 1.5% by mass).

[0034] Alkaline compound (AB) The photolithography composition of the present invention is preferably further containing an alkaline compound (AB). By adding the alkaline compound (AB), the pH of the photolithography composition can be adjusted.

[0035] The basic compound (AB) is selected from the group consisting of primary amines, secondary amines and tertiary amines; preferably selected from the group consisting of secondary aliphatic amines with C2-32, tertiary aliphatic amines with C3-48, aromatic amines with C6-30, heterocyclic amines with C5-30, and derivatives thereof.

[0036] Specific examples of basic compounds (AB) include: triethylamine, triethanolamine, tripropylamine, tributylamine, tri-n-octylamine, triisopropanolamine, diethylamine, diisopropylamine, di-n-propylamine, diisobutylamine, di-n-propylamine, diethanolamine, tris(2-(2-methoxyethoxy)ethyl)amine, 1,4-diazabicyclo[2.2.2]octane, piperidine, benzylamine, N,N-dicyclohexylmethylamine, etc. Specific examples of basic compounds (AB) preferably include: triethylamine, triethanolamine, tris(2-(2-methoxyethoxy)ethyl)amine, 1,4-diazabicyclo[2.2.2]octane, or benzylamine; more preferably: triethanolamine, or tris(2-(2-methoxyethoxy)ethyl)amine; even more preferably: tris(2-(2-methoxyethoxy)ethyl)amine.

[0037] The molecular weight of the basic compound (AB) is preferably 50 to 400 (more preferably 100 to 380; further preferably 200 to 360; even more preferably 300 to 350).

[0038] The basic compound (AB) can be used alone or in combination of two or more. The content of the basic compound (AB), based on the film-forming component (C), is preferably 0-40% by mass (more preferably 0-10% by mass; further preferably 0.1-5% by mass; even more preferably 0.5-2% by mass). The content of the basic compound (AB), based on the solvent (B), is preferably 0.001-10% by mass (more preferably 0.050-1% by mass; further preferably 0.10-0.5% by mass). It is also suitable for the composition to be free of the basic compound (AB) (0.00% by mass).

[0039] Solvent (B) The solvent (B) used in this invention is not particularly limited as long as it is capable of dissolving each of the incorporated components. Solvent (B) is preferably composed of an organic solvent (B1). Solvent (B) consisting solely of an organic solvent (B1) is also a suitable form. Organic solvent (B1) is preferably composed of a hydrocarbon solvent, ether solvent, ester solvent, alcohol solvent, ketone solvent, or any mixture thereof. Specific examples of the solvent include: water, n-pentane, isopentane, n-hexane, isohexane, n-heptane, isoheptane, 2,2,4-trimethylpentane, n-octane, isooctane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbenzene, isopropylbenzene, diethylbenzene, isobutylbenzene, triethylbenzene, diisopropylbenzene, n-pentylnaphthalene, trimethylbenzene, methanol, ethanol, n-propylbenzene Alcohols, isopropanol, n-butanol, isobutanol, secondary butanol, tertiary butanol, n-pentanol, isopentanol, 2-methylbutanol, secondary pentanol, tertiary pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, secondary hexanol, 2-ethylbutanol, secondary heptanol, heptanol-3, n-octanol, 2-ethylhexanol, secondary octanol, n-nonanol, 2,6-dimethylheptanol-4, n-decanol, secondary undecylol, trimethylnonanol, secondary tetradecylol, di... Heptadecanol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, phenylmethyl methanol, diacetone alcohol, cresol, ethylene glycol, propylene glycol, 1,3-butanediol, pentanediol-2,4, 2-methylpentanediol-2,4, hexanediol-2,5, pentanediol-2,4, 2-ethylhexanediol-1,3, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, glycerol, acetone, methyl ethyl ketone Methyl n-propyl ketone, methyl n-butyl ketone, diethyl ketone, methyl isobutyl ketone, methyl n-pentyl ketone, ethyl n-butyl ketone, methyl n-hexyl ketone, diisobutyl ketone, trimethyl nonanone, cyclohexanone, cyclopentanone, methyl cyclohexanone, 2,4-pentanedione, acetone-acetone, diacetone alcohol, acetophenone, frankincense, ethyl ether, isopropyl ether, n-butyl ether (di-n-butyl ether, DBE), n-hexyl ether, 2-ethylhexyl ether, ethylene oxide, 1,2-Epoxypropane, dioxolane, 4-methyldioxolane, dialkyl, dimethyldialkyl, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-n-hexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethylbutyl ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol mono-2-ethylbutyl ether n-Butyl ether, diethylene glycol di-n-butyl ether, diethylene glycol mono-n-hexyl ether, ethoxytriethylene glycol, tetraethylene glycol di-n-butyl ether, propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, diethyl carbonate, acetic acid Methyl acetate, ethyl acetate, γ-butyrolactone (GBL), γ-valerolactone, n-propyl acetate, isopropyl acetate, n-butyl acetate (n-butyl acetate, nBA), isobutyl acetate, butyl acetate 2, n-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, n-nonyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, ethylene glycol diacetate, methoxytriglycol acetate Acetate), tributyl acetate, ethyl propionate, ethyl 3-ethoxypropionate, n-butyl propionate, isoamyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate (EL), n-butyl lactate, n-amyl lactate, diethyl malonate, dimethyl phthalate, diethyl phthalate, propylene glycol 1-monomethyl ether 2-acetate (PGMEA), propylene glycol monoethyl Ether acetate, propylene glycol monopropyl ether acetate, 3-methoxybutyl acetate, N-methylformamide, N,N-dimethylformamide, N,N-diethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpropionic acid, N-methylpyrrolidone, dimethyl sulfide, diethyl sulfide, thiophene, tetrahydrothiophene, dimethyl sulfide, cyclobutane, and 1,3-propanesulfonic acid lactone (1,3-Propanesultone). These solvents can be used alone or in mixtures of two or more. As solvent (B), PGME, PGMEA, EL, GBL, n-butanol, tributanol, n-octanol, ethyl 3-ethoxypropionate, 3-methoxybutyl acetate, cyclopentanone, tributyl acetoacetate, or any mixture thereof are preferred; more preferably PGME, PGMEA, or mixtures thereof. A suitable embodiment of the invention is that the organic solvent (B1) is a mixture of PGME and PGMEA, with a PGME / PGMEA ratio of 0.1 to 10 by mass (more preferably 0.1 to 1; further preferably 0.2 to 0.5; even more preferably 0.2 to 0.3).

[0040] Due to its relationship with other layers and films, the solvent (B) may also be substantially water-free. For example, the water content in the solvent (B) is preferably 0.1% by mass or less, more preferably 0.01% by mass or less, and even more preferably 0.001% by mass or less. A water-free (0% by mass) solvent (B) is also a suitable form.

[0041] The content of solvent (B), based on the photolithography composition, is preferably 10 to 99.999% by mass (more preferably 75 to 95% by mass; even more preferably 80 to 90% by mass).

[0042] Film-forming component (C) The photolithography composition of the present invention is preferably composed of a film-forming component (C). In the present invention, the film-forming component (C) refers to a component constituting at least a portion of the formed membrane. The formed membrane does not necessarily need to be composed solely of the film-forming component (C). For example, the film-forming component (C) can be combined with the crosslinking agent (E) described later to form a membrane. As a suitable form, the film-forming component (C) constitutes the majority of the formed membrane, for example, constituting 60% or more per volume of the membrane (more preferably 70% or more, further preferably 80% or more, and even more preferably 90% or more).

[0043] The film-forming component (C) is preferably composed of a polymer (C1). In a suitable form of the present invention, the film-forming component (C) is a polymer (C1). Examples of polymers (C1) include: phenolic varnish derivatives, phenol derivatives, polystyrene derivatives, polyacrylic acid derivatives, polymaleic acid derivatives, polycarbonate derivatives, polyvinyl alcohol derivatives, polymethacrylic acid derivatives, and copolymers of combinations thereof.

[0044] When the photolithography composition of the present invention is a photoresist composition, it is preferable that the polymer (C1) is a commonly used polymer among photoresist compositions whose solubility in alkaline developing solutions changes due to exposure, etc. When the photolithography composition of the present invention is a chemically amplified positive photoresist composition, it is preferable that the polymer (C1) reacts with acid and its solubility in developing solutions increases. Such a polymer is, for example, an acid group protected by a protecting group, which, if an acid is added externally, will detach from the protecting group, thereby increasing its solubility in developing solutions. When the photolithography composition of the present invention is a chemically amplified negative photoresist composition, it is preferable that the polymer (C1) is cross-linked between polymers by using an acid generated by exposure as a catalyst, for example, a cross-linking agent, thereby reducing its solubility in developing solutions. Such a polymer can be arbitrarily selected from those commonly used in photolithography. Among such polymers, it is preferable that it has at least one repeating unit represented by the following formulas (c1), (c2), and (c3). When the photolithography composition of the present invention is a chemically amplified negative photoresist composition, it is preferred that the polymer (C1) has at least a repeating unit represented by formula (c1).

[0045] The repeating unit represented by formula (c1) is as follows. Here, Rc1 is H, C1-5 alkyl, C1-5 alkoxy, or COOH (preferably H or methyl; more preferably H). Rc2 is C1-5 alkyl (wherein -CH2- may be substituted with -O-). Rc2 is preferably methyl, ethyl, or methoxy (more preferably methyl). m1 is a number from 0 to 4 (preferably 0). m2 is a number from 1 to 2 (preferably 1). m1 + m2 ≦ 5. The specific examples of formula (c1) are as follows.

[0046]

[0047] The constituent units represented by formula (c2) are as follows. Here, Rc3 is H, C1-5 alkyl, C1-5 alkoxy, or COOH (preferably H or methyl; more preferably H). Rc4 is C1-5 alkyl or C1-5 alkoxy (here, the -CH2- contained in the alkyl or alkoxy group can be replaced by -O-). Rc4 is more preferably C1-5 alkoxy (here, the -CH2- contained in the alkoxy group can be replaced by -O-), in which case m3 is preferably 1. Examples of Rc4 in this form include: methoxy, tributoxy, and -O-CH(CH3)-O-CH2CH3. m3 is a number from 0 to 5 (preferably 0, 1, 2, 3, 4, or 5; more preferably 0 or 1). m3 being 0 is also a suitable form. The specific examples of formula (c2) are as follows.

[0048]

[0049] The constituent units represented by formula (c3) are as follows. Here, Rc5 is H, C1-5 alkyl, C1-5 alkoxy, or COOH (more preferably H, methyl, ethyl, methoxy, or COOH; further preferably H or methyl; even more preferably H). Rc6 is C1-15 alkyl or C1-5 alkyl ether, and Rc6 may have a cyclic structure. Rc6 is preferably methyl, isopropyl, tributyl, cyclopentyl, methylcyclopentyl, ethylcyclopentyl, methylcyclohexyl, ethylcyclohexyl, methyladamantyl, or ethyladamantyl (more preferably tributyl, ethylcyclopentyl, ethylcyclohexyl, or ethyladamantyl; further preferably tributyl). The specific examples of formula (c3) are as follows.

[0051] These constituent units are appropriately blended according to the purpose, therefore the blending ratio is not particularly limited, but it is preferred to blend them in a manner that is suitable for the solubility of alkaline developing solutions. These polymers can also be used in combination of two or more.

[0052] The mass-average molecular weight (hereinafter sometimes referred to as Mw) of the polymer (C1) is preferably 500 to 100,000 (more preferably 1,000 to 50,000; further preferably 3,000 to 20,000; even more preferably 4,000 to 20,000). In this invention, Mw can be determined by gel permeation chromatography (GPC). In the same determination, a suitable example is the use of a GPC column at 40°C, a dissolution solvent of tetrahydrofuran at a rate of 0.6 mL / min, and monodisperse polystyrene as a standard.

[0053] The film-forming component (C) can be used alone or in combination with two or more other components. The content of the film-forming component (C), based on the photolithography composition, is preferably 2 to 40% by mass (more preferably 2 to 30% by mass; further preferably 5 to 25% by mass; and even more preferably 10 to 20% by mass).

[0054] Based on the total number of repeating units in the polymer (C1), if the ratios of repeating units represented by formulas (c1), (c2), and (c3) are set as nc1, nc2, and nc3 respectively, then the following are one of the suitable forms of the present invention. nc1 = 0~100% (more preferably 30~100%; further preferably 50~100%; even more preferably 60~100%). nc2 = 0~100% (more preferably 0~70%; further preferably 0~50%; even more preferably 0~40%). nc3 = 0~50% (more preferably 0~40%; further preferably 0~30%; even more preferably 0~20%). A form that does not contain repeating units represented by formula (c3) (nc3=0) is also another suitable form of the present invention.

[0055] Acid Generating Agent (D) The photolithography composition of the present invention may contain an acid generating agent (D). In the present invention, an acid generating agent refers to a compound itself that has acid generating function. Examples of acid generating agents include photoacid generating agents (PAG) that generate acid by exposure and thermoacid generating agents (TAG) that generate acid by heating. When the photolithography composition of the present invention is a chemically amplified photoresist composition, it is preferable to contain PAG.

[0056] Examples of PAGs include strontium salts, iodonium salts, sulfonyldiazomethane, and N-sulfonoxyimino acid generators. Representative PAGs are shown below, which can be used alone or in combination of two or more.

[0057] Salmon salts are salts containing anions of carboxylate, sulfonate or aceimine, and salmon cations. Representative strontium cations include: triphenylstrontium, (4-methylphenyl)diphenylstrontium, (4-methoxyphenyl)diphenylstrontium, triphenyl(4-methoxyphenyl)strontium, (4-trimethylbutylphenyl)diphenylstrontium, (4-trimethylbutoxyphenyl)diphenylstrontium, bis(4-trimethylbutoxyphenyl)phenylstrontium, triphenyl(4-trimethylbutoxyphenyl)strontium, triphenyl(4-trimethylbutoxyphenyl)strontium, triphenyl(4-trimethylbutoxyphenyl)strontium, triphenyl(4-methylphenyl)strontium, (4-methoxy-3,5-dimethylphenyl)dimethylstrontium, (3-trimethylbutoxyphenyl)diphenylstrontium, bis(3-trimethylbutoxyphenyl)phenylstrontium, triphenyl(3-trimethylbutoxyphenyl)strontium, (3,4-di-trimethylbutoxyphenyl)diphenylstrontium, bis(3,4-di-trimethylbutoxyphenyl)phenylstrontium, triphenyl(4-trimethylbutoxyphenyl)strontium, triphenyl(4-methylphenyl)strontium, triphenyl(4-methylbutoxy ... 3,4-Bis- and tri-butoxyphenyl) strontium, (4-phenoxyphenyl) diphenyl strontium, (4-cyclohexylphenyl) diphenyl strontium, bis(p-phenyl)bis(diphenyl strontium), diphenyl(4-phenoxythiophenyl) strontium, diphenyl(4-phenylthiophenyl) strontium, diphenyl(8-phenylthiobiphenyl) strontium, (4-tri-butoxycarbonylmethyloxyphenyl) diphenyl strontium, tris(4- (4-Tributoxycarbonylmethyloxyphenyl) strontium, (4-tributoxyphenyl)bis(4-dimethylaminophenyl) strontium, trimethyl(4-dimethylaminophenyl) strontium, 2-naphthyldiphenyl strontium, dimethyl(2-naphthyl) strontium, 4-hydroxyphenyldimethyl strontium, 4-methoxyphenyldimethyl strontium, trimethyl strontium, 2-oxycyclohexylcyclohexylmethyl strontium, trinaphthyl strontium, and tribenzyl strontium. Representative sulfonates include: trifluoromethanesulfonate, nonafluorobutyrate, heptadecafluorooctyl sulfonate, 2,2,2-trifluoroethanesulfonate, pentafluorobenzenesulfonate, 4-(trifluoromethyl)benzenesulfonate, 4-fluorobenzenesulfonate, toluenesulfonate, benzenesulfonate, 4-(4-toluenesulfonyloxy)benzenesulfonate, naphthalenesulfonate, camphorsulfonate, octylsulfonate, dodecylbenzenesulfonate, butyrate, and methanesulfonate. Representative amides include: bis(perfluoromethanesulfonyl)amide, bis(perfluoroethanesulfonyl)amide, bis(perfluorobutanesulfonyl)amide, bis(perfluorobutanesulfonoxy)amide, bis[perfluoro(2-ethoxyethane)sulfonyl]amide, and N,N-hexafluoropropane-1,3-disulfonylamide. Other representative anions include: 3-sideoxy-3H-1,2-benzothiazol-2-oxide, 1,1-dioxide, tris(trifluoromethyl)sulfonyl]methane, and tris(perfluorobutyl)sulfonyl]methane. Anions containing fluorocarbons are preferred. This includes strontium salts comprising combinations of the foregoing examples.

[0058] Iodotonium salts are salts containing sulfonate and amide anions, and iodotonium cations. Representative iodotonium cations include: diphenyliodotonium, bis(4-tert-butylphenyl)iodotonium, bis(4-tert-pentylphenyl)iodotonium, 4-tert-butoxyphenylphenyliodotonium, and 4-methoxyphenylphenyliodotonium, etc., which are aryl iodotonium cations. Representative sulfonates include: trifluoromethanesulfonate, nonafluorobutyrate, heptadecafluorooctylsulfonate, 2,2,2-trifluoroethanesulfonate, pentafluorobenzenesulfonate, 4-(trifluoromethyl)benzenesulfonate, 4-fluorobenzenesulfonate, toluenesulfonate, benzenesulfonate, 4-(4-toluenesulfonyloxy)benzenesulfonate, naphthalenesulfonate, camphorsulfonate, octylsulfonate, dodecylbenzenesulfonate, butyrate, and methanesulfonate. Representative amides include: bis(perfluoromethanesulfonyl)amide, bis(perfluoroethanesulfonyl)amide, bis(perfluorobutanesulfonyl)amide, bis(perfluorobutanesulfonoxy)amide, bis[perfluoro(2-ethoxyethane)sulfonyl]amide, and N,N-hexafluoropropane-1,3-disulfonylamide. Other representative anions include: 3-sideoxy-3H-1,2-benzothiazol-2-oxide, 1,1-dioxide, trifluoro[(trifluoromethyl)sulfonyl]methane, and trifluoro[(perfluorobutyl)sulfonyl]methane. Anions containing fluorocarbons are preferred. Iodonium salts comprising combinations according to the foregoing examples are also included.

[0059] Representative sulfonyldiazomethane compounds include: bis(ethylsulfonyl)diazomethane, bis(1-methylpropylsulfonyl)diazomethane, bis(2-methylpropylsulfonyl)diazomethane, bis(1,1-dimethylethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(perfluoroisopropylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, bis(4-methylphenylsulfonyl)diazomethane, bis(2,4-dimethyl)diazomethane, etc. Bis(2-naphthylsulfonyl)diazomethane, 4-methylphenylsulfonylbenzyldiazomethane, tributylcarbonyl-4-methylphenylsulfonyldiazomethane, 2-naphthylsulfonylbenzyldiazomethane, 4-methylphenylsulfonyl-2-naphthyldiazomethane, methylsulfonylbenzyldiazomethane, and tributoxycarbonyl-4-methylphenylsulfonyldiazomethane, etc., are all disulfonyldiazomethane compounds and sulfonylcarbonyldiazomethane compounds.

[0060] As for N-sulfonoxy nitriloimide photoacid generators, examples include combinations of nitriloimide skeletons and sulfonic acids. Representative nitriloimide skeletons include: nitriloimide succinate, nitriloimide naphthalenedicarboxylate, nitriloimide phthalate, nitriloimide cyclohexyldicarboxylate, nitriloimide 5-norcamphen-2,3-dicarboxylate, and nitriloimide 7-oxabicyclo[2.2.1]-5-heptene-2,3-dicarboxylate. Representative sulfonates include: trifluoromethanesulfonate, nonafluorobutyrate, heptadecafluorooctyl sulfonate, 2,2,2-trifluoroethanesulfonate, pentafluorobenzenesulfonate, 4-trifluoromethylbenzenesulfonate, 4-fluorobenzenesulfonate, toluenesulfonate, benzenesulfonate, naphthalenesulfonate, camphorsulfonate, octylsulfonate, dodecylbenzenesulfonate, butyrate, and methanesulfonate.

[0061] Examples of photoacid generating agents of benzoin sulfonates include: benzoin tosylate, benzoin mesylate, and benzoin butyl sulfonate.

[0062] As for gallophenol trisulfonate photoacid generating agents, examples include gallophenol, phloroglucinol, catechol, resorcinol, and hydroquinone, but all of the hydroxyl groups in these are replaced by trifluoromethanesulfonate, nonafluorobutyrate, heptadecafluorooctylsulfonate, 2,2,2-trifluoroethanesulfonate, pentafluorobenzenesulfonate, 4-trifluoromethylbenzenesulfonate, 4-fluorobenzenesulfonate, toluenesulfonate, benzenesulfonate, naphthalenesulfonate, camphorsulfonate, octylsulfonate, dodecylbenzenesulfonate, butyrate, or methanesulfonate.

[0063] Examples of photoacid generating agents of nitrobenzyl sulfonates include 2,4-dinitrobenzyl sulfonates, 2-nitrobenzyl sulfonates, and 2,6-dinitrobenzyl sulfonates. Representative examples include sulfonates containing trifluoromethanesulfonate, nonafluorobutyrate, heptadecafluorooctyl sulfonate, 2,2,2-trifluoroethanesulfonate, pentafluorobenzenesulfonate, 4-trifluoromethylbenzenesulfonate, 4-fluorobenzenesulfonate, toluenesulfonate, benzenesulfonate, naphthalenesulfonate, camphorsulfonate, octylsulfonate, dodecylbenzenesulfonate, butyrate, and methanesulfonate. Also useful are similar nitrobenzyl sulfonate compounds in which the nitro group on the benzyl side is replaced by a trifluoromethyl group.

[0064] Examples of succinic acid generating agents include: bis(phenylsulfonyl)methane, bis(4-methylphenylsulfonyl)methane, bis(2-naphthylsulfonyl)methane, 2,2-bis(phenylsulfonyl)propane, 2,2-bis(4-methylphenylsulfonyl)propane, 2,2-bis(2-naphthylsulfonyl)propane, 2-methyl-2-(p-toluenesulfonyl)phenylacetone, 2-cyclohexylcarbonyl-2-(p-toluenesulfonyl)propane, and 2,4-dimethyl-2-(p-toluenesulfonyl)pentan-3-one.

[0065] Examples of photoacid generators in the form of glyoxime derivatives include: bis-O-(p-toluenesulfonyl)-α-dimethylglyoxime, bis-O-(p-toluenesulfonyl)-α-diphenylglyoxime, bis-O-(p-toluenesulfonyl)-α-dicyclohexylglyoxime, bis-O-(p-toluenesulfonyl)-2,3-pentanedioneglyoxime, etc. -O-(p-toluenesulfonyl)-2-methyl-3,4-pentanedione glycoxime, bis-O-(n-butyryl)-α-dimethylglycoxime, bis-O-(n-butyryl)-α-diphenylglycoxime, bis-O-(n-butyryl)-α-dicyclohexylglycoxime, bis-O-(n-butyryl)-2,3-pentanedione glycoxime, bis-O-(n-butyryl)-2-methyl Bis-O-(methanesulfonyl)-α-dimethylglyoxime, Bis-O-(trifluoromethanesulfonyl)-α-dimethylglyoxime, Bis-O-(1,1,1-trifluoroethanesulfonyl)-α-dimethylglyoxime, Bis-O-(tributyryl)-α-dimethylglyoxime, Bis-O-(perfluorooctylsulfonyl)-α-dimethylglyoxime, Bis-O -(cyclohexylsulfonylurea)-α-dimethylglyoxime, bis-O-(benzenesulfonylurea)-α-dimethylglyoxime, bis-O-(p-fluorobenzenesulfonylurea)-α-dimethylglyoxime, bis-O-(p-tert-butylbenzenesulfonylurea)-α-dimethylglyoxime, bis-O-(xylenesulfonylurea)-α-dimethylglyoxime, and bis-O-(camphorsulfonylurea)-α-dimethylglyoxime.

[0066] Among these, preferred PAGs are strontium salts, iodonium salts, and N-sulfonoxyimines.

[0067] The most suitable anion for the produced acid varies depending on factors such as the ease of cleavage of the unstable acid group in the polymer, but generally, a non-volatile anion with low diffusivity is chosen. Suitable anions include: benzenesulfonic acid, toluenesulfonic acid, 4-(4-toluenesulfonoxy)benzenesulfonic acid, pentafluorobenzenesulfonic acid, 2,2,2-trifluoroethanesulfonic acid, nonafluorobutyric acid, heptadecanofluorooctanesulfonic acid, camphorsulfonic acid, disulfonic acid, sulfonylimid, and sulfonylmethane derivatives.

[0068] Examples of TAGs are metal-free strontium and iodonium salts, such as: strongly non-nucleophilic triarylstrontium, dialkylarylstrontium, and diarylalkylstrontium salts; strongly non-nucleophilic alkylaryliodonium and diaryliodonium salts; and strongly non-nucleophilic ammonium, alkylammonium, dialkylammonium, trialkylammonium, and tetraalkylammonium salts. Furthermore, covalent thermal acid generators are also considered useful additives, such as: 2-nitrobenzyl esters of alkyl or aryl sulfonic acids, and other esters of sulfonic acids that result in free sulfonic acid upon thermal decomposition. Examples include: diaryliodonium perfluoroalkyl sulfonate, diaryliodonium benzo(fluoroalkylsulfonyl) methylate, diaryliodonium bis(fluoroalkylsulfonyl) methylate, diaryliodonium bis(fluoroalkylsulfonyl) imine, and diaryliodonium quaternary ammonium perfluoroalkyl sulfonate. Examples of unstable esters include: 2-nitrobenzyl p-toluenesulfonic acid, 2,4-dinitrobenzyl p-toluenesulfonic acid, 2,6-dinitrobenzyl p-toluenesulfonic acid, 4-nitrobenzyl p-toluenesulfonic acid; benzenesulfonates such as 2-trifluoromethyl-6-nitrobenzyl-4-chlorobenzenesulfonate and 2-trifluoromethyl-6-nitrobenzyl-4-nitrobenzenesulfonate; phenolic sulfonates such as phenyl-4-methoxybenzenesulfonate; quaternary ammonium bis(fluoroalkylsulfonyl)methylates and quaternary alkylammonium bis(fluoroalkylsulfonyl)imines; alkylammonium salts of organic acids, such as triethylammonium salt of 10-camphorsulfonic acid. Various aromatic (anthracene, naphthalene, or benzene derivative) sulfonate ammonium salts, such as those disclosed in U.S. Patents 3,474,054, 4,200,729, 4,251,665, and 5,187,019, can also be used as TAGs.

[0069] The acid generating agent (D) can be used alone or in combination with two or more other agents. The content of the acid generating agent (D), based on the film-forming component (C), is preferably 0.5 to 20% by mass (more preferably 1.0 to 10% by mass, further preferably 2 to 6% by mass, and even more preferably 2 to 5% by mass).

[0070] Crosslinking Agent (E) The photolithography composition of the present invention may contain a crosslinking agent (E). In the present invention, a crosslinking agent refers to a compound itself that has crosslinking function. The crosslinking agent is not particularly limited as long as it crosslinks the intramolecular and / or intermolecular components (C).

[0071] Examples of crosslinking agents include: melamine compounds, guanamine compounds, glycol urea compounds or urea compounds, epoxy compounds, thioepoxide compounds, isocyanate compounds, azide compounds, and compounds containing alkenyl ether groups, all substituted with at least one group selected from hydroxymethyl, alkoxymethyl, and acetylated methyl groups. Compounds containing hydroxyl groups can also be used as crosslinking agents. Examples of epoxy compounds include: triisocyanate (2,3-epoxypropyl), trimethylolpropane triepoxide ether, trimethylolpropane triepoxide ether, and triethylolethane triepoxide ether. Regarding melamine compounds, examples include: hexamethylolmelamine, hexamethoxymethylmelamine, compounds of hexamethylolmelamine with 1-6 hydroxymethyl groups methylated by methoxy groups, and mixtures thereof; hexamethoxyethylmelamine, hexachloromethylmelamine, compounds of hexamethylolmelamine with 1-6 hydroxymethyl groups methylated by acetoxy groups, and mixtures thereof. Regarding guanidine compounds, examples include: tetramethylolguanidine, tetramethoxymethylguanidine, compounds of tetramethylolguanidine with 1-4 hydroxymethyl groups methylated by methoxy groups, and mixtures thereof; tetramethoxyethylguanidine, tetraacetoxyguanidine, compounds of tetramethylolguanidine with 1-4 hydroxymethyl groups methylated by acetoxy groups, and mixtures thereof. Examples of glycol urea compounds include: tetrahydroxymethyl glycol urea, tetramethoxyglycol urea, tetramethoxymethylglycol urea, compounds of tetrahydroxymethylglycol urea with 1 to 4 methoxymethylated hydroxymethyl groups, and mixtures thereof; and compounds of tetrahydroxymethylglycol urea with 1 to 4 acetoxymethylated hydroxymethyl groups, and mixtures thereof. Examples of urea compounds include: tetrahydroxymethyl urea, tetramethoxymethyl urea, compounds of tetrahydroxymethyl urea with 1 to 4 methoxymethylated hydroxymethyl groups, and mixtures thereof; and tetramethoxyethyl urea, etc. Examples of compounds containing alkenyl ether groups include: ethylene glycol divinyl ether, triethylene glycol divinyl ether, 1,2-propanediol divinyl ether, 1,4-butanediol divinyl ether, tetramethylene glycol divinyl ether, neopentyl glycol divinyl ether, trimethylolpropane trivinyl ether, hexanediol divinyl ether, 1,4-cyclohexanediol divinyl ether, neopentyl tetraethylene glycol trivinyl ether, neopentyl tetraethylene glycol tetravinyl ether, sorbitol tetraethyl ether, sorbitol pentavinyl ether, trimethylolpropane trivinyl ether, etc.

[0072] Examples of crosslinking agents containing hydroxyl groups are as follows.

[0073] The crosslinking temperature during film formation is preferably 50~230°C (more preferably 80~220°C; even more preferably 80~190°C).

[0074] The crosslinking agent (E) can be used alone or in combination of two or more. The content of the crosslinking agent (E), based on the film-forming component (C), is preferably 3 to 30% by mass (more preferably 5 to 20% by mass; even more preferably 5 to 12% by mass).

[0075] Surfactant (F) The photolithography composition of the present invention is preferably composed of surfactant (F). By containing surfactant (F), the coatability can be improved. Among the surfactants that can be used in the present invention, examples include: (I) anionic surfactants, (II) cationic surfactants, or (III) nonionic surfactants. More specifically, examples include: (I) alkyl sulfonates, alkylbenzene sulfonic acids, and alkylbenzene sulfonates; (II) laurylpyridinium chloride and lauryl methyl ammonium chloride; and (III) polyoxyethylene octyl ether, polyoxyethylene lauryl ether, polyoxyethylene kyne glycol ether, fluorinated surfactants (e.g., Fluorad (3M), Megafac (DIC), Sulflon (Asahi Glass), and organosiloxane surfactants (e.g., KF-53, KP341 (Shin-Etsu Chemical Industry)).

[0076] The surfactant (F) can be used alone or in combination of two or more. The content of the surfactant (F), based on the film-forming component (C), is preferably 0.05 to 0.5% by mass (more preferably 0.09 to 0.2% by mass).

[0077] Additive (G) The photolithography composition of the present invention may contain additive (G) other than components (A) to (F). Additive (G) is preferably composed of plasticizer, dye, contrast enhancer, acid, free radical generator, substrate adhesion enhancer, defoamer, or any mixture thereof. The acid in additive (G) does not contain an organic acid compound represented by formula (aa). The content of additive (G) (in the case of multiples, it is the sum) is preferably 0.1 to 20% by mass (more preferably 0.1 to 10% by mass; further preferably 1 to 5% by mass) based on the composition. The composition of the present invention may also be one embodiment of the present invention if it does not contain additive (G) (0.0% by mass). The content of additive (G) (in the case of multiples, it is the sum) is preferably 0 to 10% by mass (more preferably 0.05 to 5% by mass; further preferably 0.5 to 2.5% by mass) based on the film-forming component (C).

[0078] <Method for Manufacturing the Film> The method for manufacturing the film of the present invention comprises the following steps: (1) applying the photolithography composition of the present invention onto a substrate; (2) forming a film from the photolithography composition by depressurization and / or heating. Hereinafter, the numbers in parentheses indicate the order of the steps. For example, when steps (1), (2), and (3) are described, the order of the steps is as described above. In the present invention, the film is dried or hardened, for example, it contains a photoresist film. According to the present invention, the effect caused by standing waves can be reduced during film formation, therefore, BARC can be omitted from the substrate before applying the photolithography composition. In this way, the BARC removal step can be omitted.

[0079] Hereinafter, one aspect of the manufacturing method of the present invention will be described. The photolithography composition of the present invention is applied to the surface of a substrate (e.g., silicon / silicon dioxide coated substrate, silicon nitride substrate, silicon wafer substrate, glass substrate, and ITO substrate, etc.) using a suitable method. Here, in the present invention, "surface" includes the case where it is formed directly above the substrate and the case where it is formed with other layers in between. For example, a planarization film can be formed directly above the substrate, and the composition of the present invention can be applied directly above the planarization film. Applying the photolithography composition directly above the substrate is a suitable aspect of the present invention. The application method is not particularly limited, and examples include coating methods using a spinner or a coater. After coating, the film of the present invention is formed by depressurization and / or heating (soft baking). Heating can be omitted, and the substrate can be rotated at high speed to form a film by evaporating the solvent. When the photolithography composition of the present invention is a photoresist composition, heating is performed, for example, by a hot plate. The heating temperature is preferably 80~250℃ (more preferably 80~200℃; further preferably 90~180℃). The heating time is preferably 30~600 seconds (more preferably 30~300 seconds; further preferably 60~180 seconds). Heating is preferably performed in an atmospheric or nitrogen atmosphere. The thickness of the photoresist film varies depending on the exposure wavelength, but is preferably 100~50,000 nm. When exposure is performed using a KrF excimer laser, the thickness of the photoresist film is preferably 100~5,000 nm (more preferably 100~1,000 nm; further preferably 400~800 nm).

[0080] When the photolithography composition of the present invention is a photoresist composition, the method for manufacturing the photoresist pattern of the present invention includes the following steps: (3) forming a film using the photolithography composition according to the method described above; (4) exposing the film to radiation; and (5) developing the film to form a photoresist pattern.

[0081] The film formed using the photoresist composition is exposed through a prescribed mask. The wavelength of the light used for exposure is not particularly limited, but exposure with light having a wavelength of 13.5 to 365 nm is preferred. Specifically, i-line (wavelength 365 nm), KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), and extreme ultraviolet light (wavelength 13.5 nm) can be used, with KrF excimer laser being preferred. These wavelengths are permissible within a range of ±1%. After exposure, post-exposure baking can be performed as needed. The post-exposure baking temperature is preferably 80 to 150°C (more preferably 100 to 140°C), and the baking time is 0.3 to 5 minutes (preferably 0.5 to 2 minutes). The exposed film is developed using a developer. The developer used is preferably a 2.38% by mass aqueous solution of tetramethylammonium hydroxide (TMAH). The preferred temperature of the developer is 5–50°C (more preferably 25–40°C), and the preferred development time is 10–300 seconds (more preferably 30–60 seconds). Using such a developer allows the film to be easily dissolved and removed at room temperature. Furthermore, surfactants can be added to these developers. When using a negative photoresist composition, the unexposed portions of the photoresist layer are removed by development to form a photoresist pattern. This photoresist pattern can also be further refined by using materials such as shrink-wrap materials.

[0082] Figure 1 is a schematic diagram of the cross-sectional shape of a negative photoresist pattern under the influence of standing waves. A photoresist pattern 1 is formed on a substrate 2. If a large-amplitude waveform shape is formed in the cross-section, the top shape of the photoresist will change significantly due to a slight difference in film thickness, resulting in poor dimensional accuracy. Therefore, a smaller amplitude is preferable. Here, from the contact point between the substrate and the photoresist pattern upwards, the initial point where the thickness of the photoresist pattern is maximized is designated as the belly 3, and the point directly above it where the thickness of the photoresist pattern is minimized is designated as the node 4. Then, the distance between the belly and the node in the direction parallel to the substrate is called the belly-node distance 5. Preferably, this belly-node distance is small. Specifically, it is preferable that the belly-node distance / target pattern width (hereinafter sometimes referred to as the standing wave index) is less than 10%, more preferably less than 5%, and even more preferably less than 1%. Here, the target pattern width can be the width of the top of the photoresist assuming no standing wave influence. By reducing standing waves in the photoresist pattern, it is easier to stably form finer patterns, suppressing shapes that deviate from the intended design or pattern collapse caused by cuts. Figure 2 is a schematic diagram of the cross-sectional shape of a negative photoresist pattern without the influence of standing waves. In negative photoresist, the polymer remains insoluble due to the acid generated by exposure, making it difficult for light to reach the lower part of the pattern. Therefore, less acid is generated at the lower part, making it harder for the polymer to remain insoluble compared to the upper part. Consequently, the formed pattern tends to become an inverted cone shape. In Figure 2, there are no ventral and segmental nodes; in this case, the standing wave index is considered to be 0.

[0083] The method for manufacturing the metal pattern of the present invention comprises the following steps: forming a photoresist pattern using the method described above; (5a) forming a metal layer on the photoresist pattern; (6a) removing the remaining photoresist pattern and the metal layer thereon. Steps (5a) and (6a) are performed following steps (1) to (4). The order of the steps is as described above. The metal layer is formed by, for example, forming a metal such as gold or copper (or a metal oxide, etc.) by vapor deposition or sputtering. Then, the photoresist pattern and the metal layer formed on it are removed together by using a stripping liquid to form a metal pattern. The stripping liquid is not particularly limited as long as it is used as a stripping liquid for photoresist, and for example, N-methylpyrrolidone (NMP), acetone, or an alkaline solution is used. When the photoresist of the present invention is negative, it tends to become an inverted cone shape as described above. If it is an inverted cone, there will be a gap between the metal on the photoresist pattern and the metal formed on the part where the photoresist pattern is not formed, so it can be easily peeled off.

[0084] The method for manufacturing the patterned substrate of the present invention comprises the following steps: forming a photoresist pattern using the method described above; (5b) etching the photoresist pattern as a mask; (6b) processing the substrate. The etching can be either dry etching or wet etching, and the etching can be performed multiple times. Following steps (1) to (4), steps (5b) and (6b) are performed. The order of the steps is as described above. The photoresist pattern can be used as a mask to directly etch the substrate. Alternatively, the photoresist pattern can be used as a mask to form a pattern in the intermediate layer (BARC, planarization film) by etching, and the substrate can be etched using the intermediate layer pattern.

[0085] Furthermore, the method for manufacturing the patterned substrate of the present invention comprises the following steps: forming a photoresist pattern using the method described above; (5c) etching the photoresist pattern; (5d) etching the substrate. Steps (5c) and (5d) are performed following steps (1) to (4). The order of the steps is as described above. Here, the combination of steps (5c) and (5d) is repeated at least twice; and the substrate is formed by stacking multiple Si containing layers, at least one of which is conductive and at least one of which is electrically insulating. Preferably, conductive and electrically insulating Si containing layers are stacked alternately. Here, the thickness of the photoresist film formed from the photolithography composition is preferably 0.5 to 200 μm.

[0086] Subsequently, as needed, the substrate is further processed to form a device. This further processing can be performed using well-known methods. The manufacturing method of the device of the present invention includes any of the above methods, and preferably further includes a step of forming wiring on the processed substrate. Examples of devices include: semiconductor elements, liquid crystal display elements, organic EL display elements, plasma display elements, and solar cell elements. Preferably, a device is a semiconductor element.

[0087] [Examples] The present invention will be illustrated by way of examples as follows. However, the form of the present invention is not limited to these examples.

[0088] The following are the ingredients to be used in the future.

[0089] The (AA) organic acid compounds used are as follows: AA1: (±)-10-Camphorsulfonic Acid (TCI) AA2: p-Toluenesulfonic Acid

[0090] The basic compound (AB) used is as follows: AB1: Tris-[2-(2-methoxyethoxy)ethyl]amine (TCI)

[0091] The solvent (B) used is as follows: B1: PGMEA B2: PGMEA

[0092] The film-forming component (C) used is as follows: C1-1: CST 7030 random copolymer (p-hydroxystyrene (70), styrene (30)), Mw9,700 (Maruzen Petrochemical) C1-2: VP-3500, p-hydroxystyrene, Mw5,000 (Nippon Soda)

[0093] The acid generating agent (D) used is as follows: D1: TPS-C1 (Heraeste) D2: TPS-SA (Toyo Synthetic)

[0094] The crosslinking agent (E) used is as follows: E1: DML-POP (Honshu Chemical)

[0095] The surfactant (F) used is as follows: F1: MegafacR2011 (DIC)

[0096] <Preparation of Composition 1 in Example> Mix B1 (66.8g) and B2 (16.7g) to prepare a B1B2 mixed solvent. Add 0.067g of AA1 and 0.162g of AB1 to the mixture and stir for 5 minutes. Then add 7.457g of C1-1, 6.883g of C1-2, 0.580g of D1, 1.337g of E1, and 0.014g of F1 respectively. Mix the solution at room temperature and visually confirm the dissolution of the solid components. Composition 1 of Example is obtained.

[0097] <Preparation of Examples 2-5 and Comparative Example 1> Except for the changes in components as described below, Examples 2-5 and Comparative Example 1 were prepared in the same manner as Examples 1. [Table 1] Table 1: Amounts of each ingredient added per 100g of total weight Components of the Example Comparative composition 1 2 3 4 5 1 (AA)Ingredients (g) AA1 0.067 0.099 0.132 - 0.262 - AA2 - - - 0.082 - - (AB)Ingredients (g) AB1 0.162 0.208 0.253 0.208 - 0.070 (B) Ingredients (g) B1 66.8 66.8 66.8 66.8 66.8 66.8 B2 16.7 16.7 16.7 16.7 16.7 16.7 (C) Components (g) C1-1 7.457 7.421 7.385 7.428 7.327 7.529 C1-2 6.883 6.850 6.817 6.857 6.763 6.950 (D) Components (g) D1 0.580 0.578 0.575 0.578 0.570 0.586 D2 - - - - 0.251 - (E) Components (g) E1 1.337 1.330 1.324 1.332 1.314 1.350 (F)Ingredients (g) F1 0.014 0.014 0.014 0.014 0.014 0.014

[0098] <Example of Photoresist Pattern Formation> AZ KrF-17B (Merck Electronics Corporation, hereinafter referred to as ME) was spin-coated onto the surface of a silicon substrate (SUMCO Corp., 8-inch), and soft-baked at 180°C for 60 seconds to form a 45nm BARC. The aforementioned modulated composition was then spin-coated onto it, and soft-baked at 110°C for 60 seconds to form a photoresist film with a thickness of 780nm. This resulted in a KrF line (248nm) with a light reflectance of 7%. The resulting substrate was exposed using an exposure apparatus (Canon, FPA-3000EX5) with KrF lines. The exposure mask used included a mask with a line-to-space ratio of 1:1, a spacing of 300nm repeated multiple times, and the spacing decreasing sequentially as follows. 300nm, 280nm, 260nm, 240nm, 220nm, 200nm, 190nm, 180nm, 170nm, 160nm, 150nm, 140nm, 130nm, 120nm, 110nm, 100nm. This substrate was exposed to 100°C for 60 seconds followed by heat exposure (PEB). Then, the photoresist coating was developed using a 2.38% (w / w) TMAH aqueous solution for 60 seconds. While the coating developer was still on the substrate, pure water was flowed onto the substrate, and while rotating, the coating developer was replaced with pure water, and the substrate was dried by rotation at 2,000 rpm.

[0099] <Evaluation of Standing Wave Reduction> The reduction of standing wave was evaluated. A pattern with a spacing of 300 nm corresponding to the photoresist pattern formed in the above photoresist pattern formation example was observed. A slice was prepared from the substrate and observed using a SEM (SU8230, Hitachi High-Technologies). The length of the intersegmental distance as defined above was measured (Offline CD Measurement Software Version 6.00, Hitachi High-Technologies). The standing wave index was calculated by dividing the intersegmental distance by the desired pattern width. Evaluation was conducted using the following criteria: A: Standing wave index less than 1% B: Standing wave index greater than 1% and less than 5% C: Standing wave index greater than 5%

[0100] <Evaluation of Minimum Size> Evaluate the minimum resolving size of the photoresist pattern formed in the above photoresist pattern formation example. Start by checking whether there is pattern collapse in the large pattern, and gradually move the observation object to the smaller pattern. The pattern that is just before pattern collapse can be confirmed (the uncollapsed pattern) is taken as the minimum size.

[0101] <Evaluation of Exposure Margin> Except as follows, the same operation as in the above photoresist pattern formation example is performed. First, for a region where the online:pitch = 1:1 and the pitch is 300nm repeatedly, the exposure amount with a photoresist pattern size of 300nm is set as the optimal exposure amount (Eop). Next, the substrate is prepared in the same way, and the exposure amount is varied so that the size of the photoresist pattern corresponding to 300nm is 300nm±30nm. The range of exposure amount that will become 300nm±30nm is set as (Emax-Emin). ((Emax-Emin) / Eop) is set as the exposure margin. If this value is 10% or more, it is regarded as A; 5% or more and less than 10% is regarded as B; and less than 5% is regarded as C.

[0102] <Evaluation of Focal Depth> Except as follows, the same operation as in the above photoresist pattern formation example is performed. In an area where the online pitch is 1:1 and the pitch is 300nm multiple times, the focal position of the exposure machine with a photoresist pattern size of 300nm is set to the best focal value. The exposure amount at this time is the best exposure amount (Eop) used in the above "Evaluation of Exposure Margin". Next, the substrate is prepared in the same way, and the focal position of the exposure machine is changed in a way that corresponds to the photoresist pattern size of 300nm ± 30nm. When the focal position of the exposure machine is shifted from the best value, the width of the photoresist pattern with a focal depth of 300nm ± 30nm that is 1.2μm or more is regarded as A, the width of the photoresist pattern with a focal depth of 300nm ± 30nm is regarded as B, and the width of the photoresist pattern with a focal depth of 1.2μm or more is regarded as C.

[0103] <Evaluation of Peelability> The same operation as the above photoresist pattern formation example was performed to obtain a photoresist pattern. AZ 400T Stripper (ME) at 60°C was used as the stripping solution. The substrate was immersed in the stripping solution for 15 minutes while maintaining the temperature of the stripping solution at 60°C. It was then rotated to dry at 1,000 rpm. The photoresist pattern of 300 nm in a region with a line-to-pitch ratio of 1:1 and a pitch of 300 nm was observed at 50,000x magnification using a SEM (SU8230, Hitachi High-Technologies). Those that could be cleanly removed were classified as A, those with visible residue were classified as B, and those where the photoresist pattern remained on the substrate were classified as C. [Table 2] Table 2: Evaluation Results Components of the Example Comparative composition 1 2 3 4 5 1 Standing wave reduction B A A A A C Minimum size (nm) 220 200 220 220 200 260 Exposure margin A A A B A A Focus Depth A A A A B A Peelability A A A A A A

[0104] <Preparation of Composition 6 in Example> Mix B1 (66.8g) and B2 (16.7g) to prepare a B1B2 mixed solvent. Add 0.099g of AA1 and stir for 5 minutes. Then add 7.398g of C1-1, 6.829g of C1-2, 0.576g of D1, 0.256g of D2, 1.327g of E1, and 0.014g of F1 respectively. Mix the solution at room temperature and visually confirm the dissolution of the solid components. Composition 6 of Example is obtained.

[0105] <Evaluation of the peelability of Example Composition 6> Example Composition 6 was evaluated as described above in terms of peelability evaluation. Peelability was rated A. [Simplified Explanation of the Diagram]

[0013] Figure 1 is a schematic diagram of the cross-sectional shape of the negative photoresist pattern when it is affected by standing waves. Figure 2 is a schematic diagram of the cross-sectional shape of the negative photoresist pattern when it is not affected by standing waves.

Claims

1. A method using a composition comprising an organic acid compound (AA) for reducing standing waves in a lithography step; wherein the organic acid compound (AA) is represented by formula (aa): (where Ra is a C1-40 hydrocarbon group, at least one of the methylene groups contained therein being substituted with a carbonyl group, Xa is SO3H or COOH, na1 is 1 or 2, and na2 is 0, 1, or 2); wherein the composition further comprises a basic compound (AB) and a film-forming component (C); the basic compound (AB) is selected from the group comprising primary amines, secondary amines, and tertiary amines; the film-forming component (C) comprises a polymer (C1) having at least one repeating unit represented by the following formulas (c1), (c2), and (c3); (where Rc1 is H, C1-5 alkyl, C1-5 alkoxy, or COOH, Rc2 is a C1-5 alkyl group (here, -CH2- can be substituted with -O-), m1 is a number from 0 to 4, m2 is a number from 1 to 2, and m1+m2≦5); (here, Rc3 is H, C1-5 alkyl, C1-5 alkoxy, or COOH, Rc4 is a C1-5 alkyl or C1-5 alkoxy group (here, -CH2- in the alkyl or alkoxy group can be substituted with -O-), and m3 is a number from 0 to 5); (here, Rc5 is H, C1-5 alkyl, C1-5 alkoxy, or COOH, Rc6 is a C1-15 alkyl or C1-5 alkyl ether group, and Rc6 may have a cyclic structure).

2. The method of claim 1, wherein the constituent system is applied over a substrate to form a film.

3. The method of claim 1 or 2, wherein the composition further comprises a solvent (B).

4. A microfilm composition comprising an organic acid compound (AA), a solvent (B), and a film-forming component (C); wherein the organic acid compound (AA) is represented by formula (aa): (here, Ra is a C1-40 hydrocarbon group, at least one of the methylene groups contained therein may be substituted with a carbonyl group, Xa is SO3H or COOH, na1 is 1 or 2, na2 is 0, 1 or 2); wherein the composition further comprises a basic compound (AB); the basic compound (AB) is selected from the group comprising primary amines, secondary amines, and tertiary amines; the film-forming component (C) comprises a polymer (C1) having at least one repeating unit represented by the following formulas (c1), (c2), and (c3); (here, Rc1 is H, C1-5 alkyl, C1-5 alkoxy, or COOH, Rc2 is C1-5 alkyl (here, -CH2- may be substituted with -O-), m1 represents numbers from 0 to 4, m2 represents numbers from 1 to 2, and m1 + m2 ≦ 5); (Here, Rc3 represents H, C1-5 alkyl, C1-5 alkoxy, or COOH, Rc4 represents C1-5 alkyl or C1-5 alkoxy (here, the -CH2- contained in the alkyl or alkoxy group can be replaced by -O-), and m3 represents numbers from 0 to 5); (Here, Rc5 represents H, C1-5 alkyl, C1-5 alkoxy, or COOH, Rc6 represents C1-15 alkyl or C1-5 alkyl ether, and Rc6 may have a cyclic structure).

5. The photolithography composition of claim 4, wherein the organic acid compound (AA) is represented by formula (aa-1), (aa-2), (aa-3) or (aa-4): (here, AL is a C5-20 alicyclic ring, at least one of the methylene groups in the alicyclic ring may be substituted with a carbonyl group, Xa1 is SO3H or COOH, Ra1 is each independently a C1-5 alkyl group, n11 is 1 or 2, n12 is 0, 1 or 2, n13 is 0, 1 or 2, n14 is 0, 1 or 2); (here, Xa2 is SO3H or COOH, Ra2 is each independently a C1-15 alkyl group, n21 is 1 or 2, n22 is 0, 1 or 2, n23 is 0, 1 or 2); (here, Xa3 is SO3H or COOH, Ra3 is a C1-10 alkyl group, a C1-10 fluorinated alkyl group, or a C2-10 alkenyl group); (Here, Xa4 refers to SO3H or COOH, and Ra4 refers to C1-10 alkyl or C2-10 alkenyl groups).

6. The photolithography composition as claimed in claim 4 or 5, wherein the polymer (C1) has a mass-average molecular weight of 500 to 100,000.

7. The photolithography composition of claim 4 or 5 is further comprising additive (G).

8. The photolithography composition as requested in item 4 or 5, wherein the content of organic acid compound (AA) is 0.001 to 10 by mass based on solvent (B).

9. The photolithography composition as claimed in claim 4 or 5, wherein the photolithography composition is a negative photoresist composition.

10. A method of manufacturing a film comprising the steps of: (1) applying a photolithography composition as claimed in any one of claims 4 to 9 onto a substrate; and (2) forming a film from the photolithography composition by means of depressurization and / or heating.

11. A method for manufacturing a photoresist pattern, comprising the following steps: (3) forming a film from a photolithography composition using the method of claim 10; (4) exposing the film to radiation; and (5) developing the film to form a photoresist pattern; wherein the photolithography composition is a photoresist composition.

12. A method for manufacturing a metal pattern comprising the following steps: forming a photoresist pattern using the method of claim 11; (5a) forming a metal layer on the photoresist pattern; (6a) removing the remaining photoresist pattern and the metal layer thereon.

13. A method for manufacturing a patterned substrate, comprising the following steps: forming a photoresist pattern using the method of claim 11; (5b) etching the photoresist pattern as a mask; (6b) processing the substrate.

14. A method for manufacturing a patterned substrate, comprising the following steps: forming a photoresist pattern using the method of claim 11; (5c) etching the photoresist pattern; (5d) etching the substrate; wherein the combination of steps (5c) and (5d) is repeated at least twice; and the substrate is formed by stacking a plurality of Si containing layers, wherein at least one Si containing layer is conductive and at least one Si containing layer is electrically insulating.

15. A method for manufacturing a device, comprising the method of any one of claims 10 to 14, and further comprising the step of forming wiring on a substrate being processed; wherein, the device is a semiconductor element.

Images