Method for using a composition containing a carboxylic acid ester, a lithographic composition containing a carboxylic acid ester, and a method for producing a resist pattern

Abstract

A method for reducing standing waves in a lithography process is provided. The present invention relates to a method for reducing standing waves in a lithography process, and to a composition comprising a carboxylic acid ester (A) having a specific structure.

Description

[Technical Field]

[0001] The present invention relates to a method of using a composition containing a carboxylic acid ester for reducing standing waves in a lithography process, and also to a lithography composition containing a carboxylic acid ester, and a method of producing a resist pattern and a device using the same. [Background technology]

[0002] In recent years, there has been an increasing need for higher integration of LSIs, resulting in a demand for finer patterns. To meet these needs, lithography processes using short-wavelength light such as KrF excimer lasers (248 nm), ArF excimer lasers (193 nm), extreme ultraviolet light (EUV; 13 nm), X-rays, and electron beams are becoming more practical. To meet this demand for finer resist patterns, photosensitive resin compositions used as resists in fine processing are also required to have high resolution. Although finer patterns can be formed by exposure to short-wavelength light, high dimensional accuracy is also required. For example, there is a study to suppress fine irregularities on the resist surface by adding a specific acid generator to the resist composition itself (Patent Document 1).

[0003] In the lithography process, a resist pattern is formed by exposing and developing the resist. During exposure, multiple interference occurs between the light incident on the resist and the light reflected from the substrate or air interface, resulting in the generation of standing waves. The generation of standing waves reduces the dimensional accuracy of the pattern. To reduce standing waves, there have been attempts to form anti-reflective coatings on top and / or under the resist. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 11-125907 [Brief explanation of the drawings]

[0005] [Figure 1] FIG. 1 is a schematic diagram showing the cross-sectional shape of a negative resist pattern when it is affected by standing waves. [Figure 2] FIG. 2 is a schematic diagram of the cross-sectional shape of a negative resist pattern when not affected by standing waves. Summary of the Invention [Problem to be solved by the invention]

[0006] The inventors focused on controlling the movement of acids in chemical processes used for microfabrication. For example, in a lithography process, even if an anti-reflective coating is formed on a substrate and a resist film is then formed on top of that and exposed, standing waves may remain, and further techniques are needed. Furthermore, the bottom anti-reflective coating must be removed after resist pattern formation, which may make it unusable in the process or require other measures. The inventors have recognized that there are still one or more problems that require improvement, such as: reducing standing waves in lithography processes; reducing standing waves in resist patterns; suppressing non-uniformity in resist pattern width; suppressing resist pattern collapse; obtaining a resist pattern with a good shape; obtaining a resist film with good sensitivity; obtaining a resist film with good resolution; obtaining a finer pattern; controlling the movement of acid in chemical processes; suppressing the migration rate of acid in chemical processes; and improving the yield of lithography processes. [Means for solving the problem]

[0007] The present invention provides a method of using a composition comprising a carboxylic acid ester (A) to reduce standing waves in a lithographic process. wherein the carboxylic acid ester (A) is represented by formula (a): [ka] R 1 is C 1-10 Alkyl, or -OR 1 ' and R 2 HA-OR 2 ' and R 1 ' and R 2 ' are each independently C 1-20 is a hydrocarbon, R 3 and R 4 are each independently H or C 1-10 is alkyl, R 1 and R 3 Or R 4 , or R 2 and R 3 Or R 4 may be bonded to form a saturated or unsaturated hydrocarbon ring, n1 is 1 or 2: However, when n1=1, R 1 or R 1 ', and R 2 At least one of the ' is C 3-20 It is a hydrocarbon.

[0008] The lithographic composition according to the present invention comprises: It comprises a carboxylic acid ester (A) and a solvent (B). wherein the carboxylic acid ester (A) is represented by formula (a): [ka] R 1 is C 1-10 Alkyl, or -OR 1 ' and R 2 HA-OR 2 ' and R 1 ' and R 2 ' are each independently C 1-20 is a hydrocarbon, R 3 and R 4 are each independently H or C 1-10is alkyl, R 1 and R 3 Or R 4 , or R 2 and R 3 Or R 4 may be bonded to form a saturated or unsaturated hydrocarbon ring, n1 is 1 or 2: However, when n1=1, R 1 or R 1 ', and R 2 At least one of the ' is C 3-20 It is a hydrocarbon.

[0009] The method for producing a membrane according to the present invention comprises the following steps: (1) applying the above-described lithographic composition above a substrate; (2) Forming a film from the lithographic composition by reducing pressure and / or heating. [Effects of the Invention]

[0010] According to the present invention, one or more of the following effects can be expected. Reduce standing waves in lithography processes; reduce standing waves in resist patterns; reduce non-uniformity in resist pattern width; suppress pattern collapse of resist patterns; obtain resist patterns with good shapes; obtain resist films with good sensitivity; obtain resist films with good resolution; obtain finer patterns; control the movement of acid in chemical processes; suppress the rate of acid migration in chemical processes; improve yield in lithography processes. DETAILED DESCRIPTION OF THE INVENTION

[0011] The embodiments of the present invention will be described in detail below.

[0012] definition In this specification, unless otherwise specified, the definitions and examples set forth in this paragraph shall be followed. The singular includes the plural, and "one" and "the" mean "at least one." An element of a concept can be expressed by a plurality of species, and when an amount thereof (e.g., mass % or mole %) is stated, the amount refers to the sum of the plurality of species. "And / or" includes all combinations of elements as well as any single element. When a numerical range is indicated using "~" or "-", it includes both endpoints and the units are the same. For example, 5 to 25 mol % means 5 mol % or more and 25 mol % or less. "C x-y "," "C x ~C y " and "C x " refers to the number of carbons in a molecule or substituent. For example, C 1-6 Alkyl refers to alkyl chains having from 1 to 6 carbons (methyl, ethyl, propyl, butyl, pentyl, hexyl, etc.). When a polymer has multiple types of repeating units, these repeating units are copolymerized. This copolymerization may be alternating copolymerization, random copolymerization, block copolymerization, graft copolymerization, or a mixture of these. When polymers or resins are represented by structural formulas, the n or m in parentheses indicates the repeating number. The temperature unit is Celsius. For example, 20 degrees means 20 degrees Celsius. The additive refers to the compound itself that has that function (for example, in the case of a base generator, it refers to the compound itself that generates a base). In some embodiments, the compound is dissolved or dispersed in a solvent and added to the composition. In one embodiment of the present invention, such a solvent is preferably contained in the composition of the present invention as solvent (B) or another component.

[0013] <Method of using a composition containing a carboxylic acid ester> The present invention relates to a method of using a composition containing a carboxylic acid ester (A) (hereinafter, sometimes referred to as the "composition used in the present invention") to reduce standing waves in a lithography process. Preferably, the composition used in the present invention is applied above a substrate and used to form a film. Since the present invention can reduce standing waves, a lower anti-reflection film need not be formed below the composition used in the present invention. Therefore, applying the composition used in the present invention without forming a lower anti-reflection film is also a preferred embodiment of the present invention. Furthermore, since a further standing wave reduction effect can be achieved when a lower anti-reflection film is formed, the present invention can be used even when a lower anti-reflection film is formed. The composition used in the method of use of the present invention is preferably a lithography composition as described below.

[0014] Carboxylic acid ester (A) The carboxylic acid ester (A) (hereinafter, sometimes referred to as component (A), the same applies to (B) and subsequent components described below) is represented by formula (a). [ka] where: R 1 is C 1-10 Alkyl, or -OR 1 '; preferably C 1-10 alkyl; more preferably C 1-5 The C is alkyl. 1-5 Alkyl is preferably methyl, ethyl, isopropyl, n-butyl, or t-butyl; more preferably methyl or t-butyl; and even more preferably methyl. When n1=2, R 1 HA-OR 1 It is preferable that R 2 HA-OR 2 ' is. R 1 ' and R 2 ' are each independently C 1-20 It is a hydrocarbon. R 1 ' is preferably C 1-5 It is alkyl; more preferably methyl or ethyl; and even more preferably methyl. R 2 ' is preferably C 3-20hydrocarbons; more preferably C 3-20 Alkyl, C 6-20 Aryl or C 6-20 It is preferably arylalkyl; more preferably isopropyl, sec-butyl, t-butyl, n-butyl, n-heptyl or benzyl; even more preferably isopropyl, t-butyl or benzyl. Without being bound by theory, -OR 2 In the formula (I), the carbon adjacent to oxygen is preferably a tertiary carbon atom. This is because a tertiary carbon atom is easily eliminated, which is thought to contribute to a decrease in the rate of acid migration. In another embodiment, when n1=2, R 2 ' is preferably C 1-5 It is alkyl; more preferably methyl or ethyl; and even more preferably methyl. R 3 and R 4 are each independently H or C 1-10 alkyl; preferably H or C 1-5 alkyl; more preferably H, methyl, or t-butyl; even more preferably both are H. When n1=2, R 3 appears twice in one carboxylic acid ester (A), but these two R 3 R may be the same or different from each other; preferably they are the same. 4 The same is true. R 1 and R 3 Or R 4 , or R 2 and R 3 Or R 4 may be bonded to form a saturated or unsaturated hydrocarbon ring. When n1=2, n1 is added (CR 3 R 4 -C(=O)-) is repeated twice, and R 3 and R 4 appears twice, in which case it is preferred that the bond be connected to the nearest group. For example, 3 Among them, R 1 The R closest to 3 R 1It is preferable to combine with R 1 and R 3 or R 4 In a preferred embodiment of the present invention, R 2 and R 3 or R 4 In a preferred embodiment of the present invention, the n1 is 1 or 2; preferably n1 = 1. In another embodiment of the present invention, n1 = 2 is also preferred. When n1=1, R 1 or R 1 ', and R 2 At least one of the ' is C 3-20 hydrocarbon; preferably R 2 ' is C 3-20 It is a hydrocarbon.

[0015] Preferably, the carboxylic acid ester (A) is represented by the formula (a1). [ka] where: R 11 is C 1-5 It is alkyl; preferably methyl. R 12 is C 3-20 hydrocarbons; preferably C 3-7 R is alkyl; more preferably isopropyl, sec-butyl, t-butyl, n-butyl or n-heptyl; even more preferably isopropyl or t-butyl; and even more preferably t-butyl. 12 In the formula (I), the carbon adjacent to the oxygen atom is preferably a tertiary carbon atom. R 13 and R 14 are each independently H or C 1-5 alkyl; preferably both are H.

[0016] Although not intended to limit the present invention, specific examples of the carboxylic acid ester (A) include the following: the case where n1=1 in formula (a) or the carboxylic acid ester (A) represented by formula (a1). [ka]

[0017] In one embodiment of the present invention, the carboxylic acid ester (A) is represented by formula (a2). [ka] where: R 21 and R 22 is C 1-5 alkyl, preferably methyl or ethyl; R 23 , R 24 , R 25 , and R 26 are each independently H or C 1-5 Alkyl, preferably H, more preferably all H.

[0018] Although not intended to limit the present invention, specific examples of the carboxylic acid ester (A) include the following: the case where n1=2 in formula (a) or the carboxylic acid ester (A) represented by formula (a2). [ka]

[0019] The following compound is an example of the carboxylic acid ester (A) of the present invention. The following compound can be represented by formula (a). For example, when n1=2, R 1 = C3 alkyl (n-propyl), R 2 ' = t-butyl, two R 3 are both H and R 1 Close to R 4 is methyl and R 2 Close to R 4 =H, R 1 Close to R 4 and R 1 can be read as being bonded to form a saturated hydrocarbon ring (cyclohexyl). [ka]

[0020] Without being bound by theory, it is believed that the inclusion of the carboxylic acid ester (A) in the composition used in the present invention can reduce standing waves by contributing to suppressing the migration rate of substances (e.g., acid generated from the acid generator (D)) generated in the composition during the lithography process.

[0021] Solvent (B) The composition used in the present invention preferably contains a solvent (B). Preferred solvents (B) are the same as those described below in relation to the lithographic composition. The content of the carboxylic acid ester (A) based on the solvent (B) is preferably 1.0 to 200 mass%, more preferably 2 to 150 mass%, even more preferably 2.5 to 120 mass%, and still more preferably 2.5 to 50 mass%.

[0022] Membrane-forming component (C) The composition used in the present invention preferably comprises a film-forming component (C). Preferred film-forming components (C) are the same as those described below in the lithographic composition. The content of the carboxylic acid ester (A) based on the film-forming component (C) is preferably 10 to 3,000 mass%, more preferably 20 to 2,000 mass%, even more preferably 30 to 1,000 mass%, and still more preferably 60 to 900 mass%.

[0023] <Lithography composition> The lithographic composition according to the present invention comprises a carboxylic acid ester (A) represented by formula (a) and a solvent (B). In the present invention, the term "lithography composition" refers to a composition used in a photolithography process, such as a composition used for cleaning or film formation, and specifically includes a resist composition, a planarizing film-forming composition, a bottom anti-reflective coating-forming composition, a top anti-reflective coating-forming composition, a rinse solution, a resist remover, and the like. After undergoing the process, the lithography composition may or may not be removed; preferably, it is removed. The object formed from the lithography composition may or may not remain in the final device; preferably, it does not remain. The lithographic composition according to the present invention is a lithographic film-forming composition, more preferably a resist composition. Either a positive or negative resist composition can be used, but a negative resist composition is preferred. Furthermore, the lithography composition according to the present invention is preferably a chemically amplified resist composition, and more preferably a chemically amplified negative resist composition. In this case, in addition to the component (A) and the component (B), it preferably contains a polymer, an acid generator, and a crosslinking agent, which will be described later.

[0024] Carboxylic acid ester (A) The carboxylic acid ester (A) used in the lithographic composition of the present invention is as described above, and the preferred forms are also the same as above. The content of the carboxylic acid ester (A) is preferably 1.0 to 200 mass% based on the solvent (B); more preferably 2 to 150 mass%; even more preferably 2.5 to 120 mass%; and still more preferably 2.5 to 50 mass%.

[0025] Solvent (B) The solvent (B) used in the present invention is not particularly limited as long as it can dissolve each of the components to be blended. Here, the solvent (B) does not include those corresponding to the above-mentioned carboxylic acid ester (A). The solvent (B) preferably comprises an organic solvent (B1). In one preferred embodiment, the solvent (B) consists solely of the solvent (B1). The organic solvent (B1) preferably comprises a hydrocarbon solvent, an ether solvent, an ester solvent, an alcohol solvent, a ketone solvent, or a mixture thereof. Specific examples of the solvent include water, n-pentane, i-pentane, n-hexane, i-hexane, n-heptane, i-heptane, 2,2,4-trimethylpentane, n-octane, i-octane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbenzene, i-propylbenzene, diethylbenzene, i-butylbenzene, triethylbenzene, di-i-propylbenzene, n-amylnaphthalene, trimethylbenzene, methanol, ethanol, n-Propanol, i-Propanol, n-Butanol, i-Butanol, sec-Butanol, t-Butanol, n-Pentanol, i-Pentanol, 2-Methylbutanol, sec-Pentanol, t-Pentanol, 3-Methoxybutanol, n-Hexanol, 2-Methylpentanol, sec-Hexanol, 2-Ethylbutanol, sec-Heptanol, Heptanol-3, n-Octanol, 2-Ethylhexanol, sec-Octanol, n-Nonyl alcohol, 2,6-Dimethylheptanol-4, n-Decanol, sec-U Benzyl alcohol, trimethylnonyl alcohol, sec-tetradecyl alcohol, sec-heptadecyl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, phenylmethylcarbinol, diacetone alcohol, cresol, ethylene glycol, propylene glycol, 1,3-butylene glycol, pentanediol-2,4, 2-methylpentanediol-2,4, hexanediol-2,5, heptanediol-2,4, 2-ethylhexanediol All-1,3, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, glycerin, acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-i-butyl ketone, methyl-n-pentyl ketone, ethyl-n-butyl ketone, methyl-n-hexyl ketone, di-i-butyl ketone, trimethylnonanone, cyclohexanone, cyclopentanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone, diacetone alcohol,Acetophenone, fenchone, ethyl ether, i-propyl ether, n-butyl ether (di-n-butyl ether, DBE), n-hexyl ether, 2-ethylhexyl ether, ethylene oxide, 1,2-propylene oxide, dioxolane, 4-methyldioxolane, dioxane, dimethyldioxane, 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-n-butyl ether, diethylene glycol di-n-butyl ether, diethylene glycol mono-n-hexyl ether, ethoxytriglycol, tetraethylene glycol di-n-butyl ether, propylene glycol monomethyl ether (P GME), 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, methyl acetate, ethyl acetate, γ-butyrolactone, γ-valerolactone, n-propyl acetate, i-propyl acetate, n-butyl acetate (normal butyl acetate, nBA), i-butyl acetate, sec-butyl acetate, n-pentyl acetate, sec-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, glycol diacetate, methoxytriglycol acetate, ethyl propionate, n-butyl propionate, i-amyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate (EL), n-butyl lactate, n-amyl lactate, diethyl malonate Examples of suitable solvents include dimethyl phthalate, diethyl phthalate, propylene glycol 1-monomethyl ether 2-acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, N-methylformamide, N,N-dimethylformamide, N,N-diethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpropionamide, N-methylpyrrolidone, dimethyl sulfide, diethyl sulfide, thiophene, tetrahydrothiophene, dimethyl sulfoxide, sulfolane, and 1,3-propanesultone. These solvents can be used alone or in combination. The solvent (B) is preferably PGME, PGMEA, EL, nBA, DBE, or a mixture of any of these, more preferably PGME, EL, nBA, DBE, or a mixture of any of these. PGME, PGMEA, or a mixture of any of these is also suitable as the solvent (B) in another embodiment of the present invention.

[0026] In one embodiment, the solvent (B) does not substantially contain water in relation to other layers or films. For example, the amount of water in the entire 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. In another preferred embodiment, the solvent (B) does not contain water (0% by mass).

[0027] The content of the solvent (B) is preferably 10 to 98 mass % based on the lithographic composition; more preferably 20 to 98 mass %; even more preferably 30 to 97 mass %; and still more preferably 40 to 95 mass %.

[0028] The boiling points of the carboxylic acid ester (A) and the solvent (B) are respectively bp A , bp B and the saturated vapor pressure at 25°C and 1 atmosphere is Vpc A , vpc B Then, bp A >bp B , and VPC A <vpc B It is preferable that the following is satisfied.

[0029] Membrane-forming component (C) The lithographic composition according to the present invention preferably comprises a film-forming component (C). In the present invention, the film-forming component (C) refers to a component that constitutes at least a portion of the film to be formed. The film to be formed does not necessarily have to be composed solely of the film-forming component (C). For example, the film may be formed by combining the film-forming component (C) with a crosslinking agent (E) described below. In a preferred embodiment, the film-forming component (C) constitutes the majority of the film to be formed, for example, constituting 60% or more by volume of the film (more preferably 70% or more; even more preferably 80% or more; and even more preferably 90% or more).

[0030] The film-forming component (C) preferably comprises a polymer (C1). In a preferred embodiment of the present invention, the film-forming component (C) is a polymer (C1). Examples of the polymer (C1) include novolak derivatives, phenol derivatives, polystyrene derivatives, polyacrylic acid derivatives, polymaleic acid derivatives, polycarbonate derivatives, polyvinyl alcohol derivatives, polymethacrylic acid derivatives, and copolymers of combinations thereof.

[0031] When the lithographic composition of the present invention is a resist composition, the polymer (C1) is preferably a polymer generally used in resist compositions whose solubility in an alkaline developer changes upon exposure or the like. When the lithographic composition according to the present invention is a chemically amplified positive resist composition, the polymer (C1) is preferably one whose solubility in a developer increases upon reaction with an acid. Such a polymer has, for example, an acid group protected by a protecting group, and when an acid is added from the outside, the protecting group is eliminated, thereby increasing the solubility in a developer. When the lithographic composition according to the present invention is a chemically amplified negative resist composition, the polymer (C1) is preferably one in which the solubility in a developer is reduced by crosslinking between polymers using, for example, a crosslinking agent, with the acid generated by exposure as a catalyst. Such a polymer can be arbitrarily selected from those commonly used in lithography. Among such polymers, those having at least one repeating unit represented by the following formulas (c1), (c2), and (c3) are preferred. When the lithography composition according to the present invention is a chemically amplified negative resist composition, it is preferred that the polymer (C1) has at least a repeating unit represented by formula (c1).

[0032] The repeating unit represented by formula (c1) is as follows: [ka] where: R c1 is H, C 1-5 Alkyl, C 1-5 alkoxy, or —COOH, preferably H or methyl, more preferably H; R c2 is C 1-5 alkyl (wherein -CH2- may be replaced by -O-), preferably methyl, ethyl or methoxy, more preferably methyl; m1 is a number from 0 to 4, preferably 0, and m2 is a number of 1 to 2, preferably 1, and m1+m2≦5.

[0033] A specific example of formula (c1) is as follows: [ka]

[0034] The constitutional unit represented by formula (c2) is as follows: [ka] where: R c3 is H, C 1-5 Alkyl, C 1-5 Alkoxy or -COOH, preferably hydrogen or methyl, more preferably hydrogen. R c4 is C 1-5 Alkyl or C 1-5 Alkoxy (wherein -CH2- contained in alkyl or alkoxy may be replaced by -O-), more preferably C 1-5 It is preferably alkoxy (wherein —CH— contained in alkoxy may be replaced by —O—), and in this case, m3 is preferably 1. In this embodiment, R c4 Examples include methoxy, t-butyloxy, and —O—CH(CH3)—O—CH2CH3. m3 is a number of 0 to 5, preferably 0, 1, 2, 3, 4 or 5, and more preferably 0 or 1. In one preferred embodiment, m3 is 0.

[0035] A specific example of formula (c2) is as follows: [ka]

[0036] The constitutional unit represented by formula (c3) is as follows: [ka] where: R c5 is H, C 1-5 Alkyl, C 1-5 Alkoxy, or —COOH, more preferably H, methyl, ethyl, methoxy, or —COOH, even more preferably hydrogen or methyl, and even more preferably H. R c6 is C 1-15 Alkyl or C 1-5 alkyl ether, R c6 may have a ring structure, and is preferably methyl, isopropyl, t-butyl, cyclopentyl, methylcyclopentyl, ethylcyclopentyl, methylcyclohexyl, ethylcyclohexyl, methyladamantyl, or ethyladamantyl, more preferably t-butyl, ethylcyclopentyl, ethylcyclohexyl, or ethyladamantyl, and even more preferably t-butyl.

[0037] A specific example of formula (c3) is as follows: [ka]

[0038] These structural units are appropriately blended depending on the purpose, and there are no particular limitations on the blending ratio, but they are preferably blended so as to provide an appropriate solubility in an alkaline developer. These polymers may be used in combination of two or more kinds.

[0039] The weight 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; still more preferably 3,000 to 20,000; and even more preferably 4,000 to 20,000. In the present invention, Mw can be measured by gel permeation chromatography (GPC). In one preferred example, the GPC column is set at 40°C, the elution solvent is tetrahydrofuran at 0.6 mL / min, and monodisperse polystyrene is used as the standard.

[0040] Based on the film-forming component (C), the content of the carboxylic acid ester (A) is preferably 10 to 3,000 mass%, more preferably 20 to 2,000 mass%, even more preferably 30 to 1,000 mass%, and still more preferably 60 to 900 mass%. The content of the film-forming component (C) is preferably 2 to 40 mass % based on the lithography composition; more preferably 2 to 30 mass %; even more preferably 3 to 25 mass %; and still more preferably 3 to 20 mass %.

[0041] Based on the number of all repeating units in polymer (C1), the ratio of the repeating units represented by formulas (c1), (c2), and (c3) is defined as n c1 , n c2 and n c3 In this regard, the following is one of the preferred aspects of the present invention. n c1 =0 to 100%; more preferably 30 to 100%; even more preferably 50 to 100%; even more preferably 60 to 100%. n c2 =0 to 100%; more preferably 0 to 70%; even more preferably 0 to 50%; even more preferably 0 to 40%. n c3 = 0 to 50%; more preferably 0 to 40%; even more preferably 0 to 30%; and even more preferably 0 to 20%. c3 =0) is also another preferred embodiment of the present invention.

[0042] Acid generator (D) The lithographic composition according to the present invention may contain an acid generator (D). In the present invention, the acid generator refers to a compound having an acid-generating function. Examples of acid generators include photoacid generators (PAGs) that generate acid upon exposure and thermal acid generators (TAGs) that generate acid upon heating. When the lithographic composition according to the present invention is a chemically amplified resist composition, it preferably contains a photoacid generator.

[0043] Examples of photoacid generators include sulfonium salts, iodonium salts, sulfonyldiazomethane, and N-sulfonyloxyimide acid generators. Representative photoacid generators are shown below, and these can be used alone or in combination of two or more.

[0044] Sulfonium salts are salts of anions containing carboxylates, sulfonates, or imides with sulfonium cations. Representative sulfonium cations include triphenylsulfonium, (4-methylphenyl)diphenylsulfonium, (4-methoxyphenyl)diphenylsulfonium, tris(4-methoxyphenyl)sulfonium, (4-tert-butylphenyl)diphenylsulfonium, (4-tert-butoxyphenyl)diphenylsulfonium, bis(4-tert-butoxyphenyl)phenylsulfonium, tris(4-tert-butylphenyl)sulfonium, tris(4-tert-butoxyphenyl)sulfonium, tris(4-methylphenyl)sulfonium, (4-methoxy-3,5-dimethylphenyl)dimethylsulfonium, and (3-tert-butoxyphenyl)diphenylsulfonium. nium, bis(3-tert-butoxyphenyl)phenylsulfonium, tris(3-tert-butoxyphenyl)sulfonium, (3,4-di-tert-butoxyphenyl)diphenylsulfonium, bis(3,4-di-tert-butoxyphenyl)phenylsulfonium, tris(3,4-di-tert-butoxyphenyl)sulfonium, (4-phenoxyphenyl)diphenylsulfonium, (4-cyclohexylphenyl)diphenylsulfonium, bis(p-phenylene)bis(diphenylsulfonium), diphenyl(4-thiophenoxyphenyl)sulfonium, diphenyl(4-thiophenylphenyl)sulfonium, diphenyl(8-thiophenylbiphenyl)sulfonium, (4 Examples of sulfonium include (4-tert-butoxycarbonylmethyloxyphenyl)diphenylsulfonium, tris(4-tert-butoxycarbonylmethyloxyphenyl)sulfonium, (4-tert-butoxyphenyl)bis(4-dimethylaminophenyl)sulfonium, tris(4-dimethylaminophenyl)sulfonium, 2-naphthyldiphenylsulfonium, dimethyl(2-naphthyl)sulfonium, 4-hydroxyphenyldimethylsulfonium, 4-methoxyphenyldimethylsulfonium, trimethylsulfonium, 2-oxocyclohexylcyclohexylmethylsulfonium, trinaphthylsulfonium, and tribenzylsulfonium.Representative sulfonates include trifluoromethanesulfonate, nonafluorobutanesulfonate, heptadecafluorooctanesulfonate, 2,2,2-trifluoroethanesulfonate, pentafluorobenzenesulfonate, 4-(trifluoromethyl)benzenesulfonate, 4-fluorobenzenesulfonate, toluenesulfonate, benzenesulfonate, 4-(4-toluenesulfonyloxy)benzenesulfonate, naphthalenesulfonate, camphorsulfonate, octanesulfonate, dodecylbenzenesulfonate, butanesulfonate, and methanesulfonate. Representative imides include bis(perfluoromethanesulfonyl)imide, bis(perfluoroethanesulfonyl)imide, bis(perfluorobutanesulfonyl)imide, bis(perfluorobutanesulfonyloxy)imide, bis[perfluoro(2-ethoxyethane)sulfonyl]imide, and N,N-hexafluoropropane-1,3-disulfonylimide. Representative other anions include 3-oxo-3H-1,2-benzothiazol-2-ide, 1,1-dioxide, tris[(trifluoromethyl)sulfonyl]methanide, and tris[(perfluorobutyl)sulfonyl]methanide. Fluorocarbon-containing anions are preferred. Included are sulfonium salts based on combinations of the foregoing examples.

[0045] Iodonium salts are salts of anions, including sulfonates and imides, with iodonium cations. Representative iodonium cations include aryl iodonium cations such as diphenyliodonium, bis(4-tert-butylphenyl)iodonium, bis(4-tert-pentylphenyl)iodonium, 4-tert-butoxyphenylphenyliodonium, and 4-methoxyphenylphenyliodonium. Representative sulfonates include trifluoromethanesulfonate, nonafluorobutanesulfonate, heptadecafluorooctanesulfonate, 2,2,2-trifluoroethanesulfonate, pentafluorobenzenesulfonate, 4-(trifluoromethyl)benzenesulfonate, 4-fluorobenzenesulfonate, toluenesulfonate, benzenesulfonate, 4-(4-toluenesulfonyloxy)benzenesulfonate, naphthalenesulfonate, camphorsulfonate, octanesulfonate, dodecylbenzenesulfonate, butanesulfonate, and methanesulfonate. Representative imides include bis(perfluoromethanesulfonyl)imide, bis(perfluoroethanesulfonyl)imide, bis(perfluorobutanesulfonyl)imide, bis(perfluorobutanesulfonyloxy)imide, bis[perfluoro(2-ethoxyethane)sulfonyl]imide, and N,N-hexafluoropropane-1,3-disulfonylimide. Representative anions include 3-oxo-3H-1,2-benzothiazol-2-ide, 1,1-dioxide, tris[(trifluoromethyl)sulfonyl]methanide, and tris[(perfluorobutyl)sulfonyl]methanide. Fluorocarbon-containing anions are preferred. Iodonium salts based on combinations of the foregoing examples are also included.

[0046] 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, and bis(2,4-dimethylphenylsulfonyl)diazomethane. bissulfonyldiazomethane compounds and sulfonylcarbonyldiazomethane compounds such as bis(2-naphthylsulfonyl)diazomethane, 4-methylphenylsulfonylbenzoyldiazomethane, tert-butylcarbonyl-4-methylphenylsulfonyldiazomethane, 2-naphthylsulfonylbenzoyldiazomethane, 4-methylphenylsulfonyl-2-naphthoyldiazomethane, methylsulfonylbenzoyldiazomethane, and tert-butoxycarbonyl-4-methylphenylsulfonyldiazomethane.

[0047] N-sulfonyloxyimide photoacid generators include combinations of an imide skeleton and a sulfonic acid. Representative imide skeletons include succinimide, naphthalenedicarboxylic acid imide, phthalimide, cyclohexyldicarboxylic acid imide, 5-norbornene-2,3-dicarboxylic acid imide, and 7-oxabicyclo[2.2.1]-5-heptene-2,3-dicarboxylic acid imide. Representative sulfonate salts include trifluoromethanesulfonate, nonafluorobutanesulfonate, heptadecafluorooctanesulfonate, 2,2,2-trifluoroethanesulfonate, pentafluorobenzenesulfonate, 4-trifluoromethylbenzenesulfonate, 4-fluorobenzenesulfonate, toluenesulfonate, benzenesulfonate, naphthalenesulfonate, camphorsulfonate, octanesulfonate, dodecylbenzenesulfonate, butanesulfonate, and methanesulfonate.

[0048] Benzoin sulfonate photoacid generators include benzoin tosylate, benzoin mesylate, and benzoin butane sulfonate.

[0049] Pyrogallol trisulfonate photoacid generators include pyrogallol, phloroglucinol, catechol, resorcinol, and hydroquinone in which all hydroxyl groups have been replaced by trifluoromethanesulfonate, nonafluorobutanesulfonate, heptadecafluorooctanesulfonate, 2,2,2-trifluoroethanesulfonate, pentafluorobenzenesulfonate, 4-trifluoromethylbenzenesulfonate, 4-fluorobenzenesulfonate, toluenesulfonate, benzenesulfonate, naphthalenesulfonate, camphorsulfonate, octanesulfonate, dodecylbenzenesulfonate, butanesulfonate, or methanesulfonate.

[0050] Nitrobenzyl sulfonate photoacid generators include 2,4-dinitrobenzyl sulfonates, 2-nitrobenzyl sulfonates, and 2,6-dinitrobenzyl sulfonates, and representative sulfonates include trifluoromethanesulfonate, nonafluorobutanesulfonate, heptadecafluorooctanesulfonate, 2,2,2-trifluoroethanesulfonate, pentafluorobenzenesulfonate, 4-trifluoromethylbenzenesulfonate, 4-fluorobenzenesulfonate, toluenesulfonate, benzenesulfonate, naphthalenesulfonate, camphorsulfonate, octanesulfonate, dodecylbenzenesulfonate, butanesulfonate, and methanesulfonate. Also useful are similar nitrobenzyl sulfonate compounds in which the nitro group on the benzyl side is replaced with trifluoromethyl.

[0051] Sulfone photoacid generators 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)propiophenone, 2-cyclohexylcarbonyl-2-(p-toluenesulfonyl)propane, and 2,4-dimethyl-2-(p-toluenesulfonyl)pentan-3-one.

[0052] 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-pentanedione glyoxime, and bis-O-(p-toluenesulfonyl)-2-methyl-3,4-pentanedione glyoxime. bis-O-(n-butanesulfonyl)-α-dimethylglyoxime, bis-O-(n-butanesulfonyl)-α-diphenylglyoxime, bis-O-(n-butanesulfonyl)-α-dicyclohexylglyoxime, bis-O-(n-butanesulfonyl)-2,3-pentanedione glyoxime, bis-O-(n-butanesulfonyl)-2-methyl-3,4-pentanedione glyoxime, bis -O-(methanesulfonyl)-α-dimethylglyoxime, bis-O-(trifluoromethanesulfonyl)-α-dimethylglyoxime, bis-O-(1,1,1-trifluoroethanesulfonyl)-α-dimethylglyoxime, bis-O-(tert-butanesulfonyl)-α-dimethylglyoxime, bis-O-(perfluorooctanesulfonyl)-α-dimethylglyoxime, bis-O-(cyclohexylsulfonyl)-α-dimethylglyoxime, bis-O-(benzenesulfonyl)-α-dimethylglyoxime, bis-O-(p-fluorobenzenesulfonyl)-α-dimethylglyoxime, bis-O-(p-tert-butylbenzenesulfonyl)-α-dimethylglyoxime, bis-O-(xylenesulfonyl)-α-dimethylglyoxime, and bis-O-(camphorsulfonyl)-α-dimethylglyoxime.

[0053] Of these, preferred PAGs are sulfonium salts, iodonium salts, and N-sulfonyloxyimides.

[0054] The optimum anion for the generated acid will vary depending on factors such as the ease of cleavage of the acid-labile groups in the polymer, but anions that are nonvolatile and not very highly diffusible are generally selected. Suitable anions include benzenesulfonic acid, toluenesulfonic acid, 4-(4-toluenesulfonyloxy)benzenesulfonic acid, pentafluorobenzenesulfonic acid, 2,2,2-trifluoroethanesulfonic acid, nonafluorobutanesulfonic acid, heptadecafluorooctanesulfonic acid, camphorsulfonic acid, disulfonic acid, sulfonylimides, and sulfonylmethaneides.

[0055] Examples of thermal acid generators include metal-free sulfonium and iodonium salts, such as strongly non-acidophilic triarylsulfonium, dialkylarylsulfonium, and diarylalkylsulfonium salts, strongly non-acidophilic alkylaryliodonium and diaryl iodonium salts, and strongly non-acidophilic ammonium, alkylammonium, dialkylammonium, trialkylammonium, and tetraalkylammonium salts. 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 thermally decompose to free sulfonic acids. Examples include diaryliodonium perfluoroalkylsulfonate, diaryliodonium tris(fluoroalkylsulfonyl)methide, diaryliodonium bis(fluoroalkylsulfonyl)methide, diaryliodonium bis(fluoroalkylsulfonyl)imide, and diaryliodonium quaternary ammonium perfluoroalkylsulfonate. Examples of unstable esters include 2-nitrobenzyl tosylate, 2,4-dinitrobenzyl tosylate, 2,6-dinitrobenzyl tosylate, and 4-nitrobenzyl tosylate; benzenesulfonates such as 2-trifluoromethyl-6-nitrobenzyl 4-chlorobenzenesulfonate and 2-trifluoromethyl-6-nitrobenzyl 4-nitrobenzenesulfonate; phenolic sulfonate esters such as phenyl 4-methoxybenzenesulfonate; quaternary ammonium tris(fluoroalkylsulfonyl)methides and quaternary alkylammonium bis(fluoroalkylsulfonyl)imides; alkylammonium salts of organic acids, such as the triethylammonium salt of 10-camphorsulfonic acid. Various aromatic (anthracene, naphthalene, or benzene derivative) sulfonic acid amine salts, such as those disclosed in U.S. Patent Nos. 3,474,054, 4,200,729, 4,251,665, and 5,187,019, can also be used as TAGs.

[0056] The acid generator (D) may be a mixture of two or more compounds.

[0057] The content of the acid generator (D) is preferably 0.5 to 20 mass % based on the film-forming component (C); more preferably 1.0 to 10 mass %; even more preferably 1.0 to 5 mass %; and still more preferably 1.5 to 4 mass %.

[0058] Crosslinker (E) The lithographic composition according to the present invention may contain a crosslinking agent (E). In the present invention, the crosslinking agent refers to a compound having a crosslinking function. There are no particular limitations on the crosslinking agent, so long as it crosslinks the molecules of the component (C) intramolecularly and / or intermolecularly.

[0059] Examples of the crosslinking agent include melamine compounds, guanamine compounds, glycoluril compounds or urea compounds substituted with at least one group selected from a methylol group, an alkoxymethyl group, and an acyloxymethyl group, epoxy compounds, thioepoxy compounds, isocyanate compounds, azide compounds, and compounds containing a double bond such as an alkenyl ether group. Compounds containing a hydroxy group are also used as crosslinking agents. Examples of epoxy compounds include tris(2,3-epoxypropyl)isocyanurate, trimethylolmethane triglycidyl ether, trimethylolpropane triglycidyl ether, and triethylolethane triglycidyl ether. Examples of melamine compounds include hexamethylolmelamine, hexamethoxymethylmelamine, compounds in which 1 to 6 methylol groups of hexamethylolmelamine have been methoxymethylated, and mixtures thereof. Examples of hexamethoxyethylmelamine, hexaacyloxymethylmelamine, compounds in which 1 to 6 methylol groups of hexamethylolmelamine have been acyloxymethylated, and mixtures thereof. Examples of guanamine compounds include tetramethylolguanamine, tetramethoxymethylguanamine, compounds in which 1 to 4 methylol groups of tetramethylolguanamine have been methoxymethylated, and mixtures thereof. Examples of guanamine compounds include tetramethylolguanamine, tetramethoxymethylguanamine, compounds in which 1 to 4 methylol groups have been methoxymethylated, and mixtures thereof. Examples of tetramethoxyethylguanamine, tetraacyloxyguanamine, compounds in which 1 to 4 methylol groups of tetramethylolguanamine have been acyloxymethylated, and mixtures thereof. Examples of glycoluril compounds include tetramethylol glycoluril, tetramethoxy glycoluril, tetramethoxymethyl glycoluril, compounds in which 1 to 4 of the methylol groups of tetramethylol glycoluril have been methoxymethylated, mixtures thereof, and compounds in which 1 to 4 of the methylol groups of tetramethylol glycoluril have been acyloxymethylated, and mixtures thereof. Examples of urea compounds include tetramethylol urea, tetramethoxymethyl urea, compounds in which 1 to 4 of the methylol groups of tetramethylol urea have been methoxymethylated, mixtures thereof, and tetramethoxyethyl urea.Examples of compounds containing an alkenyl ether group 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, pentaerythritol trivinyl ether, pentaerythritol tetravinyl ether, sorbitol tetravinyl ether, sorbitol pentavinyl ether, and trimethylolpropane trivinyl ether.

[0060] Examples of crosslinking agents containing a hydroxy group include the following: [ka]

[0061] The crosslinking temperature during film formation is preferably 50 to 230°C, more preferably 80 to 220°C, and even more preferably 80 to 190°C.

[0062] The content of the crosslinking agent (E) is preferably 3 to 30 mass % based on the film-forming component (C), and more preferably 5 to 20 mass %.

[0063] Basic Compounds (F) The lithographic composition according to the present invention may further contain a basic compound (F), which has the effect of neutralizing acid generated in exposed areas and suppressing environmental impacts. In addition to the above effects, the basic compound also has the effect of suppressing the deactivation of the acid on the film surface by amine components contained in the air.

[0064] The basic compound (F) is preferably ammonia, C 1-16 Primary aliphatic amines, C 2-32 Secondary aliphatic amines, C 3-48 Tertiary aliphatic amines, C6-30 aromatic amines, and C 5-30 and derivatives thereof.

[0065] Specific examples of basic compounds include ammonia, ethylamine, n-octylamine, ethylenediamine, triethylamine, triethanolamine, tripropylamine, tributylamine, triisopropanolamine, diethylamine, tris[2-(2-methoxyethoxy)ethyl]amine, 1,8-diazabicyclo[5.4.0]undecene-7, 1,5-diazabicyclo[4.3.0]nonene-5, 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, and 1,5,7-triazabicyclo[4.4.0]dec-5-ene.

[0066] The molecular weight of the basic compound (F) is preferably 17-500, more preferably 100-350.

[0067] The content of the basic compound (F) is preferably 0.01 to 1.0 mass% based on the film-forming component (C), more preferably 0.20 to 0.8 mass%, and even more preferably 0.20 to 0.5 mass%. In consideration of the storage stability of the composition, a suitable embodiment is one in which no basic compound (F) is contained (0.00 mass%).

[0068] Surfactant (G) The lithographic composition according to the present invention preferably contains a surfactant (G). The inclusion of a surfactant can improve coatability. Examples of surfactants that can be used in the present invention include (I) anionic surfactants, (II) cationic surfactants, and (III) nonionic surfactants. More specifically, examples include (I) alkyl sulfonates, alkyl benzene sulfonic acids, and alkyl benzene sulfonates; (II) lauryl pyridinium chloride and lauryl methyl ammonium chloride; and (III) polyoxyethylene octyl ether, polyoxyethylene lauryl ether, polyoxyethylene acetylenic glycol ether, fluorine-containing surfactants (e.g., Fluorad (3M), Megafac (DIC), Sulfuron (Asahi Glass), and organosiloxane surfactants (e.g., KF-53, KP341 (Shin-Etsu Chemical Co., Ltd.)).

[0069] These surfactants can be used alone or in combination of two or more. The content of the surfactant (G) is preferably 0.05 to 0.5 mass %, more preferably 0.09 to 0.2 mass %, based on the film-forming component (C).

[0070] Additive (H) The lithographic composition according to the present invention may contain an additive (H) other than components (A) to (G). The additive (H) preferably comprises a plasticizer, a dye, a contrast enhancer, an acid, a radical generator, a substrate adhesion enhancer, an antifoaming agent, or a mixture of any of these. The content of the additive (H) (when there are multiple additives, the sum of the contents) is preferably 0.1 to 20 mass%, more preferably 0.1 to 10 mass%, and even more preferably 1 to 5 mass%, based on the composition. In one embodiment of the present invention, the composition according to the present invention does not contain any additive (H) (0.0 mass%).

[0071] <Membrane manufacturing method> The method for producing a membrane according to the present invention comprises the following steps: (1) applying a lithographic composition according to the present invention over a substrate; (2) Forming a film from the lithographic composition by reducing pressure and / or heating. Hereinafter, the numbers in parentheses indicate the order of the steps. For example, if steps (1), (2), and (3) are listed, the order of the steps will be as stated above. In the present invention, the film is a dried or hardened film, and includes, for example, a resist film. According to the present invention, since the influence of standing waves can be reduced during film formation, it is not necessary to form an anti-reflective film (e.g., an anti-reflective film under a resist) above the substrate before applying the lithography composition. If an anti-reflective film is formed under the lithography composition, it will need to be removed, and for the reasons of simplifying the manufacturing process, it is preferable not to form an anti-reflective film under the lithography composition.

[0072] One embodiment of the manufacturing method according to the present invention will now be described. The lithography composition according to the present invention is applied by an appropriate method above a substrate (e.g., a silicon / silicon dioxide-coated substrate, a silicon nitride substrate, a silicon wafer substrate, a glass substrate, an ITO substrate, or the like). In the present invention, "above" includes a case where the composition is formed directly above the substrate and a case where the composition is formed via another layer. For example, a planarizing film may be formed directly above the substrate, and the composition according to the present invention may be applied directly above the planarizing film. The application method is not particularly limited, and examples include coating methods using a spinner or coater. After coating, the film according to the present invention is formed by reducing the pressure and / or heating. Alternatively, the film may be formed by rotating the substrate at high speed to evaporate the solvent without heating. When the lithography composition according to the present invention is a resist composition, heating is carried out, for example, using a hot plate. The heating temperature is preferably 80 to 250°C, more preferably 80 to 200°C, and even more preferably 90 to 180°C. The heating time is preferably 30 to 600 seconds, more preferably 30 to 300 seconds, and even more preferably 60 to 180 seconds. The heating is preferably carried out in air or nitrogen gas atmosphere. The thickness of the resist film varies depending on the exposure wavelength, but is preferably 100 to 50,000 nm. When a KrF excimer laser is used for exposure, the thickness of the resist film is preferably 100 to 5,000 nm, more preferably 100 to 1,000 nm, and even more preferably 400 to 600 nm.

[0073] When the lithographic composition of the present invention is a resist composition, the method for producing a resist pattern of the present invention comprises the following steps. forming a film using the lithographic composition according to the method described above; (3) exposing the film to radiation; (4) The film is developed to form a resist pattern.

[0074] A film formed using the resist composition is exposed through a predetermined 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 allow for a ±1% range. After exposure, a post-exposure bake can be performed as needed. The post-exposure bake temperature is preferably 80 to 150°C, more preferably 100 to 140°C, and the bake 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 temperature of the developer is preferably 5 to 50°C, more preferably 25 to 40°C, and the development time is preferably 10 to 300 seconds, more preferably 30 to 60 seconds. By using such a developer, the film can be easily dissolved and removed at room temperature. Furthermore, a surfactant, for example, can be added to the developer. When a negative resist composition is used, the unexposed portions of the photoresist layer are removed by development to form a resist pattern. This resist pattern can be further refined by using, for example, a shrink material.

[0075] Figure 1 is a schematic diagram of the cross-sectional shape of a negative resist pattern affected by standing waves. Resist pattern 1 is formed on substrate 2. When a waveform with a large amplitude is formed in the cross section, even a small difference in film thickness can significantly change the resist top shape, resulting in poor dimensional accuracy. Therefore, a small amplitude is preferable. Here, the first point where the resist pattern thickness is maximized upward from the contact point between the substrate and the resist pattern is designated antinode 3, and the point directly above it where the resist pattern thickness is minimized is designated node 4. The distance between the antinode and the node in the direction parallel to the substrate is designated antinode distance 5. A small antinode distance is preferable. Specifically, the ratio of the antinode distance to the target pattern width (hereinafter sometimes referred to as the standing wave index) is preferably less than 10%, more preferably 5% or less. The target pattern width may refer to the width of the resist top when it is assumed not to be affected by standing waves. By reducing the standing waves that appear in the resist pattern, it is possible to suppress pattern collapse, which occurs when the resist pattern takes on a shape different from the intended one or when notches are formed, making it easier to stably form finer patterns. Figure 2 is a schematic diagram of the cross-sectional shape of a negative resist pattern when not affected by standing waves. In negative resists, the polymer is insolubilized through the acid generated by exposure, so light does not reach the bottom, generating less acid than the top, making the bottom less likely to become insolubilized than the top. As a result, the formed pattern tends to have an inverted tapered shape. In Figure 2, there are no antinodes or nodes, and in this case the standing wave index is considered to be 0.

[0076] The method for producing a metal pattern according to the present invention comprises the steps of: A resist pattern is formed by the method described above, (5a) forming a metal layer on the resist pattern; (6a) Remove the remaining resist patterns and the metal layer on them. The steps (1) to (4) are followed by steps (5a) and (6a), in the order described above. The metal layer is formed by depositing a metal such as gold or copper (which may be a metal oxide, etc.) by, for example, vapor deposition or sputtering. The resist pattern is then removed together with the metal layer formed thereon using a stripping solution, thereby forming a metal pattern. The stripping solution is not particularly limited as long as it is used as a resist stripper, but examples of the stripping solution that can be used include N-methylpyrrolidone (NMP), acetone, and alkaline solutions. When the resist according to the present invention is negative, it tends to have an inverse tapered shape, as described above. The inverse tapered shape allows for easy stripping because there is a gap between the metal on the resist pattern and the metal formed in the area where the resist pattern is not formed.

[0077] The method for manufacturing a patterned substrate according to the present invention includes the steps of: A resist pattern is formed by the method described above, (5b) Etching using the resist pattern as a mask; (6b) Processing the substrate The etching may be either dry etching or wet etching, and may be performed multiple times. Steps (1) to (4) are followed by steps (5b) and (6b). The order of the steps is as described above.

[0078] Further, the method for manufacturing a patterned substrate according to the present invention comprises the steps of: A resist pattern is formed by the method described above, (5c) Etching the resist pattern; (5d) Etching the substrate The steps (1) to (4) are followed by steps (5c) and (6d). The order of the steps is as described above. wherein the combination of steps (5c) and (5d) is repeated at least two or more times; and The substrate is composed of a plurality of Si-containing layers stacked one upon the other, at least one of which is conductive and at least one of which is electrically insulating. Preferably, conductive Si-containing layers and electrically insulating Si-containing layers are stacked alternately. Here, the thickness of the resist film formed from the lithography composition is preferably 0.5 to 200 μm.

[0079] Thereafter, the substrate is further processed as needed to form a device. This further processing can be performed by a known method. The device manufacturing method according to the present invention comprises any of the above methods, and preferably further comprises a step of forming wiring on the processed substrate. Examples of the device include a semiconductor element, a liquid crystal display element, an organic EL display element, a plasma display element, and a solar cell element. The device is preferably a semiconductor element.

[0080] The present invention will be described below with reference to various examples. However, the present invention is not limited to these examples.

[0081] The ingredients used below are listed below.

[0082] The component (A) or comparative compound used is as follows: Comparative compound CA: methyl acetoacetate (Tokyo Chemical Industry Co., Ltd., hereafter referred to as TCI) [ka] A1: t-butyl acetoacetate (TCI) [ka] A2: Methyl-4,4-dimethyl-3-oxovalerate (TCI) [ka] A3: Isopropyl acetoacetate (TCI) [ka] A4: s-Butyl acetoacetate (TCI) [ka] A5: Dimethyl-1,3-acetonedicarboxylate (TCI) [ka] A6: Diethyl-1,3-acetonedicarboxylate (TCI) [ka]

[0083] The component (B) used is as follows: B1:PGMEA B2:PGME B3:EL

[0084] The component (C) used is as follows: C1-1: CST7030 random copolymer (p-hydroxystyrene (70), styrene (30)), Mw approx. 9700 (Maruzen Petrochemicals) [ka] C1-2: VP-3500, p-hydroxystyrene, Mw approx. 5000 (Nippon Soda) [ka] C1-3: Poly-TZ-GIJ random copolymer, (p-hydroxystyrene (60), styrene (20), t-butyl acrylate), Mw approx. 12,000 (Dupont) [ka]

[0085] The component (D) used is as follows: D1: WPAG367 (Fujifilm Wako Pure Chemical Industries, Ltd.) [ka] D2: TPS-SA (Toyo Gosei) [ka] D3: TPS-C1 (Heraeus) [ka] D4: MDT Sensitizer (Heraeus) [ka] D5: Garo IN-K (DSP Gokyo Food & Chemical) [ka] D6: WPI-169 (Fujifilm Wako Pure Chemical Industries, Ltd.) [ka]

[0086] The component (E) used is as follows: E1:DML-POP, Honshu Chemical [ka]

[0087] The (F) components used are as follows: F1: Triethanolamine (TCI) F2: Tris[2-(2-methoxyethoxy)ethyl]amine (TCI)

[0088] The component (G) used is surfactant G1 (MegafacR2011, DIC).

[0089] <Preparation of Comparative Composition 1> Mix 65.1 g of solvent B1 with 27.9 g of solvent B2 to prepare a B1B2 mixed solvent. 3.710 g of C1-1, 2.474 g of C1-2, 0.577 g of E1, 0.127 g of D1, 0.106 g of D2, and 0.006 g of G1 were added to the mixture. The solution was mixed at room temperature and visually confirmed to have dissolved the solid components. Comparative Example Composition 1 was obtained.

[0090] <Preparation of Example Compositions 1 to 8 and Comparative Compositions 2 and 3> Example compositions 1 to 8 and comparative compositions 2 and 3 are prepared in the same manner as in the preparation example of comparative composition 1, except that the components are changed as shown in Tables 1 and 2 below. [Table 1] [Table 2]

[0091] <Resist Pattern Formation Example 1> AZ KrF-17B (Merck Performance Materials, hereafter referred to as MPM) was spin-coated onto the surface of a silicon substrate (SUMCO Corp., 8 inches) and soft-baked at 180°C for 60 seconds to form a 45 nm BARC film. The example composition was then spin-coated on top of this and soft-baked at 110°C for 60 seconds to form a 235 nm thick resist film on the same substrate. This configuration ensures a 7% reflectance for KrF radiation (248 nm). The resulting substrate was exposed to KrF radiation using an exposure tool (Canon, FPA-3000EX5). The exposure mask used had a line:space ratio of 1:1, with multiple 1.0 μm spaces, with the spaces decreasing in size as shown below. 1000nm, 900nm, 800nm, 700nm, 600nm, 500nm, 400nm, 300nm, 280nm, 260nm, 240nm, 22 0nm, 200nm, 190nm, 180nm, 170nm, 160nm, 150nm, 140nm, 130nm, 120nm, 110nm, 100nm. The substrate is post-exposure baked (PEB) at 100°C for 60 seconds. The resist film is then puddle-developed using a 2.38% tetramethylammonium hydroxide (TMAH) solution for 60 seconds. While the puddle developer is still on the substrate, pure water is poured onto the substrate. While rotating, the puddle developer is replaced with pure water, and the substrate is spin-dried at 2000 rpm.

[0092] <Evaluation 1 of standing wave reduction> The reduction in standing waves is evaluated. A resist pattern formed in Resist Pattern Formation Example 1 above, with a space corresponding to 150 nm, is observed. A section is prepared from the substrate and observed using an SEM (SU8230, Hitachi High-Technologies). The abdominal internode distance defined above is measured (Offline CD Measurement Software Version 6.00, Hitachi High-Technologies). The abdominal internode distance is divided by the desired pattern width to calculate the standing wave index. Evaluation is based on the following criteria. A: Standing wave index is 0% or more and 5% or less B: Standing wave index is greater than 5% and less than 10% C: Standing wave index is 10% or more

[0093] <Minimum dimension evaluation 1> The minimum dimension of the resist pattern formed in Resist Pattern Formation Example 1 above was evaluated. Checks were made to see if there was any pattern collapse, starting with larger patterns, and then gradually moving to smaller patterns. The pattern immediately before pattern collapse was confirmed (a pattern that was not collapsed) was taken as the minimum dimension. The results obtained are shown in Tables 3 and 4. [Table 3] [Table 4] As shown by Comparative Composition 1, tests were conducted under conditions in which standing waves could not be completely prevented even when a BARC was present.

[0094] <Developer Solubility (ADR) Evaluation> Example compositions 1, 5, and 7 were each applied to a silicon substrate and soft-baked at 110°C for 60 seconds to achieve a film thickness of 235 nm. The resist film was then baked at 100°C for 60 seconds without exposure, and the resulting resist film was puddle-developed using a 2.38% aqueous solution of tetramethylammonium hydroxide (TMAH). The time until the film dissolved was measured visually. The evaluation results for Example compositions 1, 5, and 7 were 50 seconds, 33 seconds, and 51 seconds, respectively.

[0095] <Preparation of Example Composition 9 and Comparative Example Composition 4> Example composition 9 and Comparative example composition 4 are prepared in the same manner as in the preparation of Comparative composition 1, except that the components are changed as shown in Table 5 below. [Table 5]

[0096] <Resist Pattern Formation Example 2> A resist pattern was formed in the same manner as in Resist Pattern Formation Example 1 above, except that the surface of a silicon substrate (SUMCO Corp., 8 inches) was first treated with a 1,1,1,3,3,3-hexamethyldisilazane solution at 90°C for 60 seconds, no BARC film was formed, and the thickness of the formed resist film was 800 nm, resulting in an optical reflectance of 53% for KrF rays (248 nm).

[0097] <Evaluation of standing wave reduction 2> For the resist pattern formed in Resist Pattern Formation Example 2, evaluation of standing wave reduction is carried out in the same manner as in Evaluation 1 of Standing Wave Reduction above, except that a pattern corresponding to 300 nm is observed.

[0098] <Minimum dimension evaluation 2> For the resist pattern formed in Resist Pattern Formation Example 2, the minimum dimension is evaluated in the same manner as in Minimum Dimension Evaluation 1. The results obtained are shown in Table 6. [Table 6]

[0099] <Preparation of Comparative Composition 5> Mix 54.53 g of solvent B2 with 23.37 g of solvent B3 to prepare a B2B3 mixed solvent. Add 21.539 g of C1-3, 0.052 g of D2, 0.065 g of D3, 0.226 g of D5, 0.129 g of D6, 0.057 g of F2, and 0.033 g of G1. Mix the solution at room temperature and visually confirm that the solid components have dissolved. Comparative Example Composition 5 is obtained.

[0100] <Preparation of Example Composition 10> Example Composition 10 is prepared similarly to the preparation of Comparative Composition 5, except that the ingredients are changed as shown in the table below. [Table 7]

[0101] <Resist Pattern Formation Example 3> A resist pattern was formed in the same manner as in Resist Pattern Formation Example 1 above, except that the surface of a silicon substrate (SUMCO Corp., 8 inches) was first treated with a 1,1,1,3,3,3-hexamethyldisilazane solution at 90°C for 60 seconds, no BARC film was formed, and the thickness of the formed resist film was 800 nm, resulting in a KrF line (248 nm) reflectance of 53%. Post-exposure baking was then performed at 110°C for 60 seconds.

[0102] <Evaluation 3 of standing wave reduction> For the resist pattern formed in Resist Pattern Formation Example 3, evaluation of standing wave reduction was carried out in the same manner as in the above Standing Wave Reduction Evaluation 1, except that the pattern corresponding to 400 nm was observed. The obtained results are shown in Table 8.

[0103] <Evaluation of minimum dimensions 3> For the resist pattern formed in Resist Pattern Formation Example 3, the minimum dimension is evaluated in the same manner as in Minimum Dimension Evaluation 1. The results obtained are shown in Table 8. [Table 8] [Explanation of symbols]

[0104] 1. Substrate 2. Resist patterns affected by standing waves 3. Belly 4. Section 5. Abdominal internode distance 11. Circuit board 12. Resist pattern not affected by standing waves

Claims

1. A method for reducing standing waves in a lithography process, comprising applying a composition comprising a carboxylic acid ester (A) and a film-forming component (C) above a substrate and using the composition to form a film: wherein the carboxylic acid ester (A) is represented by formula (a): 【Chemistry 1】 R １ is C １－１０ Alkyl, or -OR １ ' and R ２ Ha-OR ２ ' and R １ ' and R ２ ' are each independently C １－２０ is a hydrocarbon, R ３ and R ４ are each independently H or C １－１０ is alkyl, R １ and R ３ Or R ４ , or R ２ and R ３ Or R ４ may be bonded to form a saturated or unsaturated hydrocarbon ring, n1 is 1 or 2: However, when n1=1, R ２ ' is C ３－２０ is a hydrocarbon, The film-forming component (C) contains a structural unit represented by formula (c1) and a structural unit represented by formula (c2), 【Chemistry 2】 wherein R c1 is H, C 1-5 alkyl, C 1-5 alkoxy, or —COOH; R c2 is C 1-5 alkyl (in which —CH 2 — may be replaced by —O—); m1 is a number from 0 to 4, and m2 is a number between 1 and 2, and m1+m2≦5. 【Transformation 3】

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

3. A lithographic composition comprising a carboxylic acid ester (A), a film-forming component (C), and a solvent (B): wherein the carboxylic acid ester (A) is represented by formula (a): 【Chemistry 4】 R １ is C １－１０ Alkyl, or -OR １ ' and R ２ Ha-OR ２ ' and R １ ' and R ２ ' are each independently C １－２０ is a hydrocarbon, R ３ and R ４ are each independently H or C １－１０ is alkyl, R １ and R ３ Or R ４ , or R ２ and R ３ Or R ４ may be bonded to form a saturated or unsaturated hydrocarbon ring, n1 is 1 or 2: However, when n1=1, R ２ ' is C ３－２０ is a hydrocarbon, The film-forming component (C) contains a structural unit represented by formula (c1) and a structural unit represented by formula (c2), 【Transformation 5】 wherein R c1 is H, C 1-5 alkyl, C 1-5 alkoxy, or —COOH; R c2 is C 1-5 alkyl (in which —CH 2 — may be replaced by —O—); m1 is a number from 0 to 4, and m2 is a number between 1 and 2, and m1+m2≦5. 【Transformation 6】

4. The lithographic composition of claim 3 , wherein the carboxylic acid ester (A) is represented by formula (a1): 【Transformation 7】 where: R １１ is C １－５ is alkyl, R １２ is C ３－２０ is a hydrocarbon, R １３ and R １４ are each independently H or C １－５ It is alkyl.

5. The lithographic composition according to claim 3 or 4, further comprising an additive (H).

6. 6. The lithography composition according to claim 3, wherein the content of the carboxylic acid ester (A) is 1.0 to 200 mass % based on the solvent (B).

7. The boiling points of the carboxylic acid ester (A) and the solvent (B) are respectively bp Ａ , bp Ｂ The saturated vapor pressure at 25°C and 1 atmosphere is Vpc. Ａ , vpc Ｂ Then, bp Ａ >bp Ｂ , and vpc Ａ <vpc Ｂ The lithographic composition according to claim 3 , which satisfies the following:

8. The lithographic composition according to at least one of claims 3 to 7, which is a lithographic film-forming composition.

9. A method for producing a membrane comprising the steps of: (1) applying a lithographic composition according to at least one of claims 3 to 8 above a substrate; (2) Forming a film from the lithographic composition by reducing pressure and / or heating.

10. A method for producing a resist pattern, comprising the following steps: Forming a film from the lithographic composition by the method of claim 9; (3) exposing the film to radiation; (4) The film is developed to form a resist pattern: Here, the lithography composition is a resist composition.

11. A method for producing a metal pattern comprising the steps of: A resist pattern is formed by the method according to claim 10, (5a) forming a metal layer on the resist pattern; (6a) The remaining resist pattern and the metal layer thereon are removed.

12. A method for producing a patterned substrate comprising the steps of: A resist pattern is formed by the method according to claim 10, (5b) etching using the resist pattern as a mask; (6b) Processing the substrate.

13. A method for producing a patterned substrate comprising the steps of: A resist pattern is formed by the method according to claim 10, (5c) etching the resist pattern; (5d) Etching the substrate: wherein the combination of steps (5c) and (5d) is repeated at least two or more times; and The substrate comprises a plurality of Si-containing layers stacked one on top of the other, at least one of which is electrically conductive and at least one of which is electrically insulating.

14. A method for manufacturing a device comprising the method according to at least one of claims 9 to 13.

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