Aqueous solution for manufacturing electronic device, method for manufacturing resist pattern, and method for manufacturing device

Abstract

Provided is an aqueous solution for producing an electronic device, which is capable of suppressing defects. Provided is an aqueous solution for producing an electronic device, which contains (A) a sulfonic acid derivative having a specific structure, (B) a water-containing solvent, and (C) a hydroxyl group-containing compound having a specific structure.

Description

Technical Field

[0001] The present invention relates to an aqueous solution for manufacturing an electronic device, a method for manufacturing a resist pattern, and a method for manufacturing a device. Background Art

[0002] In recent years, the demand for high-density LSIs has been growing, and this has led to a need for finer patterns. To meet this demand, photolithography processes using short-wavelength KrF excimer lasers, ArF excimer lasers, extreme ultraviolet rays, X-rays, electron beams, and the like have gradually become practical. To meet this demand for finer resist patterns, photosensitive resin compositions used as resists during fine processing are required to have high resolution. While exposure to short-wavelength light allows for finer patterns, the formation of very fine structures can lead to a decrease in yield, such as the collapse of fine patterns.

[0003] Patent Document 1 discloses that a rinsing liquid containing a sulfonic acid compound and a nonionic surfactant can suppress pattern collapse, etc. Patent Document 2 discloses that a rinsing liquid containing a nonionic surfactant can suppress pattern collapse and also exhibit excellent melting performance.

[0004] [Prior art literature]

[0005] [Patent Document]

[0006] [Patent Document 1] Japanese Patent Application Laid-Open No. 2012-198456

[0007] [Patent Document 2] Japanese Patent Application Laid-Open No. 2014-219577 Summary of the Invention

[0008] [Problems to be solved by the invention]

[0009] The inventors believe that one or more problems still need to be improved. Examples include: reducing defects in fine resist patterns; suppressing the formation of bridges in resist patterns; preventing resist pattern collapse in fine resist patterns; suppressing unevenness in resist pattern width; reducing residue after removing the aqueous solution for manufacturing electronic devices; lowering the surface tension of the aqueous solution for manufacturing electronic devices; providing an aqueous solution for manufacturing electronic devices with low handling risks; providing an aqueous solution for manufacturing electronic devices with excellent storage stability (e.g., long-term storage); and providing an aqueous solution for manufacturing electronic devices with minimal impact on the resist pattern.

[0010] The present invention is completed based on the above technical background, and provides an aqueous solution for manufacturing electronic devices.

[0011] [Methods used to solve the problem]

[0012] The aqueous solution for manufacturing electronic devices of the present invention comprises:

[0013] Sulfonic acid derivatives (A);

[0014] solvent (B); and

[0015] a hydroxyl group-containing compound (C),

[0016] in,

[0017] The sulfonic acid derivative (A) is represented by formula (a):

[0018]

[0019] Where,

[0020] A1 is C 3-30 A hydrocarbon group, which may be substituted with a halogen;

[0021] α is 1 or 2;

[0022] X α+ H + NH4 + , or α-valent metal ions,

[0023] The solvent (B) contains water;

[0024] The hydroxyl-containing compound (C) is represented by formula (c):

[0025]

[0026] Where,

[0027] R c1 、R c2 、R c3 and R c4 are each independently hydrogen, fluorine or C 1-5 alkyl;

[0028] L c1 and L c2 Each independently is C 1-20 Alkylene, C 5-20 Cycloalkylene, C 2-4 Alkenylene, C 2-4 Alkynylidene or C 6-20 Arylene; and these groups may be substituted with fluorine, C 1-5 an alkyl group or a hydroxy group; and

[0029] h is 0, 1 or 2.

[0030] The method for producing a resist pattern of the present invention uses the above-mentioned aqueous solution for producing an electronic device.

[0031] The method for manufacturing a device of the present invention includes the above-mentioned method for manufacturing a resist pattern.

[0032] [Effects of the Invention]

[0033] By using the aqueous solution for manufacturing an electronic device of the present invention, one or more of the following effects can be expected.

[0034] The invention can reduce defects in fine resist patterns. It can suppress the formation of bridges in resist patterns. It can prevent resist pattern collapse in fine resist patterns. It can suppress unevenness in resist pattern width. It can reduce residue after removing the aqueous solution used to manufacture electronic devices. It can reduce the surface tension of the aqueous solution used to manufacture electronic devices. It can reduce the handling risk of the aqueous solution used to manufacture electronic devices. It can provide excellent storage stability of the aqueous solution used to manufacture electronic devices. It can reduce the impact of the aqueous solution used to manufacture electronic devices on the resist pattern. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] Figure 1 This is a schematic diagram showing the state when the resist wall is being rinsed. DETAILED DESCRIPTION

[0036] [Modes for Carrying Out the Invention]

[0037] The embodiments of the present invention are described in detail below.

[0038] [definition]

[0039] In this specification, unless otherwise specified, the definitions and examples described in that paragraph shall apply.

[0040] The singular includes the plural, and “a” or “the” means “at least one.” Certain conceptual elements may be expressed in multiple forms, and when describing the amount (eg, mass % or mole %), the amount refers to the total of these multiple forms.

[0041] "And / or" includes all combinations of elements and also includes the case where the elements are used alone.

[0042] When "~ / to" or "-" is used to express a numerical range, 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.

[0043] “C x-y ”, “C x ~C y ” and “C x " refers to the number of carbon atoms in a molecule or a substituent. For example, C 1-6 The alkyl group means an alkyl chain having 1 or more and 6 or less carbon atoms (such as methyl, ethyl, propyl, butyl, pentyl, and hexyl).

[0044] When a polymer has multiple repeating units, these repeating units are copolymerized. These copolymerizations can be alternating, random, block, graft, or a mixture thereof. When a polymer or resin is represented by a structural formula, n, m, etc., following the parentheses indicates the number of repeating units.

[0045] The temperature unit is Celsius. For example, 20 degrees means 20 degrees Celsius.

[0046] The additive refers to the compound itself having the function (for example, in the case of a base generator, the compound itself that generates a base). Alternatively, the compound may be dissolved or dispersed in a solvent and added to the composition. As one embodiment of the present invention, the composition of the present invention preferably contains such a solvent as solvent (B) or other components.

[0047] <Aqueous solutions for manufacturing electronic devices>

[0048] The aqueous solution for producing an electronic device of the present invention contains a sulfonic acid derivative (A) (hereinafter sometimes referred to as component (A). The same applies to other components), a solvent (B), and a hydroxyl group-containing compound (C).

[0049] Here, the aqueous solution for manufacturing electronic devices refers to a solution used in the manufacturing process of electronic devices. It may be used in the manufacturing process of electronic devices, or it may be removed or disappear during the process. Examples of electronic devices include display devices, LEDs, and semiconductor devices. The aqueous solution for manufacturing electronic devices is preferably an aqueous solution for manufacturing semiconductor substrates; more preferably, a process cleaning solution for manufacturing semiconductor substrates; even more preferably, a photolithography cleaning solution; and even more preferably, a resist pattern cleaning solution. The aqueous solution for manufacturing electronic devices, which is an aqueous solution for manufacturing semiconductor substrates, can also be considered an aqueous solution for manufacturing semiconductor substrates consisting solely of the aqueous solution for manufacturing electronic devices of the present invention.

[0050] As another aspect of the present invention, the aqueous solution for manufacturing an electronic device may be a rinsing composition for rinsing an exposed and developed resist pattern.

[0051] Sulfonic acid derivatives (A)

[0052] The sulfonic acid derivative (A) used in the present invention is represented by formula (a):

[0053]

[0054] Where,

[0055] A1 is C 3-30 Hydrocarbyl (preferably C 8-28 More preferably C 12-28 ; More preferably C12-25 ; More preferably C 12-20 The hydrocarbon group may be substituted with a halogen or may be unsubstituted (preferably unsubstituted). A1 is preferably an alkyl group, an alkyl group substituted with a phenyl group, or a phenyl group substituted with an alkyl group (more preferably an alkyl group or a phenyl group substituted with an alkyl group; further preferably an alkyl group). The alkyl group contained in A1 may be linear, branched, or cyclic (preferably linear or branched; more preferably linear).

[0056] α is 1 or 2 (preferably 1).

[0057] X α+ H + NH4 + Or α-valent metal ions. X α+ Preferably H + NH4 + , lithium ions, sodium ions, potassium ions, magnesium ions (more preferably H + or NH4 + ; More preferably H + ). For example, X α+ Mg 2+ There are two groups formed by bonding A1 and sulfonic group, which are listed in brackets and α, and Mg 2+ Ionically bonded. They partially or fully ionize in aqueous solution.

[0058] The component (A) is preferably represented by the formula (a-1) or (a-2). In a preferred embodiment, the component (A) is represented by the formula (a-2).

[0059] Formula (a-1) is as follows:

[0060]

[0061] Where, α, X α+ As mentioned above,

[0062] na is 1 or 2; preferably 1.

[0063] R a1 C 1-20 Alkyl (preferably C 3-20 More preferably C 10-20 ). The condition is that when na is 2, R a1 They may be the same or different, but the total number of carbon atoms is 20 or less. a1 The alkyl group is preferably linear, branched or cyclic (more preferably linear or branched; further preferably linear).

[0064] In another preferred embodiment of the present invention, the component (A) is represented by the formula (a-1).

[0065] Examples of the formula (a-1) include decylbenzenesulfonic acid, undecylbenzenesulfonic acid, dodecylbenzenesulfonic acid, tridecylbenzenesulfonic acid, tetradecylbenzenesulfonic acid, pentadecylbenzenesulfonic acid, hexadecylbenzenesulfonic acid, heptadecylbenzenesulfonic acid, octadecylbenzenesulfonic acid, nonadecylbenzenesulfonic acid, and the following compounds.

[0066]

[0067] Formula (a-2) is as follows:

[0068]

[0069] Where, α, X α+ as above; and

[0070] R a2 C 3-20 Alkyl (preferably C 8-20 More preferably C 10-20 ; More preferably C 10-19 ; More preferably C 13-19 ). R a2 The alkyl group is preferably linear, branched or cyclic (more preferably linear or branched; further preferably linear).

[0071] Examples of the formula (a-2) include decanesulfonic acid, undecanesulfonic acid, dodecanesulfonic acid, tridecanesulfonic acid, tetradecanesulfonic acid, pentadecanesulfonic acid, hexadecanesulfonic acid, heptadecanesulfonic acid, octadecanesulfonic acid, nonadecanesulfonic acid, and the following compounds.

[0072]

[0073]

[0074] One of the benefits of the aqueous solution for manufacturing electronic devices of the present invention is the suppression of defects in the resist pattern after development. While not being limited by theory, it is believed that the presence of a sulfonic acid-derived moiety in component (A) ensures dispersibility in the aqueous solution, while the presence of other moieties reduces surface tension. It is believed that due to its high affinity for water in the aqueous solution for manufacturing electronic devices, component (A) is more likely to be present on the water side, thus preventing it from remaining in the photosensitive resin pattern, thereby reducing the risk of defects in the pattern.

[0075] The component (A) may be one type or a mixture of any two or more types.

[0076] The content of component (A) is preferably 0.001 to 10 mass % (more preferably 0.01 to 5 mass %; further preferably 0.01 to 1 mass %; further preferably 0.02 to 0.4 mass %) based on the aqueous solution for producing electronic devices.

[0077] Solvent (B)

[0078] The solvent (B) contains water, which is preferably deionized water.

[0079] Considering use in electronic device manufacturing processes (more preferably, semiconductor manufacturing processes), the solvent (B) is preferably a solvent with low impurities. The impurity concentration of the solvent (B) is preferably 1 ppm or less (more preferably 100 ppb or less; even more preferably 10 ppb or less).

[0080] Based on the solvent (B), the water content is preferably 90 to 100% by mass (more preferably 98 to 100% by mass; further preferably 99 to 100% by mass; and further preferably 99.9 to 100% by mass). As a preferred embodiment of the present invention, the solvent (B) is essentially composed of water. However, it is permitted as a preferred embodiment of the present invention that an additive is included in the aqueous solution for manufacturing an electronic device of the present invention in a state of being dissolved and / or dispersed in a solvent other than water (for example, a surfactant). As a more preferred embodiment of the present invention, the water content contained in the solvent (B) is 100% by mass.

[0081] As specific examples of solvent (B) other than water, preferred examples include cyclohexanone, cyclopentanone, propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol 1-monomethyl ether 2-acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, γ-butyrolactone, ethyl lactate, or any mixture thereof. These are preferred in terms of the storage stability of the solution. These solvents can be used by mixing two or more of them.

[0082] The content of the solvent (B) is preferably 80 to 99.999 mass % (more preferably 90 to 99.99 mass %; further preferably 95 to 99.99 mass %; further preferably 98 to 99.99 mass %) based on the aqueous solution for producing electronic devices.

[0083] The water content of the solvent (B) is preferably 80 to 99.99 mass % (more preferably 90 to 99.99 mass %; further preferably 95 to 99.99 mass %; further preferably 98 to 99.99 mass %) based on the aqueous solution for producing electronic devices.

[0084] Hydroxyl-containing compound (C)

[0085] The hydroxyl-containing compound (C) used in the present invention is represented by formula (c):

[0086]

[0087] Where,

[0088] R c1 、R c2 、R c3 and R c4 are independently hydrogen, fluorine or C 1-5 Alkyl (preferably each independently hydrogen, fluorine, methyl, ethyl, tert-butyl or isopropyl; more preferably each independently hydrogen, methyl or ethyl).

[0089] L c1 and L c2 Each independently is C 1-20 Alkylene, C 5-20 Cycloalkylene, C 2-4 Alkenylene, C 2-4 Alkynylidene or C 6-20 These groups may optionally be substituted with fluorine, C 1-5 Here, the so-called alkenylene group means a divalent hydrocarbon group having one or more double bonds, and the so-called alkynylene group means a divalent hydrocarbon group having one or more triple bonds. Preferably, L c1 and L c2 are each independently fluorinated C 1-5 Alkylene, C 2-4 Alkenylene, C 2-4 Alkyne or phenylene (C6 arylene); more preferably C substituted by fluorine 2-4 Alkylene, C2 alkenylene, C2 alkynylene or phenylene; more preferably C2 alkenylene or C2 alkynylene; most preferably C2 alkynylene (acetylene). The effects of the present invention can be obtained even without using a fluorine-containing component.

[0090] h is 0, 1 or 2 (preferably 0 or 1; more preferably 0).

[0091] Specific examples of the hydroxyl group-containing compound (C) include 3-hexyne-2,5-diol, 2,5-dimethyl-3-hexyne-2,5-diol, 3,6-dimethyl-4-octyne-3,6-diol, 1,4-butynediol, 2,4-hexadiyne-1,6-diol, 1,4-butanediol, 2,2,3,3-tetrafluoro-1,4-butanediol, 2,2,3,3,4,4,5,5-octafluoro-1,6-hexanediol, cis-1,4-dihydroxy-2-butene, 1,4-benzenedimethanol, 4,7-dihydroxy-2,4,7,9-tetramethyl-5-decyne, and combinations thereof.

[0092] The content of the hydroxyl group-containing compound (C) is preferably 0.001 to 10 mass % (more preferably 0.005 to 5 mass %; further preferably 0.01 to 1 mass %; further preferably 0.01 to 0.1 mass %) based on the aqueous solution for producing electronic devices.

[0093] Although not intending to be limited by theory, it is believed that the inclusion of the component (C) can suppress aggregation of the component (A) during the process of manufacturing an electronic device (eg, a resist pattern cleaning process).

[0094] The aqueous solution for manufacturing electronic devices of the present invention has the aforementioned (A), (B) and (C) components as essential components, but may contain more compounds as needed. This will be explained in detail below. In addition, based on the aqueous solution for manufacturing electronic devices, the components other than (A) to (C) (in the case of multiple components, their sum) in the entire composition are preferably 0 to 10% by mass (more preferably 0 to 5% by mass; further preferably 0 to 3% by mass; further preferably 0.0001 to 1% by mass). It is also a preferred embodiment of the present invention that the aqueous solution for manufacturing electronic devices of the present invention does not contain components other than (A) to (C) (0% by mass).

[0095] Nitrogen-containing compounds (D)

[0096] The aqueous solution for producing an electronic device of the present invention may further contain a nitrogen-containing compound (D). The nitrogen-containing compound (D) may have one or more nitrogen atoms in the compound.

[0097] By combining component (D) with the aqueous solution for manufacturing electronic devices of the present invention, pattern collapse can also be suppressed. Although not limited by theory, it is believed that the inclusion of the nitrogen-containing compound (D) can reduce the effect of component (A) on the resist pattern.

[0098] As (D)component, for example:

[0099] (i) Ammonia,

[0100] (ii) aliphatic primary amines having 1 to 16 carbon atoms and their derivatives (e.g., methylamine, ethylamine, isopropylamine, n-butylamine, tert-butylamine, cyclohexylamine, ethylenediamine, tetraethylenediamine, etc.),

[0101] (iii) aliphatic secondary amines having 2 to 32 carbon atoms and their derivatives (e.g., dimethylamine, diethylamine, methylethylamine, dicyclohexylamine, N,N-dimethylmethylenediamine, etc.),

[0102] (iv) Aliphatic tertiary amines having 3 to 48 carbon atoms and their derivatives (for example, trimethylamine, triethylamine, tripropylamine, dimethylethylamine, tricyclohexylamine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetraethylethylenediamine, N,N,N',N",N"-pentamethyldiethylenetriamine, tris[2-(dimethylamino)ethyl]amine, tris[2-(2-methoxyethoxy)ethyl]amine, etc.),

[0103] (v) Aromatic amines having 6 to 30 carbon atoms and their derivatives (e.g., aniline, benzylamine, naphthylamine, N-methylaniline, 2-methylaniline, 4-aminobenzoic acid, phenylalanine, etc.); and

[0104] (vi) Heterocyclic amines having 5 to 30 carbon atoms and their derivatives (for example, pyrrole, oxazole, thiazole, imidazole, 4-methylimidazole, pyridine, picoline, butylpyridine, etc.).

[0105] The component (D) is preferably selected from the group consisting of (i), (ii) and (iv), and more preferably selected from the group consisting of ammonia, n-butylamine, ethylenediamine, triethylamine, tripropylamine and N,N,N',N'-tetraethylethylenediamine.

[0106] The molecular weight of the component (D) is preferably 17 to 500 (more preferably 17 to 150; further preferably 60 to 143).

[0107] The content of component (D) is preferably 0.0001 to 1 mass % (more preferably 0.0005 to 0.5 mass %; even more preferably 0.0005 to 0.1 mass %) based on the aqueous solution for producing electronic devices. It is also an embodiment of the present invention that the aqueous solution for producing electronic devices does not contain component (D).

[0108] Surfactant (E)

[0109] The aqueous solution for manufacturing electronic devices of the present invention may further contain a surfactant (E). Component (E) is useful for improving coating properties and solubility. Component (E) is different from components (A), (C), and (D) described above.

[0110] Examples of the component (E) include polyoxyethylene alkyl ether compounds such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; polyoxyethylene alkylaryl ether compounds such as polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether; polyoxyethylene / polyoxypropylene block copolymer compounds; sorbitan fatty acid ester compounds such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan trioleate, and sorbitan tristearate; and polyoxyethylene sorbitan fatty acid ester compounds such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, and polyoxyethylene sorbitan tristearate. In addition, fluorine-based surfactants such as trade names EFTOP EF301, EF303, EF352 (Tohkem Products), trade names MAGAFACE F171, F173, R-08, R-30, R-2011 (DIC), Fluorad FC430, FC431 (Sumitomo 3M), trade names AsahiGuard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (AGC) and organosiloxane polymer KP341 (Shin-Etsu Chemical) can be mentioned.

[0111] The content of the component (E) is preferably 0.001 to 5% by mass (more preferably 0.005 to 1% by mass; further preferably 0.01 to 0.1% by mass) based on the aqueous solution for producing the electronic device.

[0112] It is also a preferred embodiment of the present invention that the component (E) is not contained.

[0113] Additives (F)

[0114] The aqueous solution for manufacturing electronic devices of the present invention may further contain an additive (F). In the present invention, the additive (F) comprises an acid, a base, a broad-spectrum germicide, an antibacterial agent, a preservative, or a fungicide. The acid in the additive (F) is different from component (A). The base in the additive (F) is different from component (D). The additive (F) more preferably contains an antibacterial agent (more preferably, it consists solely of an antibacterial agent).

[0115] Acids or bases can be used to adjust the pH of the treatment liquid and improve the solubility of additive components. Examples of the acid include aromatic carboxylic acids.

[0116] Component (F) may include an antibacterial agent, a bactericidal agent, a preservative, or a broad-spectrum fungicide, as needed. These chemicals can be used to prevent the growth of bacteria and fungi over time. Examples of these chemicals include alcohols such as phenoxyethanol and isothiazolinones. Bestcide (Nippon Soda) is a more effective antibacterial agent, bactericidal agent, and broad-spectrum fungicide.

[0117] The content of the additive (F) is preferably 0.0001 to 10 mass % (more preferably 0.0001 to 0.1 mass %; even more preferably 0.0002 to 0.001 mass %) based on the aqueous solution for manufacturing electronic devices. No additive (F) is also a preferred embodiment of the present invention.

[0118] The aqueous solution for manufacturing electronic devices of the present invention may be filtered with a filter to remove impurities and / or insoluble matter after its components are dissolved.

[0119] <Method for Manufacturing Resist Pattern>

[0120] The present invention also provides a method for producing a resist pattern using the aqueous solution for manufacturing electronic devices. The photosensitive resin composition (resist composition) used in this method can be either positive or negative; the positive type is more preferred. A representative method for producing a resist pattern using the aqueous solution for manufacturing electronic devices of the present invention comprises the following steps:

[0121] (1) applying a photosensitive resin composition to a substrate with one or more intermediate layers or without an intermediate layer to form a photosensitive resin layer;

[0122] (2) exposing the photosensitive resin layer to radiation;

[0123] (3) developing the exposed photosensitive resin layer; and

[0124] (4) The developed layer is washed with the above aqueous solution for manufacturing electronic devices.

[0125] The following describes this in detail.

[0126] First, a photosensitive resin composition is applied (e.g., laminated) on top of a substrate such as a silicon substrate or a glass substrate that has been pretreated as needed to form a photosensitive resin layer. A known method can be used for lamination, but a coating method such as spin coating is preferred. The photosensitive resin composition can be laminated directly on the substrate or laminated via one or more intermediate layers (e.g., BARC). Alternatively, an antireflection film (e.g., TARC) can be laminated on top of the photosensitive resin layer (on the opposite side to the substrate). Layers other than the photosensitive resin layer will be described later. By pre-forming an antireflection film on top of or below the photosensitive resin film, the cross-sectional shape and exposure margin can be improved.

[0127] Representative examples of positive- or negative-working photosensitive resin compositions used in the resist pattern production method of the present invention include compositions comprising a quinonediazide-based photosensitizer and an alkali-soluble resin, and chemically amplified photosensitive resin compositions. From the perspective of forming high-resolution, fine resist patterns, chemically amplified photosensitive resin compositions are preferred, such as chemically amplified PHS-acrylate hybrid EUV resist compositions. Positive-working photosensitive resin compositions are more preferred.

[0128] While not being limited by theory, the inventors believe the following: While EUV exposure resist compositions are intended to form finer resist patterns, the properties of these resist compositions (e.g., high hydrophobicity) make defects more likely to form in the resulting resist patterns. It is believed that the use of the aqueous solution of the present invention can prevent these defects and allow for the cleaning of fine resist patterns.

[0129] Examples of the quinonediazide photosensitizer used in the positive-type photosensitive resin composition containing the quinonediazide photosensitizer and the alkali-soluble resin include 1,2-benzoquinonediazide-4-sulfonic acid, 1,2-naphthoquinonediazide-4-sulfonic acid, 1,2-naphthoquinonediazide-5-sulfonic acid, esters or amides of these sulfonic acids, and examples of the alkali-soluble resin include copolymers of polyvinylphenol, polyvinyl alcohol, acrylic acid, or methacrylic acid.

[0130] Examples of chemically amplified photosensitive resin compositions include positive-working chemically amplified photosensitive resin compositions comprising a compound that generates an acid upon irradiation with radiation (photoacid generator), and a resin whose polarity increases under the action of the acid generated by the photoacid generator and whose solubility in a developer differs between exposed and unexposed areas; or negative-working chemically amplified photosensitive resin compositions comprising an alkali-soluble resin, a photoacid generator, and a crosslinking agent, wherein the crosslinking agent crosslinks the resin under the action of an acid, and whose solubility in a developer differs between exposed and unexposed areas.

[0131] Examples of resins whose polarity increases under the action of acid and whose solubility in a developer differs between exposed and unexposed areas include resins having groups on the main chain, side chain, or both the main chain and side chain that decompose upon the action of acid to generate alkali-soluble groups. Representative examples include polymers obtained by introducing acetal or ketal groups as protective groups into hydroxystyrene polymers (PHS) (e.g., Japanese Patent Application Laid-Open No. 2-19847), and similar polymers obtained by introducing tert-butoxycarbonyloxy or p-tetrahydropyranyloxy groups as acid-degradable groups (e.g., Japanese Patent Application Laid-Open No. 2-209977).

[0132] The photoacid generator may be any compound that generates an acid upon exposure to radiation, and examples thereof include onium salts such as diazonium salts, ammonium salts, phosphonium salts, iodonium salts, sulfonium salts, selenium salts, and arsonium salts; organic halogen compounds, organic metal / organic halides, photoacid generators having an o-nitrobenzyl-type protecting group; compounds that generate sulfonic acid upon photolysis, such as imidosulfonates; disulfone compounds, diazoketonesulfones, and diazoniumdisulfone compounds. Furthermore, compounds obtained by introducing these groups or compounds that generate an acid upon exposure to radiation into the main chain or side chain of a polymer may also be used.

[0133] The chemically amplified photosensitive resin composition may further contain an acid-decomposable dissolution inhibitory compound, a dye, a plasticizer, a surfactant, a photosensitizer, an organic basic compound, and a compound that promotes solubility in a developer, as needed.

[0134] The photosensitive resin composition is applied to a substrate using an appropriate coating apparatus such as a spin coater or a coating machine, and then heated to remove the solvent from the photosensitive resin composition, thereby forming a photosensitive resin layer. The heating temperature is preferably 70 to 150°C (more preferably 90 to 150°C). The heating time is preferably 10 to 600 seconds (more preferably 10 to 180 seconds; even more preferably 30 to 120 seconds).

[0135] In the resist pattern manufacturing method of the present invention, the presence of films and layers other than the photosensitive resin layer is also allowed. The substrate and the photosensitive resin layer may be separated by an intermediate layer without direct contact. The intermediate layer is a layer formed between the substrate and the photosensitive resin layer, also referred to as a lower film. Examples of the lower film include: substrate modification film, planarization film, lower anti-reflection film (BARC), inorganic hard mask intermediate layer (silicon oxide film, silicon nitride film and silicon oxide nitride film), and adhesion film. Planarization film, such as SOC. Regarding the formation of the inorganic hard mask intermediate layer, reference may be made to Japanese Patent No. 5336306. The intermediate layer may be composed of one layer or multiple layers. In addition, an upper film may be formed on the photosensitive resin layer. The upper film is, for example, an upper anti-reflection film (TARC).

[0136] In the process for producing a resist pattern of the present invention, the layer structure can be determined using a known technique depending on the process conditions, and examples thereof include the following layer structures.

[0137] Substrate / photosensitive resin layer

[0138] Substrate / underlayer film / photosensitive resin layer

[0139] Substrate / planarization film / photosensitive resin layer

[0140] Substrate / planarization film / photosensitive resin layer / upper film

[0141] Substrate / planarization film / BARC / photosensitive resin layer

[0142] Substrate / planarization film / photosensitive resin layer / upper film

[0143] Substrate / planarization film / inorganic hard mask intermediate layer / photosensitive resin layer

[0144] Substrate / planarization film / adhesion film / photosensitive resin layer

[0145] Substrate / substrate modification layer / planarization film / photosensitive resin layer

[0146] Substrate / Substrate modification layer / Planarization film / Adhesion film / Photosensitive resin layer

[0147] These layers can be cured by heating and / or exposure after coating, or formed using a known method such as CVD. These layers can be removed by a known method (etching, etc.), and the layers above each can be used as a mask for patterning.

[0148] In a preferred embodiment of the present invention, the photosensitive resin composition is applied directly to the substrate without an intermediate layer. In another embodiment of the present invention, no TARC is formed on the photosensitive resin layer.

[0149] As another embodiment of the present invention, as described in WO2022 / 129015, a thickened layer is formed on the photosensitive resin layer to form a thickened resist pattern.

[0150] The photosensitive resin layer is exposed through a specific mask. When other layers are included (such as the upper film), exposure can also be performed simultaneously. The wavelength of the radiation (light) used for exposure is not particularly limited, but it is preferably exposed with light with a wavelength of 13.5 to 248 nm. Specifically, KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), and extreme ultraviolet light (EUV, wavelength 13.5 nm) can be used, and EUV is more preferred. These wavelengths allow a range of ±5%, preferably a range of ±1%. After exposure, post-exposure heating (PEB) can be performed as needed. The temperature of PEB is preferably 70 to 150°C (more preferably 80 to 120°C), and the heating time is preferably 0.3 to 5 minutes (more preferably 0.5 to 2 minutes).

[0151] Next, development is performed using a developer. The development of the resist pattern manufacturing method of the present invention is preferably performed using a 2.38% by mass (±1% tolerance) tetramethylammonium hydroxide (TMAH) aqueous solution. In addition, a surfactant or the like may be added to these developers. 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 20 to 60 seconds). As a development method, known methods such as paddle / puddle development can be used.

[0152] As described above, the resist pattern of the present invention includes not only a resist pattern obtained by exposing and developing a resist film but also a resist pattern in which the wall is thickened by further covering with other layers or films.

[0153] The resist pattern (developed photosensitive resin layer) formed up to the above steps is in an unwashed state. The resist pattern can be cleaned using the aqueous solution for manufacturing electronic devices of the present invention. The time for the aqueous solution for manufacturing electronic devices to contact the resist pattern, that is, the treatment time, is preferably more than 1 second. In addition, the treatment temperature can also be arbitrary. The method for bringing the aqueous solution for manufacturing electronic devices into contact with the resist is also arbitrary, for example, by immersing the resist substrate in the aqueous solution for manufacturing electronic devices, or by dripping the aqueous solution for manufacturing electronic devices on the surface of a rotating resist substrate.

[0154] In the method for manufacturing resist pattern of the present invention, before and / or after the aqueous solution for utilizing electronic devices to carry out cleaning treatment, the resist pattern after development can be cleaned with other cleaning solutions.Other cleaning solutions are preferably water, more preferably pure water (DW, deionized water, etc.).The cleaning before this treatment is useful in order to clean the developer attached to the resist pattern.The cleaning after this treatment is useful in order to clean the aqueous solution for manufacturing electronic devices.By injecting pure water to the resist pattern after development and replacing the developer, cleaning the pattern simultaneously, further while maintaining the state of soaking the pattern with pure water, by injecting the aqueous solution for manufacturing electronic devices and replacing pure water, cleaning the pattern simultaneously, this method is a preferred embodiment of manufacturing method of the present invention.

[0155] Cleaning with the aqueous solution for manufacturing electronic devices can also be performed by a known method.

[0156] For example, the resist substrate can be immersed in an aqueous solution for manufacturing electronic devices, or the aqueous solution for manufacturing electronic devices can be dropped onto the surface of a rotating resist substrate. These methods can also be appropriately combined.

[0157] One of the conditions that easily causes pattern collapse is the narrowest distance between the walls of the resist pattern. In the case where the walls of the resist pattern are parallel to each other, this is a harsh condition. In this specification, the spacing distance at the smallest distance on a circuit unit is defined as the minimum spatial dimension. A circuit unit preferably becomes a semiconductor in a subsequent step. In addition, an embodiment in which a semiconductor includes one circuit unit in the horizontal direction and multiple circuit units in the vertical direction is also preferred. Of course, if the frequency of occurrence of the narrow distance between the walls is low, unlike the test sample, the frequency of defects is reduced, and therefore the frequency of defective products is reduced.

[0158] In the present invention, the minimum space size of the resist pattern in one circuit unit is preferably 5 to 30 nm, more preferably 10 to 20 nm, and even more preferably 10 to 17 nm.

[0159] <Method of manufacturing device>

[0160] The device manufacturing method of the present invention includes: a method for manufacturing a resist pattern using an aqueous solution for manufacturing an electronic device. Preferably, the device manufacturing method of the present invention includes: etching using the resist pattern manufactured by the above method as a mask and processing a substrate.

[0161] After processing, the resist film is peeled off as needed. Preferably, the device is a semiconductor.

[0162] In the manufacture method of the present invention, the intermediate layer and / or substrate can be processed by etching using the resist pattern as a mask. For etching, known methods such as dry etching and wet etching can be used, and dry etching is more suitable. For example, the resist pattern can be used as an etching mask to etch the intermediate layer, and the intermediate layer pattern obtained can be used as an etching mask to etch the substrate, thereby processing the substrate. In addition, the resist pattern can also be used as an etching mask to etch the layer (such as the intermediate layer) below the resist layer, while directly etching the substrate. The processed substrate becomes, for example, a patterned substrate. The formed pattern can be utilized to form wiring on the substrate.

[0163] These layers are preferably removable by dry etching with O2, CF4, CHF3, Cl2 or BCl3, preferably O2 or CF4.

[0164] As a preferred embodiment, the method for manufacturing a device of the present invention further includes forming wiring on the processed substrate.

[0165] <Stress applied to the resist wall>

[0166] As described in Namatsu et al. Appl. Phys. Lett. 1995 (66) p2655-2657, and schematically as Figure 1 As shown, the stress applied to the wall during rinsing and drying can be expressed by the following formula:

[0167] σ max =(6γcosθ / D)x(H / W) 2

[0168] Where,

[0169] σ max : Maximum stress applied to the resist,

[0170] γ: surface tension of the wash,

[0171] θ: contact angle,

[0172] D: the interval between the walls,

[0173] H: height of the wall,

[0174] W: Width of the wall.

[0175] These lengths can be determined by known methods, for example by SEM photographs.

[0176] From the above formula, we can see that the shorter D or W is, the more stress will be caused. In this specification, the so-called "spacing size" is as follows: Figure 1 The description means one unit in the resist pattern unit array having W and D.

[0177] This means that the finer the resist pattern (the narrower the pitch size), the greater the stress applied to the resist pattern. As such, the finer the pattern, the more stringent the conditions, and the more improvements are needed in aqueous solutions (such as rinse compositions) used to manufacture electronic devices.

[0178] The present invention will be described below with reference to the following examples. However, the present invention is not limited to these examples.

[0179] <Preparation Example of Example 11>

[0180] Decanesulfonic acid as the sulfonic acid derivative (A) was added to deionized water to a concentration of 2,000 ppm, and 3-hexyne-2,5-diol as the hydroxyl-containing compound (C) was added to a concentration of 800 ppm. The mixture was stirred. Complete dissolution was visually confirmed. The solution was filtered (pore size = 10 nm) to obtain the aqueous solution of Example 11.

[0181] <Preparation Examples of Examples 12 to 17, Comparative Examples 11 to 14, and Reference Example 11>

[0182] Using the sulfonic acid derivative (A), hydroxyl group-containing compound (C) and nitrogen-containing compound (D) described in Table 1, aqueous solutions of Examples 12 to 17, Comparative Examples 11 to 14 and Reference Example 11 were prepared in the same manner as in the preparation example of Example 11 above, so that the concentrations thereof were as described in Table 1.

[0183] Comparative Example 14 is an example in which deionized water without any addition of any substance was filtered.

[0184] [Table 1]

[0185]

[0186] In Tables 1 to 3, A1: decanesulfonic acid,

[0187]

[0188] A2: Tetradecanesulfonic acid,

[0189]

[0190] A3: Dodecylbenzenesulfonic acid,

[0191]

[0192] A4: Alkylsulfonic acid mixture (a mixture of the following structures having 13 to 18 carbon atoms),

[0193]

[0194] A5: Alkylbenzenesulfonic acid mixture (a mixture of the following structures having 13 to 18 carbon atoms in the alkyl chain)

[0195]

[0196] ·comp.A6: 2-methylhexanoic acid,

[0197]

[0198] C1: 3-hexyne-2,5-diol,

[0199] C2: 2,5-dimethyl-3-hexyne-2,5-diol,

[0200] C3: 3,6-dimethyl-4-octyne-3,6-diol,

[0201] C4: 4,7-dihydroxy-2,4,7,9-tetramethyl-5-decyne,

[0202] C5: cis-2-butene-1,4-diol,

[0203] ·comp.C6: is a compound of the following structure, and R a1 is methyl; R a2 is isobutyl; EO is ethylene oxide; PO is propylene oxide; r11, s11, r21 and s21 are integers satisfying r11+r21=3.5 and s11+s21=0, respectively.

[0204]

[0205] ·comp.C7: a compound having the above structure, and R a1 is methyl; R a2 is isobutyl; EO is ethylene oxide; PO is propylene oxide; r11, s11, r21 and s21 are integers satisfying r11+r21=5 and s11+s21=2, respectively.

[0206] <Defect evaluation (1)>

[0207] A silicon substrate was treated with hexamethyldisilazane (HMDS) at 90°C for 30 seconds. A PHS-acrylate chemically amplified resist for EUV was applied thereon by spin coating and heated on a hot plate at 110°C for 60 seconds to obtain a resist film with a thickness of 35 nm. Afterwards, a 2.38% by mass TMAH aqueous solution of the developer was poured in and kept for 30 seconds (suspension immersion method). The developer began to flow in a covered liquid state, and the developer was replaced with water while the substrate was rotated. When it was covered with water, it was stopped. Afterwards, in a water-covered liquid state, the aqueous solution of Example 11 was poured in while the substrate was rotated at a low speed for 30 seconds while being washed, and the aqueous solution of Example 11 was replaced with water. The substrate was rotated at a high speed and dried to obtain a cleaned resist film.

[0208] The surface of the cleaned resist film was observed using a defect inspection device LS9110 (Hitachi High-Technologies), and the number of foreign particles adhering to the resist film surface was counted. The results are shown in Table 1.

[0209] Regarding the aqueous solutions of Examples 12 to 17, Comparative Examples 11 to 14, and Reference Example 11, evaluation was performed in the same manner as above using each aqueous solution to prepare a substrate, and the number of foreign matter was counted.

[0210] Comparative Example 14 is different from Example 11 in that the substrate is spin-dried immediately after being coated with water, but otherwise the same as Example 11.

[0211] <Preparation Examples of Examples 21 to 27 and Comparative Example 21>

[0212] Using the sulfonic acid derivative (A), hydroxyl group-containing compound (C) and nitrogen-containing compound (D) described in Table 2, aqueous solutions of Examples 21 to 27 and Comparative Example 21 were prepared in the same manner as in the preparation example of Example 11 above to have the concentrations described in Table 2.

[0213] Comparative Example 21 is an example in which deionized water without any additions was filtered.

[0214] [Table 2]

[0215]

[0216] <Defect Evaluation (2)>

[0217] A silicon substrate was treated with HMDS at 90°C for 30 seconds. A PHS-acrylate chemically amplified resist for EUV was applied by spin coating and heated on a hotplate at 110°C for 60 seconds to produce a 35nm thick resist film. The substrate was exposed through a mask (18nm line / space 1:1) using an EUV exposure system (NXE:3400, ASML). PEB was then performed on a hotplate at 110°C for 60 seconds. A 2.38% by mass TMAH aqueous solution was added as a developer and held for 30 seconds. The developer began to flow while the substrate was covered with water. The developer was replaced with water while the substrate was rotated, and the flow was stopped when the developer was covered with water. Then, while the substrate was covered with water, the aqueous solution of Example 21 was added and washed while rotating at low speed for 30 seconds, replacing the aqueous solution of Example 21 with water. The substrate was rotated at high speed and dried to produce a cleaned resist pattern.

[0218] The number of foreign particles adhering to the cleaned resist pattern surface was counted using a UVision4 defect inspection system (Applied Materials), and the shape of the foreign particles was observed using an eDR7280 defect observation system (KLA-Tencor). Evaluation was performed based on the following criteria. The results are shown in Table 2.

[0219] A: The number of defects is less than 30% relative to the number of foreign matter in Comparative Example 21.

[0220] B: The number of defects is 30% or more and less than 100% relative to the number of foreign matter in Comparative Example 21.

[0221] C: The number of defects is 100% or more and less than 300% relative to the number of foreign matter in Comparative Example 21.

[0222] D: All patterns are dissolved.

[0223] Regarding the aqueous solutions of Examples 22 to 27, evaluation substrates were prepared in the same manner as above using each aqueous solution, and the evaluation was performed based on the above-mentioned criteria.

[0224] Comparative Example 21 is different from Example 21 in that the substrate is spin-dried immediately after being covered with water, but other than that, the same procedures are followed.

[0225] <Number of pattern collapse>

[0226] The same procedure as in defect evaluation (2) was carried out to obtain a cleaned resist pattern.

[0227] The number of collapsed patterns in the cleaned resist patterns was counted using a defect inspection system, UVision4 (Applied Materials), and a defect observation system, eDR7280 (KLA-Tencor). The results are shown in Table 2.

[0228] <Limited pattern size>

[0229] A silicon substrate was treated with HMDS at 90°C for 30 seconds. A PHS-acrylate chemically amplified resist for EUV was applied by spin coating and heated on a hotplate at 110°C for 60 seconds to form a 50nm thick resist film. The substrate was exposed through a mask (16nm line / space 1:1) using an EUV exposure system (NXE:3400, ASML). The exposure dose was varied to alter the resulting line width. PEB was then performed on a hotplate at 110°C for 60 seconds. A 2.38% by mass TMAH aqueous solution was added as a developer and held for 30 seconds. The developer began to flow while the substrate was covered with water. The developer was replaced with water while the substrate was rotated, and the flow was stopped when the substrate was covered with water. Then, while the substrate was covered with water, the aqueous solution of Example 21 was added and rinsed while rotating at low speed for 30 seconds. The aqueous solution of Example 21 was replaced with water. The substrate is rotated at high speed and dried to obtain a cleaned resist pattern.

[0230] The cleaned resist pattern was observed using a CG6300 SEM (Hitachi High-Technologies) to check line width and pattern collapse. The minimum line width without pattern collapse was defined as the "limit pattern size." The results are shown in Table 2.

[0231] Regarding the aqueous solutions of Examples 22 to 27, the "limit pattern size" was obtained in the same manner as described above using each aqueous solution.

[0232] Comparative Example 21 differed from Example 21 in that the substrate was spin-dried immediately after being coated with water, but otherwise was identical. In this case, pattern collapse was observed at a line width of 16.4 nm. However, no collapse was observed at a line width of 16.8 nm, so the limit pattern size was set to 16.8 nm.

[0233] <Preparation Examples of Examples 31 to 34 and Comparative Example 31>

[0234] Using the sulfonic acid derivative (A), hydroxyl group-containing compound (C) and nitrogen-containing compound (D) described in Table 3, the aqueous solutions of Examples 31 to 34 and Comparative Example 31 were prepared in the same manner as in the preparation example of Example 11 above to have the concentrations described in Table 3.

[0235] Comparative Example 31 is an example in which deionized water without any additions was filtered.

[0236] [Table 3]

[0237]

[0238] LWR's review

[0239] The same method as the above-mentioned limit pattern size measurement was used to obtain a cleaned resist pattern with a line width of 16.0 nm. The LWR (Line Width Roughness) of the cleaned resist pattern was measured using a length measurement SEM CG5000. The results are reported in Table 2.

[0240] Comparative Example 31 shows the measurement results when the line width was 16.8 nm.

Claims

1. An aqueous solution for manufacturing electronic devices, comprising: Sulfonic acid derivatives (A); solvent (B); and a hydroxyl group-containing compound (C); in, The sulfonic acid derivative (A) is represented by formula (a): Where, A1 is C 3-30 A hydrocarbon group, which may be substituted with a halogen; α is 1 or 2; X α+ H + NH4 + , or α-valent metal ions, The solvent (B) contains water; and The hydroxyl-containing compound (C) is represented by formula (c): Where, R c1 、R c2 、R c3 and R c4 are each independently hydrogen, fluorine or C 1-5 alkyl; L c1 and L c2 Each independently is C 1-20 Alkylene, C 5-20 Cycloalkylene, C 2-4 Alkenylene, C 2-4 Alkynylidene or C 6-20 Arylene; and these groups may be substituted with fluorine, C 1-5 an alkyl group or a hydroxy group; and h is 0, 1 or 2.

2. The aqueous solution for manufacturing electronic devices according to claim 1, wherein A1 is an alkyl group, an alkyl group substituted with a phenyl group, or a phenyl group substituted with an alkyl group; Optionally, the alkyl group contained in A1 is a linear, branched or cyclic alkyl group.

3. The aqueous solution for manufacturing an electronic device according to claim 1 or 2, wherein the content of the sulfonic acid derivative (A) is 0.001 to 10% by mass based on the aqueous solution for manufacturing an electronic device; Optionally, the content of the solvent (B) is 80 to 99.999% by mass based on the aqueous solution for manufacturing electronic devices; Optionally, the solvent (B) contains water in an amount of 80 to 99.999% by mass based on the aqueous solution for manufacturing electronic devices; or Optionally, the content of the hydroxyl group-containing compound (C) is 0.001 to 10% by mass based on the aqueous solution for manufacturing electronic devices.

4. The aqueous solution for producing an electronic device according to one or more of claims 1 to 3, further comprising a nitrogen-containing compound (D); Optionally, the aqueous solution for manufacturing an electronic device further comprises a surfactant (E).

5. The aqueous solution for producing an electronic device according to one or more of claims 1 to 4, further comprising an additive (F); in, The additive (F) comprises an acid, a base, a broad-spectrum bactericide, an antimicrobial agent, a preservative, or a fungicide; Optionally, the content of the nitrogen-containing compound (D) is 0.0001 to 1% by mass based on the aqueous solution for manufacturing electronic devices; Optionally, the content of the surfactant (E) is 0.001 to 5% by mass based on the aqueous solution for manufacturing electronic devices; or Optionally, the content of the additive (F) is 0.0001 to 10% by mass based on the aqueous solution for manufacturing electronic devices.

6. The aqueous solution for producing electronic devices according to one or more of claims 1 to 5, which is an aqueous solution for producing semiconductors: Optionally, the aqueous solution for manufacturing electronic devices is an aqueous solution for manufacturing semiconductor substrates; Optionally, the aqueous solution for manufacturing electronic devices is a cleaning solution for semiconductor substrate manufacturing processes; Optionally, the aqueous solution for manufacturing electronic devices is a photolithography cleaning solution; or Optionally, the aqueous solution for manufacturing electronic devices is a resist pattern cleaning solution.

7. A method for producing a resist pattern using the aqueous solution for producing an electronic device according to one or more of claims 1 to 6.

8. A method for manufacturing a resist pattern, comprising the steps of: (1) applying a photosensitive resin composition to a substrate with one or more intermediate layers or without an intermediate layer to form a photosensitive resin layer; (2) exposing the photosensitive resin layer to radiation; (3) developing the exposed photosensitive resin layer; and (4) The developed layer is washed with the aqueous solution for manufacturing electronic devices according to one or more of claims 1 to 6. 9 . The method for manufacturing a resist pattern according to claim 8 , wherein the photosensitive resin composition is a chemically amplified photosensitive resin composition, and optionally, extreme ultraviolet light is used for exposure.

10. The method for manufacturing a resist pattern according to one or more of claims 7 to 9, wherein a minimum space size of the resist pattern in one circuit unit is 5 to 30 nm.

11. A method for manufacturing a device, comprising the method for manufacturing a resist pattern according to one or more of claims 7 to 10.

12. The method for manufacturing a device according to claim 11, further comprising the steps of: The substrate is processed by etching using the resist pattern produced by the method according to one or more of claims 7 to 10 as a mask.

13. The method for manufacturing a device according to claim 11 or 12, further comprising: Wiring is formed on the processed substrate.

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