Electronic device manufacturing solution, resist pattern manufacturing method, and device manufacturing method

Abstract

To provide a liquid for manufacturing electronic devices, a method for manufacturing a resist pattern, and a method for manufacturing a device.

Description

[Technical field]

[0001] The present invention relates to a liquid for manufacturing electronic devices, a method for manufacturing a resist pattern, and a method for manufacturing a device. [Background technology]

[0002] In recent years, the need for high integration of LSIs has been increasing, and finer patterns are being demanded. In order to meet such needs, lithography processes using short-wavelength light such as KrF excimer laser (248 nm), ArF excimer laser (193 nm), extreme ultraviolet light (EUV; 13 nm), X-rays, electron beams, etc. are being put to practical use. In order to meet such 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 light with a short wavelength, the production yield, such as collapse of the fine pattern, becomes a problem because a very fine structure is created.

[0003] In this situation, Patent Document 1 discusses a rinse solution for lithography that is excellent in performance such as pattern collapse margin, defects, and LWR, similar to conventional systems containing surfactants, and also has excellent melting properties.

[0004] As another attempt, the use of a surfactant containing fluorine has been investigated (Patent Document 2 and Patent Document 3). [Prior art documents] [Patent documents]

[0005] [Patent Document 1] JP 2014-219577 A [Patent Document 2] International Publication No. 2018 / 095885 [Patent Document 3] International Publication No. 2017 / 220479 Summary of the Invention [Problem to be solved by the invention]

[0006] The inventors have found that there are one or more problems that still require improvement, such as the following: reducing defects in a fine resist pattern; suppressing the occurrence of bridges in a resist pattern; preventing the resist pattern from collapsing in a fine resist pattern; suppressing non-uniformity in the resist pattern width; reducing residues after removing the electronic device manufacturing liquid; reducing the surface tension of the electronic device manufacturing liquid; providing an electronic device manufacturing liquid with little environmental impact; providing an electronic device manufacturing liquid with low handling risk; providing an electronic device manufacturing liquid with excellent storage stability (e.g., long-term storage); providing an electronic device manufacturing liquid with little effect on the resist pattern. The present invention has been made based on the above-mentioned technical background, and provides a solution for manufacturing electronic devices. [Means for solving the problem]

[0007] The electronic device manufacturing solution according to the present invention comprises: Anionic surfactant (A), A solvent (B), and Quaternary Ammonium Compounds (C) The present invention comprises at least

[0008] The method for producing a resist pattern according to the present invention uses the above-mentioned electronic device manufacturing liquid.

[0009] The method for producing a resist pattern according to the present invention comprises the following steps. (1) applying a photosensitive resin composition to a substrate, with or without one or more intermediate layers, to form a photosensitive resin layer; (2) exposing the photosensitive resin layer to radiation; (3) developing the exposed photosensitive resin layer; and (4) Rinse the developed layer with the electronics manufacturing fluids described above.

[0010] The device manufacturing method according to the present invention comprises the above-mentioned method for manufacturing a resist pattern. Effect of the Invention

[0011] By using the electronic device manufacturing solution according to the present invention, one or more of the following effects can be expected. It is possible to reduce defects in fine resist patterns. It is possible to suppress the occurrence of bridges in the resist pattern. It is possible to prevent the resist pattern from collapsing in a fine resist pattern. It is possible to suppress non-uniformity in the width of the resist pattern. It is possible to reduce residues after removing the electronic device manufacturing liquid. It is possible to reduce the surface tension of the electronic device manufacturing liquid. It is possible to reduce the environmental impact of the electronic device manufacturing liquid. It is possible to reduce the danger of handling the electronic device manufacturing liquid. It is possible to improve the storage stability of the electronic device manufacturing liquid. It is possible to reduce the impact of the electronic device manufacturing liquid on the resist pattern. [Brief description of the drawings]

[0012] [Figure 1] FIG. 1 is a schematic diagram showing a state in which a resist wall is being rinsed. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0013] The embodiment of the present invention will be described in detail below.

[0014] [Definition] In this specification, unless otherwise specifically stated, the definitions and examples set forth in this paragraph shall be followed. The singular includes the plural, and "a" or "the" means "at least one." An element of a concept may 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 the elements as well as its use alone. 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 an alkyl chain 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. These copolymerizations may be alternating copolymerization, random copolymerization, block copolymerization, graft copolymerization, or a mixture of these. When polymers or resins are shown by structural formulas, the n or m in parentheses indicates the number of repeats. Temperature is measured in degrees Celsius. For example, 20 degrees means 20 degrees Celsius. The additive refers to a compound having that function (for example, in the case of a base generator, it is a compound that generates a base). The compound may be 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 according to the present invention as the solvent (B) or another component.

[0015] <Electronic device manufacturing fluid> The electronic device manufacturing fluid according to the present invention comprises at least an anionic surfactant (A), a solvent (B), and a quaternary ammonium compound (C). Here, the electronic device manufacturing liquid is used during the process of manufacturing electronic devices. It is sufficient that the liquid is used in the manufacturing process of electronic devices, and it may be removed or lost during the process. Examples of electronic devices include display devices, LEDs, and semiconductor devices. The electronic device manufacturing liquid is preferably an electronic device manufacturing aqueous solution, more preferably a semiconductor substrate manufacturing aqueous solution, more preferably a semiconductor substrate manufacturing process cleaning liquid, further preferably a lithography cleaning liquid, and even further preferably a resist pattern cleaning liquid. In one embodiment of the present invention, the electronic device manufacturing liquid is a rinse composition used for rinsing an exposed and developed resist pattern.

[0016] Anionic surfactant (A) The electronic device manufacturing liquid according to the present invention contains an anionic surfactant (A) (hereinafter, sometimes referred to as component (A). The same applies to other components.) Component (A) is not particularly limited as long as it is a compound having a lipophilic group and a hydrophilic group, and the hydrophilic portion dissociates into anions. One of the effects of component (A) is that it helps prevent the resist pattern from collapsing after development. This is thought to be due to the surfactant effect of component (A) increasing the contact angle between the resist pattern and the electronic device manufacturing fluid. Examples of the hydrophilic group of the component (A) include carboxylates, sulfonates, sulfates, and phosphates, with carboxylates being preferred. The component (A) is preferably a carboxy-containing compound, more preferably an alkyl carboxylic acid compound, and even more preferably a compound represented by formula (a).

[0017] Equation (a) is as follows: R a1 -COOH(a) Where: R a1 is C 3-12 Alkyl, preferably linear or branched C 3-10 alkyl, more preferably linear or branched C 3-9 Alkyl, even more preferably linear or branched C 3-8 It is an alkyl. It is believed that the alkyl in formula (a) can reduce the surface tension of the electronics manufacturing fluid and the carboxy can improve the solubility of the electronics manufacturing fluid, thereby providing a better balance between solubility and low surface tension.

[0018] Specific examples of component (A) include 2-methylpropanoic acid, n-butanoic acid, 2-methylbutanoic acid, n-pentanoic acid, n-hexanoic acid, n-heptanoic acid, n-octanoic acid, 2-methylpentanoic acid, 2-methylhexanoic acid, 5-methylhexanoic acid, 2-methylheptanoic acid, 4-methyl-n-octanoic acid, 2-ethylhexanoic acid, 2-propylpentanoic acid, 2,2-dimethylpentanoic acid, and 3,5,5-trimethylhexanoic acid.

[0019] The content of the component (A) is preferably 0.01 to 10 mass %, more preferably 0.02 to 5 mass %, and even more preferably 0.02 to 1 mass %, based on the electronic device manufacturing fluid.

[0020] Solvent (B) The electronics manufacturing fluid according to the present invention comprises a solvent (B). The solvent (B) preferably comprises water. The water is preferably deionized water. Considering that the solvent (B) is used in the manufacturing process of electronic devices, it is preferable that the solvent (B) has a small amount of impurities. The impurity concentration of the solvent (B) is preferably 1 ppm or less, more preferably 100 ppb or less, and further preferably 10 ppb or less. The content of water based on the solvent (B) is preferably 90 to 100 mass%, more preferably 98 to 100 mass%, even more preferably 99 to 100 mass%, and even more preferably 99.9 to 100 mass%. In one preferred embodiment of the present invention, the solvent (B) consists essentially of water. However, a preferred embodiment of the present invention is one in which an additive is dissolved and / or dispersed in a solvent other than water and contained in the electronic device manufacturing liquid of the present invention. In a more preferred embodiment of the present invention, the content of water in the solvent (B) is 100 mass%.

[0021] Specific examples of the solvent (B) other than water 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, and mixtures thereof. These are preferred in terms of the storage stability of the solution. Two or more of these solvents can also be mixed and used.

[0022] The content of component (B) is preferably 80 to 99.99 mass%, more preferably 90 to 99.99 mass%, even more preferably 95 to 99.99 mass%, and still more preferably 98 to 99.99 mass%, based on the electronic device manufacturing fluid. The content of water contained in the solvent (B) is preferably 80 to 99.99 mass %, more preferably 90 to 99.99 mass %, even more preferably 95 to 99.99 mass %, and still more preferably 98 to 99.99 mass %, based on the electronic device manufacturing liquid.

[0023] Quaternary Ammonium Compounds (C) The electronic device manufacturing fluid according to the present invention comprises a quaternary ammonium compound (C). An example of the component (C) is a quaternary ammonium hydroxide. It is believed that the inclusion of component (C) in electronic device manufacturing fluids can significantly improve the effects of preventing defects and collapse. Without being bound by theory, it is believed that this is because component (C) is highly basic, and therefore has a large effect of ionizing component (A).

[0024] The component (C) is preferably a quaternary ammonium hydroxide, and more preferably represented by the following formula (c): [ka] Where: R c1 , R c2 , R c3 , and R c4 are each independently -halogen; -unsubstituted or halogen, C 3-25 Cycloalkyl, C 4-25 Aryl or hydroxy substituted linear or branched C 1-25 Alkyl; -unsubstituted or halogen, linear or branched C 1-25 Alkyl, C 3-25 Cycloalkyl, C 4-25 Aryl or hydroxy substituted linear or branched C 2-25 of alkenylene; -unsubstituted or halogen, linear or branched C 1-25 Alkyl, C 4-25 aryl or hydroxy substituted C 3-25 cycloalkyl; or -unsubstituted or halogen, linear or branched C 1-25 Alkyl, C 3-25 Cycloalkyl or hydroxy substituted C 4-25 Aryl. In the present invention, alkenylene refers to a divalent hydrocarbon having one or more double bonds. Preferably, R c1 , R c2 , R c3 , and R c4 are each independently - unsubstituted or phenyl or hydroxy substituted, linear or branched C 1-18 Alkyl; - unsubstituted, linear or branched C 1-5 Alkyl or hydroxy substituted, C 5-15 cycloalkyl; or -Unsubstituted, linear or branched C 1-5 Alkyl or hydroxy substituted, C 6-12 It is aryl. More preferably, R c1 , R c2 , R c3 , and R c4 are each independently methyl, ethyl, propyl, butyl, hexadecyl, hydroxyethyl, benzyl, adamantyl, or phenyl. R c1 , R c2 , R c3 , and R c4 The total number of carbon atoms contained therein is preferably 4 to 25, and more preferably 4 to 20. R c1 , R c2 , R c3 , and R c4 may all be different, but preferably three or four are the same and the rest are different.

[0025] Specific examples of the component (C) include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrahexylammonium hydroxide, hexadecyltrimethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, trimethylphenylammonium hydroxide, benzyltrimethylammonium hydroxide, benzyltriethylammonium hydroxide, and N,N,N-trimethyl-1-adamantylammonium hydroxide.

[0026] The content of the component (C) is preferably 0.00001 to 1 mass %, more preferably 0.0001 to 0.1 mass %, and even more preferably 0.0002 to 0.01 mass %, based on the electronic device manufacturing fluid.

[0027] The electronic device manufacturing fluid according to the present invention essentially contains the above-mentioned components (A), (B) and (C), but may contain further components as necessary. These will be described in detail below. The components other than (A), (B) and (C) (when there are multiple components, the sum of the components) in the entire composition is preferably 0 to 10 mass %, more preferably 0 to 5 mass %, even more preferably 0 to 3 mass %, and even more preferably 0 to 1 mass % based on the electronic device manufacturing fluid. An embodiment in which the electronic device manufacturing fluid according to the present invention does not contain any components other than (A), (B) and (C) (0 mass %) is also one embodiment of the present invention.

[0028] Hydroxy-Containing Compounds (D) The electronic device manufacturing solution according to the present invention may further contain a hydroxy-containing compound (D). The hydroxy-containing compound (D) is a compound different from the components (A) and (B), and may have one or more hydroxy groups in the compound, but preferably has one to three hydroxy groups and may be substituted with fluorine. 3-30 Here, the fluorine substitution replaces the H in the compound with F, but this substitution does not replace the H in the hydroxy. It is believed that by further including component (D), it is possible to further reduce the limit size at which the particles do not collapse.

[0029] The component (D) is preferably represented by the following formula (d): [ka] Where: R d1 , R d2 , R d3 , and R d4 are each independently hydrogen, fluorine, or C 1-5 Each of them is independently alkyl, preferably hydrogen, fluorine, methyl, ethyl, t-butyl, isopropyl or isopentyl, and more preferably hydrogen, methyl or ethyl. L d1 and L d2 are each independently 1-20Alkylene, C 1-20 Cycloalkylene, C 2-4 Alkenylene, C 2-4 Alkynylene, or C 6-20 These groups are fluorine, C 1-5 It may be substituted with alkyl or hydroxy. Here, alkenylene means a divalent hydrocarbon group having one or more double bonds, and alkynylene means a divalent hydrocarbon group having one or more triple bonds. Preferably, L d1 and L d2 each independently represents an optionally fluorine-substituted group; C 1-5 Alkylene, C 2-4 Alkynylene, or phenylene (C6 arylene). d1 and L d2 Each independently is preferably fluorine-substituted, C 2-4 Alkylene, acetylene (C alkynylene) or phenylene, even more preferably fluorine-substituted, C 2-4 Alkylene, acetylene. In another aspect of the invention, L d1 and L d2 are also preferably not fluorine-substituted, and each independently represents 1-5 Alkylene, C 2-4 More preferably, each independently is an alkynylene of the formula: 2-4 More preferably, each independently represents an alkylene, acetylene, or phenylene of C 2-4 The alkylenes are acetylene and acetylene. h is 0, 1, or 2, preferably 0 or 1, and more preferably 0.

[0030] Specific examples of the component (D) 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, 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 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, and 1,4-benzenedimethanol.

[0031] The content of the component (D) is preferably 0.001 to 10 mass %, more preferably 0.002 to 5 mass %, and even more preferably 0.005 to 1 mass %, based on the electronic device manufacturing fluid. In one preferred embodiment of the present invention, the component (D) is not included.

[0032] Additive (E) The electronic device manufacturing fluid according to the present invention may further contain an additive (E) different from the components (A) to (D). In the present invention, the additive (E) comprises one or more selected from the group consisting of a second surfactant, an acid, a base, a germicide, an antibacterial agent, an antiseptic, and an antifungal agent.

[0033] The second surfactant is a surfactant other than an anionic surfactant, for example, a nonionic surfactant. The second surfactant can be included in the electronic device manufacturing liquid to improve the coating property and solubility. A preferred embodiment of the present invention is one in which the second surfactant is not included. An acid or a base can be used to adjust the pH value of the processing solution or to improve the solubility of each component. Germicides, antibacterial agents, preservatives and fungicides are used to prevent the growth of bacteria and fungi over time and include, for example, alcohols such as phenoxyethanol and isothiazolones.

[0034] The content of the component (E) is preferably 0.0001 to 10 mass %, more preferably 0.0003 to 0.1 mass %, and even more preferably 0.0005 to 0.01 mass %, based on the electronic device manufacturing liquid. In one preferred embodiment of the present invention, the component (E) is not contained.

[0035] The electronic device manufacturing solution according to the present invention can be manufactured by dissolving each component in a solvent and then filtering the solution through a filter to remove impurities and / or insoluble matters.

[0036] <Method of manufacturing resist pattern> The present invention also provides a method for producing a resist pattern using the above-mentioned electronic device manufacturing liquid. The photosensitive resin composition (resist composition) used in this method may be either positive or negative, and is preferably positive. A representative resist pattern production method to which the electronic device manufacturing liquid of the present invention is applied comprises the following steps. (1) applying a photosensitive resin composition to a substrate, with or without one or more intermediate layers, to form a photosensitive resin layer; (2) exposing the photosensitive resin layer to radiation; (3) developing the exposed photosensitive resin layer; and (4) Rinse the developed layer with the electronics manufacturing fluids described above.

[0037] The details are explained below. First, a photosensitive resin composition is applied (for example, laminated) above a substrate such as a silicon substrate or a glass substrate, which has been pretreated as necessary, to form a photosensitive resin layer. A known method can be used for lamination, but a coating method such as spin coating is preferable. The photosensitive resin composition can be laminated directly on the substrate, or can be laminated via one or more intermediate layers (for example, BARC). An anti-reflective film (for example, TARC) may be laminated above the photosensitive resin layer (opposite side to the substrate). Layers other than the photosensitive resin layer will be described later. By forming an anti-reflective film above or below the photosensitive resin layer, the cross-sectional shape and exposure margin can be improved.

[0038] Representative examples of the positive or negative photosensitive resin composition used in the resist pattern production method of the present invention include, for example, those containing a quinone diazide-based photosensitizer and an alkali-soluble resin, and chemically amplified photosensitive resin compositions. From the viewpoint of forming a high-resolution fine resist pattern, chemically amplified photosensitive resin compositions are preferred, such as chemically amplified PHS-acrylate hybrid EUV resist compositions. These are more preferably positive photosensitive resin compositions.

[0039] Examples of the quinone diazide photosensitizer used in the positive photosensitive resin composition containing the quinone diazide photosensitizer and the alkali-soluble resin include 1,2-benzoquinone diazide-4-sulfonic acid, 1,2-naphthoquinone diazide-4-sulfonic acid, 1,2-naphthoquinone diazide-5-sulfonic acid, esters or amides of these sulfonic acids, and examples of the alkali-soluble resin include novolak resins, polyvinylphenols, polyvinyl alcohols, copolymers of acrylic acid or methacrylic acid, etc. Preferable examples of the novolak resin include those produced from one or more phenols such as phenol, o-cresol, m-cresol, p-cresol, xylenol, etc., and one or more aldehydes such as formaldehyde, paraformaldehyde, etc.

[0040] Examples of chemically amplified photosensitive resin compositions include positive-type chemically amplified photosensitive resin compositions containing a compound that generates an acid when irradiated with radiation (photoacid generator) and a resin whose polarity increases due to the action of the acid generated from the photoacid generator, changing its solubility in a developer between exposed and unexposed areas; and negative-type chemically amplified photosensitive resin compositions which are composed of an alkali-soluble resin, a photoacid generator, and a crosslinking agent, in which crosslinking of the resin occurs due to the action of the acid, changing the solubility in a developer between exposed and unexposed areas.

[0041] Resins whose polarity increases under the action of acid and whose solubility in the developer changes between exposed and unexposed areas include resins that have groups in the main chain or side chain, or both the main chain and side chain, that decompose under the action of acid to generate alkali-soluble groups.Typical examples include polymers in which acetal or ketal groups have been introduced as protective groups into hydroxystyrene polymers (PHS), and similar polymers in which t-butoxycarbonyloxy or p-tetrahydropyranyloxy groups have been introduced as acid-decomposable groups.

[0042] The photoacid generator may be any compound that generates an acid upon irradiation with radiation, and examples thereof include onium salts such as diazonium salts, ammonium salts, phosphonium salts, iodonium salts, sulfonium salts, selenonium salts, and arsonium salts, organic halogen compounds, organometallic / organic halides, photoacid generators having an o-nitrobenzyl-type protecting group, compounds that generate sulfonic acid upon photolysis such as iminosulfonates, disulfone compounds, diazoketosulfones, and diazodisulfone compounds, etc. Compounds in which these groups or compounds that generate acid upon exposure to radiation are introduced into the main chain or side chain of a polymer can also be used.

[0043] The chemically amplified photosensitive resin composition may further contain, as necessary, an acid-decomposable dissolution inhibiting compound, a dye, a plasticizer, a surfactant, a photosensitizer, an organic basic compound, a compound that promotes solubility in a developer, and the like.

[0044] The photosensitive resin composition is applied on a substrate by a suitable application device and application method such as a spinner or coater, and is heated on a hot plate to remove the solvent in the photosensitive resin composition, forming a photosensitive resin layer. The heating temperature varies depending on the solvent or resist composition used, but is generally 70 to 150°C, preferably 90 to 150°C, for 10 to 180 seconds, preferably 30 to 120 seconds, when using a hot plate, and for 1 to 30 minutes when using a clean oven.

[0045] In the resist pattern manufacturing method of the present invention, the presence of a film or layer other than the photosensitive resin layer is also permitted. The substrate and the photosensitive resin layer may not be in direct contact with each other, and an intermediate layer may be interposed. The intermediate layer is a layer formed between the substrate and the photosensitive resin layer, and is also called an underlayer film. Examples of the underlayer film include a substrate modification film, a planarization film, a bottom antireflective film (BARC), an inorganic hard mask intermediate layer (a silicon oxide film, a silicon nitride film, and a silicon oxide nitrogen film), and an adhesion film. For the formation of the inorganic hard mask intermediate layer, reference can be made to Japanese Patent No. 5336306. The intermediate layer may be composed of one layer or multiple layers. In addition, a top antireflective film (TARC) may be formed on the photosensitive resin layer.

[0046] In the resist pattern production process of the present invention, the layer structure can be formed by a known method in accordance with the process conditions. For example, the following laminate structure can be mentioned. Substrate / lower film / photosensitive resin layer Substrate / Planarization film / BARC / Photosensitive resin layer Substrate / Planarization film / BARC / Photosensitive resin layer / TARC Substrate / planarization film / inorganic hard mask intermediate layer / photosensitive resin layer / TARC Substrate / planarization film / inorganic hard mask intermediate layer / BARC / photosensitive resin layer / TARC Substrate / flattening film / adhesion film / BARC / photosensitive resin layer / TARC Substrate / Substrate modification layer / Planarization film / BARC / Photosensitive resin layer / TARC Substrate / Substrate modification layer / Planarization film / Adhesion film / BARC / Photosensitive resin layer / TARC These layers can be formed by known techniques such as curing by heating and / or exposure to light after application, or by CVD, etc. These layers can be removed by known techniques (such as etching), and each layer can be patterned using the upper layer as a mask.

[0047] The photosensitive resin layer is exposed through a predetermined mask. When other layers are included (such as TARC), they may be exposed together. The wavelength of the radiation (light) used for exposure is not particularly limited, but it is preferable to expose with light having a wavelength of 13.5 to 248 nm. Specifically, KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), and extreme ultraviolet ray (wavelength 13.5 nm) can be used, and extreme ultraviolet ray is more preferable. These wavelengths allow a range of ±5%, preferably ±1%. After exposure, post-exposure baking (PEB) can be performed as necessary. The temperature of post-exposure baking is appropriately selected from 70 to 150°C, preferably 80 to 120°C, and the heating time is appropriately selected from 0.3 to 5 minutes, preferably 0.5 to 2 minutes.

[0048] Then, development is carried out with a developer. For development in the resist pattern production method of the present invention, a 2.38 mass % (±1% is acceptable) aqueous solution of tetramethylammonium hydroxide (TMAH) is preferably used. Surfactants and the like can also be added to these developers. The temperature of the developer is generally 5 to 50°C, preferably 25 to 40°C, and the development time is generally appropriately selected from 10 to 300 seconds, preferably 20 to 60 seconds. As the development method, a known technique such as paddle development can be used. As described above, the resist pattern of the present invention includes not only resist films that have been exposed and developed, but also resist patterns in which the walls have been thickened by covering them with other layers or films.

[0049] The resist pattern (developed photosensitive resin layer) created by the above steps is in an unwashed state. This resist pattern can be washed with the electronic device manufacturing liquid according to the present invention. The time for which the electronic device manufacturing liquid is in contact with the resist pattern, i.e., the treatment time, is preferably 1 second or more. The treatment temperature may also be arbitrary. The method for contacting the electronic device manufacturing liquid with the resist is also arbitrary, and can be carried out, for example, by immersing the resist substrate in the electronic device manufacturing liquid or by dropping the electronic device manufacturing liquid onto the surface of a rotating resist substrate.

[0050] In the resist pattern manufacturing method according to the present invention, the developed resist pattern can be washed with another washing liquid before and / or after the washing process with the electronic device manufacturing liquid. The other washing liquid is preferably water, more preferably pure water (DW, deionized water, etc.). Washing before the washing process is useful for washing the developer attached to the resist pattern. Washing after the washing process is useful for washing the electronic device manufacturing liquid. A preferred embodiment of the manufacturing method according to the present invention is a method in which pure water is poured into the developed resist pattern to replace the developer, and the pattern is washed while the electronic device manufacturing liquid is poured in to replace the developer while the pattern is kept immersed in the pure water. The cleaning with the aqueous solution of the electronics manufacturing process may be carried out by known methods. For example, the resist substrate may be immersed in the electronic device manufacturing solution, or the electronic device manufacturing solution may be dropped onto the surface of a rotating resist substrate. These methods may be used in combination as appropriate.

[0051] One of the conditions that easily cause pattern collapse is the location where the spacing between the walls of the resist pattern is the narrowest. This is a severe condition when the walls of the resist pattern are parallel to each other. In this specification, the minimum space size is the distance between the locations where the spacing is the smallest on one circuit unit. It is preferable that one circuit unit becomes one semiconductor in a later process. It is also preferable that one semiconductor includes one circuit unit in the horizontal direction and multiple circuit units in the vertical direction. Of course, unlike the test sample, if the frequency of occurrence of locations where the spacing between the walls is narrow is low, the frequency of occurrence of defects will decrease, and the frequency of occurrence of defective products will decrease. In the present invention, the minimum space size of the resist pattern in one circuit unit is preferably from 10 to 30 nm, more preferably from 10 to 20 nm, and even more preferably from 10 to 17 nm.

[0052] <Device manufacturing method> The device manufacturing method of the present invention comprises a method for manufacturing a resist pattern using an electronic device manufacturing liquid. Preferably, the device manufacturing method of the present invention comprises processing a substrate by etching using the resist pattern manufactured by the above method as a mask. After processing, the resist film is peeled off as necessary. In the manufacturing method of the present invention, the intermediate layer and / or the substrate can be processed by etching using the resist pattern as a mask. The etching can be performed by known techniques such as dry etching and wet etching, and dry etching is more preferable. For example, the intermediate layer can be etched using the resist pattern as an etching mask, and the substrate can be etched using the obtained intermediate layer pattern as an etching mask to process the substrate. In addition, the resist pattern can be used as an etching mask to etch the layer below the resist layer (e.g., the intermediate layer), while etching the substrate as it is. The processed substrate becomes, for example, a patterned substrate. The formed pattern can be used to form wiring on the substrate. These layers can be removed by dry etching, preferably with O2, CF4, CHF3, Cl2 or BCl3, preferably with O2 or CF4. In one preferred embodiment, the method for producing a device according to the present invention further comprises forming wiring on the processed substrate.

[0053] <Stress on the resist wall> As described in Namatsu et al. Appl. Phys. Lett. 1995(66) pp. 2655-2657 and shown diagrammatically in FIG. 1, the stress acting on the resist pattern wall 1 during rinsing and drying can be expressed by the following formula: σ max =(6γcosθ / D)x(H / W) 2 σ max : Maximum stress applied to the resist, γ: Surface tension of the rinse θ: contact angle, D: distance between walls H: wall height, W: wall width These lengths can be measured by known methods, for example, SEM photography.

[0054] As can be seen from the above formula, a short D or a short W causes more stress. In this specification, pitch size 3 means one unit of the resist pattern unit array having W and D as shown in FIG. This means that the finer (narrower pitch size) the resist pattern required, the greater the stress on the resist pattern. Thus, the finer the pattern, the stricter the conditions become, and the more improvements are needed in the electronics manufacturing process. (e.g. rinse compositions).

[0055] Preferred embodiments are listed below. [Embodiment 1] Anionic surfactant (A), A solvent (B), and Quaternary Ammonium Compounds (C) An electronic device manufacturing solution comprising at least The surfactant (A) is preferably a carboxy-containing compound, more preferably an alkyl carboxylic acid compound, and further preferably represented by formula (a). R a1 -COOH formula (a) Here, R a1 is C 3-12 alkyl, preferably R a1 is linear or branched C 3-10 alkyl, more preferably linear or branched C 3-9 Alkyl, even more preferably linear or branched C 3-8 It is an alkyl. The surfactant (A) is preferably selected from the group consisting of 2-methylpropanoic acid, n-butanoic acid, 2-methylbutanoic acid, n-pentanoic acid, n-hexanoic acid, n-heptanoic acid, n-octanoic acid, 2-methylpentanoic acid, 2-methylhexanoic acid, 5-methylhexanoic acid, 2-methylheptanoic acid, 4-methyl-n-octanoic acid, 2-ethylhexanoic acid, 2-propylpentanoic acid, 2,2-dimethylpentanoic acid, 3,5,5-trimethylhexanoic acid. The solvent (B) preferably contains water, more preferably consists essentially of water, and further preferably has a water content of 100% by mass. The electronics manufacturing fluid is preferably an aqueous electronics manufacturing fluid.

[0056] [Embodiment 2] 2. The electronics manufacturing fluid of embodiment 1, wherein the quaternary ammonium compound (C) is a quaternary ammonium hydroxide. The quaternary ammonium compound (C) is preferably represented by the formula (c). [ka] Where: R c1 , R c2 , R c3 , and R c4 are each independently halogen, unsubstituted or halogen, C 3-25 Cycloalkyl, C 4-25 Aryl or hydroxy substituted linear or branched C 1-25 Alkyl, unsubstituted or halogen, linear or branched C 1-25 Alkyl, C 3-25 Cycloalkyl, C 4-25 Aryl or hydroxy substituted linear or branched C 2-25 Alkenylene, unsubstituted or halogen, linear or branched C 1-25 Alkyl, C 4-25 aryl or hydroxy substituted C 3-25 Cycloalkyl, unsubstituted, or halogen, linear or branched C 1-25Alkyl, C 3-25 Cycloalkyl or hydroxy substituted C 4-25 is aryl, Preferably, unsubstituted or phenyl or hydroxy substituted, linear or branched C 1-18 Alkyl, unsubstituted, or linear or branched C 1-5 Alkyl or hydroxy substituted, C 5-15 Cycloalkyl, or unsubstituted, linear or branched C 1-5 Alkyl or hydroxy substituted, C 6-12 is aryl, More preferably, it is selected from the group consisting of methyl, ethyl, propyl, butyl, hexadecyl, hydroxyethyl, benzyl, adamantyl, and phenyl. The quaternary ammonium compound (C) is preferably selected from the group consisting of tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrahexylammonium hydroxide, hexadecyltrimethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, trimethylphenylammonium hydroxide, benzyltrimethylammonium hydroxide, benzyltriethylammonium hydroxide, N,N,N-trimethyl-1-adamantylammonium hydroxide.

[0057] [Embodiment 3] The electronic device manufacturing fluid according to embodiment 1 or 2, wherein the content of the anionic surfactant (A) is 0.01 to 10 mass %, preferably 0.02 to 5 mass %, and more preferably 0.02 to 1 mass %, based on the electronic device manufacturing fluid. Preferably, the content of the solvent (B) is 80 to 99.99 mass% based on the electronic device manufacturing liquid, Preferably, the content of water contained in the solvent (B) is 80 to 99.99 mass % based on the electronic device manufacturing fluid. The content of the quaternary ammonium compound (C) is preferably 0.00001 to 1 mass %, more preferably 0.0001 to 0.1 mass %, and even more preferably 0.0002 to 0.01 mass %, based on the electronic device manufacturing solution.

[0058] [Embodiment 4] The electronic device manufacturing solution according to any one of embodiments 1 to 3, further comprising a hydroxy-containing compound (D). The hydroxy-containing compound (D) is preferably represented by the following formula (d): [ka] Where: R d1 , R d2 , R d3 , and R d4 are each independently hydrogen, fluorine, or C 1-5 Each of them is independently alkyl, preferably hydrogen, fluorine, methyl, ethyl, t-butyl, isopropyl or isopentyl, and more preferably hydrogen, methyl or ethyl. L d1 and L d2 are each independently 1-20 Alkylene, C 1-20 Cycloalkylene, C 2-4 Alkenylene, C 2-4 Alkynylene, or C 6-20 These groups are fluorine, C 1-5 It may be substituted with alkyl or hydroxy. Here, alkenylene means a divalent hydrocarbon having one or more double bonds, and alkynylene means a divalent hydrocarbon group having one or more triple bonds. Preferably, L d1 and L d2 each independently represents an optionally fluorine-substituted group; C 1-5 Alkylene, C 2-4 Alkynylene, or phenylene (C6 arylene). d1 and L d2Each independently is preferably fluorine-substituted, C 2-4 Alkylene, acetylene (C alkynylene) or phenylene, even more preferably fluorine-substituted, C 2-4 Alkylene, acetylene. In another embodiment of the present invention, it is also preferred that L is not fluorine-substituted. d1 and L d2 are each independently 1-5 Alkylene, C 2-4 More preferably, each independently is an alkynylene of the formula: 2-4 More preferably, each independently represents an alkylene, acetylene, or phenylene of C 2-4 The alkylenes are acetylene and acetylene. h is 0, 1, or 2, preferably 0 or 1, and more preferably 0.

[0059] [Embodiment 5] 5. The electronic device manufacturing solution according to any one of embodiments 1 to 4, further comprising an additive (E). Where: The additive (E) comprises one or more selected from the group consisting of a second surfactant, an acid, a base, a germicide, an antibacterial agent, an antiseptic, and an antifungal agent. The content of the additive (E) is preferably 0.0001 to 10 mass %, more preferably 0.0003 to 0.1 mass %, and further preferably 0.005 to 0.01 mass %, based on the electronic device manufacturing fluid.

[0060] [Embodiment 6] The electronic device manufacturing solution according to any one of embodiments 1 to 5, which is a semiconductor manufacturing solution: Preferably, the electronics manufacturing fluid is a semiconductor substrate manufacturing aqueous solution; Preferably the electronics manufacturing fluid is a semiconductor substrate manufacturing process cleaning fluid; Preferably the electronics manufacturing fluid is a lithography cleaning fluid; Preferably, the electronic device manufacturing liquid is a resist pattern cleaning liquid; or Preferably the electronics manufacturing fluid is a rinse composition.

[0061] [Embodiment 7] A method for producing a resist pattern, which uses the electronic device manufacturing liquid according to any one of the first to sixth embodiments.

[0062] [Embodiment 8] A method for producing a resist pattern comprising the steps of: (1) applying a photosensitive resin composition to a substrate, with or without one or more intermediate layers, 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 electronic device manufacturing solution according to any one of the first to sixth embodiments.

[0063] [Embodiment 9] 9. The method for producing a resist pattern according to embodiment 8, wherein the photosensitive resin composition is a chemically amplified photosensitive resin composition, and the exposure is preferably performed using extreme ultraviolet light.

[0064] [Embodiment 10] 10. The method for producing a resist pattern according to any one of embodiments 7 to 9, wherein the minimum space size of the resist pattern in one circuit unit is 10 to 30 nm.

[0065] [Embodiment 11] A method for producing a device, comprising the method for producing a resist pattern according to any one of embodiments 7 to 10.

[0066] [Embodiment 12] The method for producing a device according to embodiment 11, further comprising etching a substrate using the resist pattern produced by the method according to any one of embodiments 7 to 10 as a mask.

[0067] [Embodiment 13] 13. A method for producing a device according to embodiment 11 or 12, further comprising forming wiring on the processed substrate.

[0068] The present invention will be described below with reference to various examples. However, the present invention is not limited to these examples.

[0069] <Preparation of Electronic Device Manufacturing Solution of Example 101> Add 2-methylbutanoic acid as component (A) to deionized water so that the concentration is 0.7% by mass, and hexadecyltrimethylammonium hydroxide as component (C) to the deionized water so that the concentration is 0.005% by mass, and stir the mixture. Confirm that the mixture is completely dissolved by visual inspection. Filter the mixture (pore size = 10 nm) to obtain the electronic device manufacturing solution of Example 101.

[0070] <Preparation of Electronic Device Manufacturing Solutions of Examples 102 to 109 and Comparative Examples 101 and 102> Using the components (A) and (C) as shown in Table 1, and in the concentrations as shown in Table 1, the electronic device manufacturing solutions of Examples 102 to 109 and Comparative Examples 101 and 102 are prepared in the same manner as in Example 101 above. Comparative Example 101 was obtained by filtering deionized water to which nothing was added, and Comparative Example 102 did not contain component (A). [Table 1]

[0071] <Preparation of evaluation board 1> A BARC composition (AZ Kr-F17B, Merck Electronics Co., Ltd. (hereinafter referred to as ME)) is applied by spin coating onto a silicon substrate and heated on a hot plate at 180°C for 60 seconds to obtain a BARC with a film thickness of 80 nm. A PHS-acrylate-based chemically amplified resist (DX6270P, ME) is applied on top of this and heated on a hot plate at 120°C for 90 seconds to obtain a resist film with a film thickness of 620 nm. This substrate is exposed through a mask (250 nm line / space 1:1) using a KrF exposure tool (FPA3000 EX5, Canon). The exposure dose is 25 mJ / cm2. 2 ~40mJ / cm 2 , so that the resulting line width changes. Then, PEB is performed on a hot plate at 100°C for 60 seconds, and a developer solution of 2.38 mass% TMAH aqueous solution is poured in and then held for 60 seconds (puddle). With the developer puddled, water is started to flow, and while rotating the substrate, the developer is replaced with water, and the puddle is stopped with water, and left to stand for 60 seconds. Then, while puddling with water, the aqueous solution of Example 101 prepared above is poured in, and while rotating the substrate, the water is replaced with the electronic device manufacturing solution of Example 101, and the puddle is stopped with the electronic device manufacturing solution of Example 101, and left to stand for 10 seconds. The substrate is spin-dried for 30 seconds to dry the substrate. For Examples 102 to 109 and Comparative Example 102, evaluation boards are produced in the same manner as described above using the respective electronic device manufacturing solutions. Comparative Example 101 differs from Example 101 above in that the substrate is spin-dried immediately after the water puddle condition, but is otherwise similar.

[0072] <Evaluation of collapse prevention> The evaluation substrate of Preparation 1 is used to evaluate the performance of preventing pattern collapse. The resist pattern is observed using an SEM device S-9220 (Hitachi High-Technologies) to observe the presence or absence of pattern collapse. The evaluation criteria are as follows. In Comparative Example 101, when the line width becomes narrower than 190 nm, the resist pattern collapse is confirmed. The results are shown in Table 1. A: No pattern collapse was observed in resist patterns with line widths of 150 nm or more and 177 nm or less. B: Pattern collapse is observed in resist patterns with line widths of 150 nm or more and 197 nm or less. C: Pattern collapse is observed in resist patterns with line widths greater than 200 nm.

[0073] <Preparation of Electronic Device Manufacturing Solutions of Examples 201 to 206 and Comparative Examples 201 to 204> Using the components (A), (C), and (D) as shown in Table 2, the electronic device manufacturing fluids of Examples 201 to 206 and Comparative Examples 201 to 204 are prepared in the same manner as in Example 101 above, so as to have the concentrations shown in Table 2. In addition, Comparative Example 203 was obtained by filtering deionized water to which nothing was added. [Table 2]

[0074] <Preparation of evaluation board 2> A silicon substrate is treated with hexamethyldisilazane (HMDS) at 90°C for 30 seconds. An EUV PHS-acrylate-based chemically amplified resist is applied on top of it by spin coating, and heated on a hot plate at 110°C for 60 seconds to obtain a resist film with a thickness of 50 nm. This substrate is exposed through a mask (16 nm line / space 1:1) using an EUV exposure device (NXE:3400, ASML). The exposure amount is changed so that the resulting line width changes. After that, PEB is performed on a hot plate at 100°C for 60 seconds, and a developer of 2.38 mass% TMAH aqueous solution is poured in and held for 30 seconds (puddle). With the developer puddled, water is started to flow, and the developer is replaced with water while rotating the substrate, and the flow is stopped while puddling with water and left to stand for 60 seconds. After that, pour the electronic device manufacturing liquid of Example 201 into the water puddle, replace the water with the electronic device manufacturing liquid of Example 201 while rotating the substrate, and stop for 10 seconds in the state of being puddled with the electronic device manufacturing liquid of Example 201. This substrate is spin-dried to dry the substrate. For the electronic device manufacturing liquids of Examples 202 to 206 and Comparative Examples 201, 202, and 204, the evaluation substrates are prepared in the same manner as above using their respective aqueous solutions. Comparative Example 201 is different from Example 201 above in that after replacing the developer with water and paddling with water, the substrate is spin-dried immediately, but the rest is the same.

[0075] <Evaluation of Critical Pattern Size (16 nm Line / Space)> The resist pattern formed on the evaluation substrate of Fabrication 2 is observed for line width and the presence or absence of pattern collapse using a length-measuring SEM CG5000 (Hitachi High-Technologies). As the exposure dose increases, the line width decreases. The minimum line width size at which pattern collapse does not occur is defined as the "critical pattern size". The results are shown in Table 2.

[0076] <Evaluation of LWR (16 nm Line / Space)> The LWR of the resist pattern formed on the evaluation substrate of Fabrication 2 is evaluated. Using a length-measuring SEM CG5000, the LWR (Line Width Roughness) of a resist pattern with a line width of 16 nm is measured. The results are shown in Table 2.

Explanation of Symbols

[0077] 1. Resist pattern wall 2. Electronic device manufacturing liquid 3. Pitch size

Claims

1. Anionic surfactant (A), Solvent (B), and Quaternary ammonium compounds (C) Electronic equipment manufacturing fluid comprising at least: Here, The surfactant (A) is preferably a carboxyl-containing compound, more preferably an alkylcarboxylic acid compound, and even more preferably represented by formula (a), R ａ１ -COOH formula (a) (Here, R ａ１ is C ３－１２ It is alkyl, preferably R ａ１ C is a linear or branched C ３－１０ (It is alkyl.) The solvent (B) preferably comprises water, or The electronic equipment manufacturing solution is preferably an aqueous solution for electronic equipment manufacturing.

2. The electronic equipment manufacturing solution according to claim 1, wherein the quaternary ammonium compound (C) is a quaternary ammonium hydroxide: Preferably, the quaternary ammonium compound (C) is represented by formula (c). 【Chemistry 1】 (Here, R ｃ１ 、 R ｃ２ 、 R ｃ３ 、 and R ｃ４ are each independently a halogen, unsubstituted, or halogen, C ３－２５ cycloalkyl, C ４－２５ aryl or hydroxy-substituted, straight-chain or branched C １－２５ alkyl, unsubstituted, or halogen, straight-chain or branched C １－２５ alkyl, C ３－２５ cycloalkyl, C ４－２５ aryl or hydroxy-substituted, straight-chain or branched C ２－２５ alkenylene, unsubstituted, or halogen, straight-chain or branched C<00000!17> alkyl, C ４－２５ aryl or hydroxy-substituted, C ３－２５ cycloalkyl, or unsubstituted, or halogen, straight-chain or branched C １－２５ alkyl, C ３－２５ cycloalkyl or hydroxy-substituted, C ４－２５ aryl).

3. The electronic equipment manufacturing liquid according to claim 1 or 2, wherein the content of the anionic surfactant (A) is 0.01 to 10% by mass, based on the electronic equipment manufacturing liquid: Preferably, the solvent (B) content is 80 to 99.99% by mass, based on the electronic equipment manufacturing liquid. Preferably, the water content in solvent (B) is 80 to 99.99% by mass, based on the electronic equipment manufacturing liquid, or Preferably, the content of quaternary ammonium compound (C) is 0.00001 to 1% by mass, and more preferably 0.0001 to 0.1% by mass, based on the electronic equipment manufacturing liquid.

4. The electronic equipment manufacturing liquid according to claim 1 or 2, further comprising a hydroxyl-containing compound (D).

5. The electronic equipment manufacturing liquid according to claim 1 or 2, further comprising additive (E): Here, Additive (E) comprises one or more selected from the group consisting of a second surfactant, acid, base, disinfectant, antibacterial agent, preservative, and fungicide; Preferably, the content of additive (E) is 0.0001 to 10% by mass, based on the electronic equipment manufacturing solution.

6. The semiconductor manufacturing aqueous solution, according to claim 1 or 2, is an electronic equipment manufacturing liquid: Preferably, the electronic equipment manufacturing solution is an aqueous solution for semiconductor substrate manufacturing; Preferably, the electronic equipment manufacturing fluid is a semiconductor substrate manufacturing process cleaning fluid; Preferably, the electronic equipment manufacturing fluid is a lithography cleaning fluid; or Preferably, the electronic equipment manufacturing fluid is a resist pattern cleaning fluid.

7. A method for manufacturing a resist pattern using the electronic equipment manufacturing liquid described in claim 1 or 2.

8. A method for manufacturing a resist pattern comprising the following steps: (1) Apply a photosensitive resin composition to a substrate with or without an intermediate layer to form a photosensitive resin layer. (2) Expose the photosensitive resin layer to radiation, (3) Develop the exposed photosensitive resin layer, (4) Wash the developed layer with the electronic equipment manufacturing solution according to claim 1 or 2.

9. The method for producing a resist pattern according to claim 8, wherein the photosensitive resin composition is a chemically amplified photosensitive resin composition, and exposure is preferably performed using extreme ultraviolet light.

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

11. A method for manufacturing a device, comprising the method for manufacturing a resist pattern described in claim 7.

12. A method for manufacturing a device according to claim 11, further comprising etching a resist pattern manufactured by the method of claim 7 as a mask and processing a substrate.

13. A method for manufacturing a device according to claim 11, further comprising forming wiring on a processed substrate.

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