Resist pattern replacement solution, and method for manufacturing a resist pattern using the same.

Abstract

To provide a replacement liquid of liquid filling between resist patterns and a method for producing resist patterns using the same.SOLUTION: There is provided a replacement liquid of liquid filling between resist patterns comprising a sulfonyl group-containing compound (A); a nitrogen-containing compound (B); and a solvent (C).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a resist pattern substitution solution and a method for manufacturing a resist pattern using the same. The present invention further relates to a method for manufacturing a processed substrate and a method for manufacturing a device. [Background technology]

[0002] In recent years, the need for higher integration in LSIs has increased, requiring miniaturization of resist patterns. To meet these needs, lithography processes using short-wavelength lasers such as KrF excimer lasers (248 nm), ArF excimer lasers (193 nm), extreme ultraviolet (EUV; 13 nm), X-rays, and electron beams are being put into practical use. To accommodate this miniaturization of resist patterns, high-resolution photosensitive resin compositions used as resists during microfabrication are also required. However, as miniaturization progresses as described above, there is a tendency for resist patterns to collapse, the number of defects to increase, and the pattern roughness to deteriorate.

[0003] Resist pattern collapse is thought to occur when negative pressure is created between patterns due to the surface tension of water during the washing of the pattern with water (deionized water) after development. To improve resist pattern collapse, there is a method of washing with a rinsing solution containing specific components instead of conventional water (for example, Patent Document 1). In addition, there is a method of applying a composition containing specific components to the resist pattern after drying to improve the surface roughness of the resist (for example, Patent Document 2). [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] International Publication No. 2018 / 095885 [Patent Document 2] International Publication No. 2016 / 060116 [Overview of the project] Problems to be Solved by the Invention

[0005] The present inventor has recognized that there are one or more problems for which improvements are still needed. Examples of these problems include the following. preventing resist pattern collapse in fine resist patterns; reducing defects in fine resist patterns; suppressing variation in the surface energy of a resist film; reducing developer-derived components remaining in a resist pattern film; suppressing swelling of a resist pattern; reducing the frequency of water droplet generation in the step of drying a resist pattern; increasing the hardness and / or elastic modulus of a resist pattern; suppressing variation in the shape of a resist pattern. Means for Solving the Problems

[0006] The inter-resist-pattern replacement solution according to the present invention is (A) a sulfonyl group-containing compound, (B) a nitrogen-containing compound, and (C) a solvent comprising wherein (A) the sulfonyl group-containing compound is represented by formula (a), Chemical Formula R 11 is C 1-20 alkyl, C wherein part or all of hydrogen atoms are substituted with halogen or -OH 1-20 alkyl, unsubstituted or R-substituted C 13 -substituted C 6-10 aryl, -OH, or nitrogen, and H that is ionically bonded to nitrogen + may be changed to NH4 + , and R 12 is -OH, C 1-15 alkyl, or C wherein part or all of hydrogen atoms are substituted with halogen 1-15 alkyl, R 13 is C 1-5Alkyl, or C in which some or all of the hydrogen atoms are substituted with halogens 1-5 It is alkyl, R 11 , R 12 or R 13 The alkyl groups in this combination may form a ring, and two or more of these groups may form a ring by bonding with each other. n 11 = 1, 2 or 3; and (C) The solvent consists of water.

[0007] The method for manufacturing a resist pattern according to the present invention comprises the following steps: (1) Applying 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) Apply a developer to the exposed photosensitive resin layer to form a resist pattern; (4) Apply the resist pattern replacement liquid described above to the resist pattern to replace the liquid present between the resist patterns; and (5) Remove the resist pattern replacement solution.

[0008] The method for manufacturing a processed substrate according to the present invention comprises the following steps: The resist pattern is manufactured using the method described above; and (6) The resist pattern is used as a mask for processing.

[0009] The method for manufacturing the device according to the present invention comprises the following steps: A processed substrate is manufactured using the method described above. [Effects of the Invention]

[0010] By using the resist pattern substitution solution according to the present invention, one or more of the following effects can be desired. It can prevent the resist pattern from collapsing in fine resist patterns; reduce defects in fine resist patterns; suppress variations in the surface energy of the resist film; reduce developer-derived components remaining in the resist pattern film; suppress swelling of the resist pattern; reduce the frequency of water droplet formation during the resist pattern drying process; increase the hardness and / or modulus of elasticity of the resist pattern; and suppress variations in the shape of the resist pattern. [Modes for carrying out the invention]

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

[0012] definition In this specification, unless otherwise specified, the definitions and examples set forth in this paragraph shall prevail. The singular form includes the plural form, and "one" or "that" means "at least one." An element of a certain concept can be expressed by multiple types, and when a quantity (e.g., mass %) is given, that quantity represents the sum of those multiple types. "and / or" includes all combinations of elements, as well as their use individually. When a numerical range is indicated using "~" or "-", it includes both endpoints and has the same unit. For example, 5~25 mol% means between 5 mol% and 25 mol%. "C x-y "C x ~C y " and "C x The notation, such as "...", refers to the number of carbon atoms in the molecule or substituent. For example, C 1~6 Alkyl refers to an alkyl chain having between 1 and 6 carbon atoms (such as methyl, ethyl, propyl, butyl, pentyl, and hexyl). When a polymer has multiple types of repeating units, these repeating units copolymerize. These copolymerizations may be alternating copolymerization, random copolymerization, block copolymerization, graft copolymerization, or a mixture of these. When polymers and resins are shown in structural formulas, the n, m, etc., in parentheses indicate the number of repeating units. The unit of temperature used is Celsius. For example, 20 degrees means 20 degrees Celsius. An additive refers to the compound itself that has the function (for example, in the case of a base generator, it is the compound itself that generates a base). The compound may also be dissolved or dispersed in a solvent and added to the composition. In one embodiment of the present invention, it is preferable that the solvent is included in the composition according to the present invention as (C) solvent or other component.

[0013] <Resist pattern replacement solution> The resist pattern substitution solution according to the present invention (hereinafter sometimes referred to as the substitution solution) comprises (A) a sulfonyl group-containing compound, (B) a nitrogen-containing compound, and (C) a solvent. Here, the resist pattern replacement solution is characterized by being applied between resist patterns to replace the liquid present between them. In other words, the resist pattern replacement solution according to the present invention is applied between resist patterns in a wet state after development, and is different from the resist pattern processing solution applied to resist patterns after they have been dried after development.

[0014] (A) Sulfonyl group-containing compound The (A) sulfonyl group-containing compound used in the present invention is represented by formula (a). [ka] R 11 C 1-20 Alkyl, C, where some or all of the hydrogen atoms are substituted with halogens (preferably fluorine) or -OH groups. 1-20 alkyl, unsubstituted, or R 13 C replaced by 6-10It is an aryl, -OH, or nitrogen. Here, nitrogen is n 11 When = 1, -NH2 is n 11 =2 means -NH-. H is ionically bonded to nitrogen. + NH4 + You can change it to this. For example, n 11 When =2, H of -NH- + NH4 + It is also permissible to modify the compound to form an ammonium salt. A preferred embodiment of the present invention involves H ionically bonded to nitrogen. + NH4 + It will not be changed to C mentioned above. 1-20 Alkyl is n 11 When C is 2 or 3, 1-20 This refers to a divalent or trivalent saturated hydrocarbon group. 12 is -OH, C 1-15 Alkyl, or C in which some or all of the hydrogen atoms are substituted with halogens 1-15 It is alkyl. R 13 C 1-5 Alkyl, or C in which some or all of the hydrogen atoms are substituted with halogens 1-5 It is alkyl. R 11 , R 12 or R 13 The alkyl groups in this combination may form a ring, or two or more of them may bond to each other to form a ring. n 11 = 1, 2, or 3; preferably 1 or 2; more preferably 1. 11 =2 is another preferred embodiment. Although not bound by theory, it is thought that having a sulfonyl group (more preferably a sulfonic acid or sulfonilimide skeleton) makes it possible to remove residual components of the developer (more preferably an alkaline aqueous solution, and even more preferably an aqueous solution of tetramethylammonium hydroxide (TMAH)) remaining on the resist pattern.

[0015] In one preferred form, equation (a) can be expressed as equation (a-1). R 14-SO3H (a-1) Here, R 14 C 1-20 Alkyl, C where some or all of the hydrogen atoms are substituted with fluorine or -OH groups. 1-20 alkyl, unsubstituted, or R 13 C replaced by 6-10 It is aryl or -OH, R 13 C 1-5 It is alkyl.

[0016] Formula (a-1) is preferably represented by formula (a-1-1), (a-1-2), or (a-1-3).

[0017] R 15 -SO3H (a-1-1) Here, R 15 is -OH, C 1-9 Alkyl, or C where some or all of the hydrogen atoms are substituted with fluorine or -OH groups. 1-9 It is alkyl. 15 Preferably, -OH, linear C 1-3 C11 is an alkyl, hydroxymethyl, hydroxyethyl, or C11 is a C11 that has some or all of its hydrogen atoms replaced by fluorine. 1-8 Alkyl; more preferably C, where all hydrogen atoms are substituted with fluorine, such as -OH, methyl, ethyl, hydroxymethyl, or hydrogen atoms. 1-4 Alkyl or C(H))(H)))) 5-8 It is alkyl. Examples of these include sulfuric acid, methanesulfonic acid, ethanesulfonic acid, trifluoromethanesulfonic acid, hydroxymethanesulfonic acid, nonafluorobutanesulfonic acid, and tridecafluorooctanesulfonic acid.

[0018] C m H 2m+1 SO3H (a-1-2) Here, m is a number between 10 and 20. Preferably m is a number between 11 and 19, more preferably a number between 12 and 18, and even more preferably a number between 13 and 18. Examples of these include decanesulfonic acid, 1-dodecanesulfonic acid, and 1-tetradecanesulfonic acid. For example, alkylsulfonic acids represented by (a-1-2) having 11 to 19 carbon atoms (m=11 to 19 as described above) are a suitable embodiment of the (A) sulfonyl group-containing compound of the present invention.

[0019] [ka] Here, R 16 is hydrogen or C 1-5 The alkyl group is preferably hydrogen, methyl, or t-butyl, and more preferably hydrogen or methyl. Examples of these include benzenesulfonic acid and toluenesulfonic acid.

[0020] In one preferred form, equation (a) can be expressed as equation (a-2). [ka] Here, L 11 C 1-5 It is an alkylene or -NH-; preferably C 1-3 Alkylene or -NH-; more preferably -NH-. H ionically bonded to nitrogen. + NH4 + This may be changed. A preferred embodiment of the present invention is H ionically bonded to nitrogen. + NH4 + It will not be changed. Each independently, R 17 and R 18 is -OH, C 1-15 Alkyl, or C, in which some or all of the hydrogen atoms are substituted with fluorine. 1-15 It is alkyl; preferably, C where all of the -OH or hydrogen atoms are substituted with fluorine. 1-5 It is alkyl. R 17 and R 18The alkyl groups may be bonded to each other to form a ring. Examples of these include ethanedisulfonic acid, bis(trifluoromethanesulfonyl)amide, bis(nonafluorobutanesulfonyl)imide and cyclohexafluoropropane-1,3-bis(sulfonylamide). For example, the compound on the left below is cyclohexafluoropropane-1,3-bis(sulfonylamide), and may be included in formula (a-2). In this case, L 11 is -NH-, and R 17 is fluoroethyl (C2), and R 18 is fluoromethyl (C1), and R 17 and R 18 can be read as an embodiment in which they are bonded to each other to form a ring. The compound on the right below is a compound in which H that ionically bonds to the nitrogen of the compound on the left below + is changed to NH4 + to obtain an ammonium salt.

Chemical

[0021] The molecular weight of the sulfonyl group-containing compound (A) is preferably 90 to 600; more preferably 90 to 300; still more preferably 220 to 350.

[0022] The content of the sulfonyl group-containing compound (A), based on the total mass of the inter-resist-pattern replacement solution, is preferably 0.01 to 10% by mass, more preferably 0.05 to 3% by mass, and still more preferably 0.1 to 1% by mass.

[0023] (B) Nitrogen-containing compound The replacement solution according to the present invention comprises (B) a nitrogen-containing compound. The (B) nitrogen-containing compound plays a role in controlling the acidity of the replacement solution according to the present invention. Without being bound by theory, it is considered that when the (B) nitrogen-containing compound is not included, deprotection of the resist is induced by acidic components (e.g., the (A) sulfonyl group-containing compound and (D) polymer), resulting in pattern collapse. The nitrogen-containing compound (B) is (B1) a monoamine compound, (B2) a diamine compound, or (B3) a heteroaryl having 1 to 3 nitrogen atoms.

[0024] (B1) Monoamine compound (B1) The monoamine compound is represented by formula (b1). Chemical formula Here, R 21 , R 22 and R 23 are each independently H, C 1-5 alkyl, or C 1-5 alkanol, R 21 , R 22 and R 23 alkyl groups may form a ring, two or more of these may bond to each other, and the -CH2- moiety of the alkyl group in R 21 , R 22 and R 23 may be substituted with -O-. In the present invention, the (B1) monoamine compound includes ammonia (when R 21 , R 22 and R 23 are all H). Ammonia is also a preferred embodiment as the (B1) monoamine compound. Examples of the (B1) monoamine compound other than ammonia include the following compounds. (i) primary amines, for example propylamine, butylamine, pentylamine, 2-methylbutylamine, 2-aminoethanol, 3-amino-1-propanol, aminoethoxyethanol, cyclohexylamine, and cyclopentylamine, (ii) secondary amines, for example diethylamine, dipropylamine, dibutylamine, dimethanolamine, diethanolamine, piperidine, morpholine, and pyrrolidine, and (iii) Tertiary amines, such as triethylamine, tripropylamine, N-methyldiethylamine, trimethanolamine, and triethanolamine.

[0025] (B2) Diamine compound (B2) Diamine compounds are represented by formula (b2). [ka] Here, R 31 , R 32 , R 33 and R 34 These are H and C, respectively, independently. 1-5 Alkyl, or C 1-5 Alkanol, R 31 , R 32 , R 33 and R 34 The alkyl group in R may form a ring, and two or more of these rings may be bonded to each other. 31 , R 32 , R 33 and R 34 The -CH2- portion of the alkyl group may be substituted with -O-. L 31 is C 1-5 It is an alkylene, and the -CH2- portion of the alkylene may be substituted with -O-. (B2) Examples of diamine compounds include: Ethylenediamine, 1,2-diaminopropane, 1,3-Diaminopropane N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetraethylethylenediamine, N,N,N',N'-tetrapropylethylenediamine, N,N,N',N'-tetraisopropylethylenediamine, N,N,N',N'-tetrabutylethylenediamine, N,N,N',N'-Tetraisobutylethylenediamine, N,N,N',N'-tetramethyl-1,2-propylenediamine, N,N,N',N'-tetraethyl-1,2-propylenediamine, N,N,N',N'-tetrapropyl-1,2-propylenediamine, N,N,N',N'-tetraisopropyl-1,2-propylenediamine, N,N,N',N'-tetramethyl-1,3-propylenediamine, N,N,N',N'-tetraethyl-1,3-propylenediamine, N,N,N',N'-tetrapropyl-1,3-propylenediamine, N,N,N',N'-tetraisopropyl-1,3-propylenediamine, N,N,N',N'-Tetraisobutyl-1,3-Propylenediamine, N,N,N',N'-tetramethyl-1,2-butylenediamine, N,N,N',N'-tetraethyl-1,2-butylenediamine, N,N-dimethylaminoethylamine, N,N-diethylaminoethylamine, N,N-dimethylaminopropylamine, N,N-diethylaminopropylamine, N-methylaminoethylamine, N-ethylaminoethylamine, N-(2-aminoethylamino)ethanol, Piperazine, and 1,4-Diazabicyclo[2.2.2]octane.

[0026] (B3) Heteroaryl compounds containing 1 to 3 nitrogen atoms Heteroaryl compounds containing 1 to 3 nitrogen atoms are preferably five-membered or six-membered rings, such as pyridine, imidazole, and triazine. The number of nitrogen atoms is preferably 1 or 2, and more preferably 1.

[0027] (B) The nitrogen-containing compound content is preferably 0.01 to 20% by mass; more preferably 0.01 to 5% by mass; even more preferably 0.01 to 1% by mass; and even more preferably 0.1 to 1% by mass, based on the total mass of the resist pattern substitution solution.

[0028] (B) The molecular weight of the nitrogen-containing compound is preferably 17 to 170; more preferably 17 to 150; even more preferably 17 to 120; and even more preferably 50 to 120.

[0029] (C) Solvent The displacement solution according to the present invention comprises a solvent (C). The solvent (C) comprises water. The water is preferably deionized water. For use in fine resist patterns, the solvent (C) is preferably low in impurities. A preferred solvent (C) has impurities of 1 ppm or less; more preferably 100 ppb or less; and even more preferably 10 ppb or less. Filtration of the solution is also a preferred embodiment of the present invention for use in fine processes. (C) The water content based on the total mass of the solvent is preferably 90 to 100% by mass; more preferably 98 to 100% by mass; even more preferably 99 to 100% by mass; and even more preferably 99.9 to 100% by mass. In a preferred embodiment of the present invention, the solvent (C) consists substantially of water alone. However, an embodiment in which additives are contained in the replacement solution of the present invention in a state in which they are dissolved and / or dispersed in a solvent other than water (e.g., a surfactant) is also acceptable as a preferred embodiment of the present invention.

[0030] Specific examples of (C) solvents other than water include, for example, 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 mixtures thereof. These are preferred in terms of the storage stability of the solution. Two or more of these solvents can also be used in mixture form.

[0031] (C) The solvent content is preferably 80 to 99.98% by mass, more preferably 90 to 99.5% by mass, and even more preferably 95 to 99% by mass, based on the total mass of the resist pattern substitution solution. Furthermore, based on the total mass of the resist pattern substitution solution, the amount of water contained in solvent (C) is preferably 80 to 99.94% by mass; more preferably 90 to 99.94% by mass; and even more preferably 95 to 99.94% by mass.

[0032] The displacement solution according to the present invention is essential for the above-mentioned components (A) to (C), but may contain further compounds as needed. These will be described in detail below. The components other than (A) to (C) in the overall composition (if there are multiple components, their sum) are preferably 0 to 10% by mass; more preferably 0 to 5% by mass; and even more preferably 0 to 3% by mass, based on the total mass of the displacement solution. An embodiment in which the displacement solution according to the present invention does not contain any components other than (A) to (C) (0% by mass) is also a preferred embodiment of the present invention.

[0033] (D) Polymer The displacement solution according to the present invention may further contain (D) polymer. (D) The polymer is preferably a water-soluble polymer from the viewpoint of affinity with the substitution solution. Of these, it is more preferable that the repeating unit has at least one group selected from the group consisting of sulfo(-SO3H), carboxy(-COOH), hydroxy(-OH), and carbonyl(-CO-) and salts thereof. (D) The polymer is even more preferably a repeating unit having sulfo(-SO3H) and / or carboxy(-COOH). (D) Examples of polymers include polyacrylic acid, polymethacrylic acid, polymaleic acid, polyvinyl sulfonic acid, polystyrene sulfonic acid, vinyl ether alkyl fluoride polymer, poly2-acrylamido-2-methyl-1-propanesulfonic acid, polytrifluoromethylacrylic acid, and salts thereof, and copolymers of any of these. In addition, polyacrylamide or poly(trifluoromethyl)-4-penten-2-ol can also be used as the (D) polymer.

[0034] (D) By including polymers, the fall prevention effect and defect suppression effect can be improved.

[0035] (D) The mass-average molecular weight of the polymer is preferably 1,000 to 100,000, more preferably 2,000 to 50,000, and particularly preferably 3,000 to 20,000. Here, the mass-average molecular weight is the polystyrene-equivalent mass-average molecular weight, which can be measured by gel permeation chromatography using polystyrene as the standard.

[0036] (D) The polymer content is preferably 0.1 to 20% by mass, more preferably 0.2 to 15% by mass; even more preferably 0.5 to 10% by mass; and even more preferably 1 to 8% by mass, based on the total mass of the resist pattern substitution solution.

[0037] (E) Surfactants The displacement solution according to the present invention may further contain (E) a surfactant. The (E) surfactant is a different component from (A) to (D). The inclusion of a surfactant can improve the applicability. In the present invention, (E) surfactant refers to the compound itself having the above-described function. The compound may be dissolved or dispersed in a solvent and contained in the composition (liquid), but it is preferable that such a solvent is contained in the composition as (C) solvent or other component. The same applies to various additives that may be contained in the composition hereafter. Examples of surfactants that can be used in the present invention include anionic surfactants, cationic surfactants, or nonionic surfactants. More specifically, examples include laurylpyridinium chloride and laurylmethylammonium chloride, polyoxyethylene octyl ether, polyoxyethylene lauryl ether and polyoxyethylene acetylene glycol ether, fluorine-containing surfactants (e.g., Florard (trade name, Sumitomo 3M), Megafac (trade name, DIC), Sulfuron (trade name, Asahi Glass)), or organosiloxane surfactants (e.g., KP341, trade name, Shin-Etsu Chemical Co., Ltd.).

[0038] (E) The surfactant content is preferably 0.01 to 5% by mass, and more preferably 0.03 to 1% by mass, based on the total mass of the displacement solution according to the present invention. (E) It is also a preferred embodiment that the solution does not contain a surfactant (0.0% by mass).

[0039] (F) Additives The displacement solution used in the present invention may further contain additive (F). Additive (F) is a different component from (A) to (E). Additive (F) preferably comprises an acid, a base, a surfactant other than surfactant (E), a bactericide, an antimicrobial agent, a preservative, an antifungal agent, or a combination thereof; more preferably comprises an acid, a base, a bactericide, an antimicrobial agent, a preservative, or an antifungal agent. (F) The content of the additive is preferably 0.0005 to 20% by mass, and more preferably 0.0005 to 1% by mass, based on the total mass of the resist pattern replacement solution. (F) It is also a preferred embodiment that the additive is not included (0.0% by mass).

[0040] <Method for manufacturing resist patterns> The method for manufacturing a resist pattern according to the present invention comprises the following: (1) Applying 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) Apply a developer to the exposed photosensitive resin layer to form a resist pattern; (4) Apply the resist pattern replacement liquid according to the present invention to the resist pattern to replace the liquid present between the resist patterns; and (5) Remove the resist pattern replacement solution. For clarity, the numbers in parentheses indicate the order. For example, step (4) is performed before step (5).

[0041] The details are explained below. A photosensitive resin composition is applied to a substrate (e.g., silicon / silicon dioxide coated substrate, silicon nitride substrate, silicon wafer substrate, glass substrate, and ITO substrate, etc.) by an appropriate method. Here, in the present invention, "above" includes cases where it is formed directly on top of the substrate and cases where it is formed via other layers. For example, a planarization film or a resist underlayer film may be formed directly on top of the substrate, and the photosensitive resin composition may be applied directly on top of that. The application method is not particularly limited, but examples include coating by a spinner or coater. After coating, a photosensitive resin layer is formed by heating as needed. Heating is performed, for example, by a hot plate. The heating temperature is preferably 60 to 140°C; more preferably 90 to 110°C. The temperature here refers to the heating atmosphere, for example, the heating surface temperature of the hot plate. The heating time is preferably 30 to 900 seconds; more preferably 60 to 300 seconds. Heating is preferably performed in an atmosphere of air or nitrogen gas. The thickness of the photosensitive resin layer is selected according to the purpose. It is also possible to make the thickness of the photosensitive resin layer greater than 1 μm.

[0042] In the resist pattern manufacturing method according to the present invention, the presence of films and layers other than the photosensitive resin layer is also permitted. An intermediate layer may be interposed so that the substrate and the photosensitive resin layer do not come into direct contact. An intermediate layer is a layer formed between the substrate and the photosensitive resin layer, and is also called a lower layer film. Examples of lower layers include substrate modification films, planarization films, lower layer anti-reflective films (BARC), inorganic hard mask intermediate layers (silicon oxide films, silicon nitride films, and silicon nitrogen oxide films), and adhesion films. The intermediate layer may consist of one layer or multiple layers. In addition, an upper layer anti-reflective film (TARC) may be formed on top of the photosensitive resin layer.

[0043] The photosensitive resin layer is exposed to radiation through a predetermined mask. If other layers are included (such as a TARC layer), they may also be exposed. The wavelength of the light used for exposure is not particularly limited, but exposure with light having a wavelength of 13.5 to 248 nm is preferred. Specifically, KrF excimer lasers (wavelength 248 nm), ArF excimer lasers (wavelength 193 nm), and extreme ultraviolet light (wavelength 13.5 nm) can be used. These wavelengths are allowed within a range of ±1%. After exposure, post-exposure baking (PEB) can be performed as needed. The PEB temperature is appropriately selected from 70 to 150°C; preferably 80 to 120°C, and the baking time is 30 to 300 seconds; preferably 30 to 120 seconds. Baking is preferably performed in an air or nitrogen gas atmosphere.

[0044] Next, a developer is applied to the exposed photosensitive resin layer to form a resist pattern. Conventional development methods for photoresist, such as paddle development, immersion development, and agitation immersion development, can be used. Preferably, the development method is paddle development. As the developer, an alkaline aqueous solution containing inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, and sodium silicate; organic amines such as ammonia, ethylamine, propylamine, diethylamine, diethylaminoethanol, and triethylamine; and quaternary amines such as TMAH is used, preferably a 2.38% by mass (±1% is acceptable) TMAH aqueous solution. Furthermore, surfactants and the like can be added to these developers. The developer temperature is generally 5-50°C; preferably 25-40°C, and the development time is generally 10-300 seconds; preferably 20-60 seconds, which can be appropriately selected.

[0045] With developer remaining between the resist patterns, further steps may be taken as needed: (3.1) Apply the cleaning solution to the resist pattern and clean the resist pattern. It may further contain the following. The cleaning solution used here can be one used in known methods, for example, water (deionized water) or a known rinsing solution. With developer or the above-mentioned washing solution remaining between the resist patterns, the replacement solution according to the present invention is applied to the resist patterns to replace the liquid present between the resist patterns.

[0046] When a developer is applied to a photosensitive resin layer to form a resist pattern, components contained in the developer (e.g., alkaline components, TMAH) may remain within the resist pattern film. While not bound by theory, the inventors reasoned as follows: Residual components derived from the developer are difficult to remove with the above-mentioned washing solutions (water or rinsing solution). By applying the substitution solution according to the present invention to the resist pattern, it is thought that the sulfonyl group-containing compounds contained in the substitution solution according to the present invention can remove residual components derived from the developer from the resist pattern film. As a result, attraction due to neutralization energy may also occur. In other words, steps (4) and / or (5) reduce the amount of residual components derived from the developer from the resist pattern. It is believed that residual components derived from the developer present in the resist pattern film cause the resist pattern to swell, and that the uneven distribution of alkaline components within the resist pattern leads to uneven surface energy within the resist pattern. Uneven surface energy of the resist pattern is thought to trigger the formation of water droplets during drying of the pattern, which can cause the pattern to collapse. By applying the replacement solution according to the present invention, residual components derived from the developer are reduced, thereby suppressing swelling of the resist pattern, increasing the hardness of the resist pattern, and further, homogenizing the surface energy of the resist pattern, which is thought to have the effect of suppressing resist pattern collapse. Therefore, it is preferable not to dry the resist pattern before applying the replacement solution of the present invention. That is, it is preferable that the resist pattern is not dried between steps (3) and (4). Furthermore, as a preferred embodiment of the present invention, the replacement solution of the present invention can also be said to be a resist film surface modifier comprising the above-mentioned components (A), (B), (C), etc. The resist film referred to here is not limited to a patterned film, but it is more preferable that it be a patterned resist film. Furthermore, the resist pattern obtained in step (5) is considered to have higher hardness and / or elastic modulus than the resist pattern obtained in steps (3) and earlier.

[0047] The following stresses are known to be applied to the resist wall during drying. As equation (8) in Namatsu et al. Appl. Phys. Lett. 1995 (66) pp. 2655-2657, σ max =6γcosθ / Dx(H / W) 2 As described above, the stress on the wall during drying can be expressed by the following formula. A schematic diagram is also shown in FIG. 5 of the same report. σ max : Maximum stress applied to the resist, γ: Surface tension of the liquid θ: contact angle, D: distance between walls H: Wall height, W: Wall width The lengths of D, H, and W can be measured by known methods (e.g., SEM imaging). As can be seen from the above equation, shorter D or shorter W causes more stress.

[0048] After applying the displacement solution according to the present invention, the displacement solution is removed. The removal method is not particularly limited, but is preferably carried out by applying a cleaning solution to the resist pattern. The preferred cleaning solution is water or a rinse solution, as described above. Finally, a dried resist pattern is formed, for example, by rotating the substrate at high speed.

[0049] The method of applying the above-mentioned cleaning solution and the displacement solution according to the present invention is not particularly limited, but the contact time with the resist pattern, i.e., the processing time, is preferably 1 second or longer. The processing temperature may also be arbitrary. The method of contact is also arbitrary; for example, it can be done by immersing the substrate in the liquid or by dropping the liquid onto the rotating surface of the substrate.

[0050] In the resist pattern manufacturing method of the present invention, a preferred embodiment of the manufacturing method of the present invention is to replace the developer with water, replace the water with the replacement solution according to the present invention, replace the replacement solution with a washing solution, and then dry the substrate by high-speed rotation.

[0051] The resist patterns produced by the method of the present invention have suppressed defects such as bridging and also suppressed resist pattern collapse. In this specification, bridging refers to the presence of an unintended structure in the grooves of the resist pattern and is a type of defect. Causes include resist patterns (walls) connecting with each other or foreign matter that should be flowed away becoming trapped in the grooves. If the target groove is filled with bridging, it becomes impossible to design the target circuit in subsequent processes such as etching. The mechanism by which the occurrence of defects such as bridging is suppressed when using the displacement solution according to the present invention has not been elucidated, and obtaining such an effect was unexpected.

[0052] <Method for manufacturing processed substrates and devices> After manufacturing the resist pattern as described above, the process is as follows: (6) Processing is performed using the resist pattern as a mask. This process is carried out to form a processed substrate according to the present invention. The resist pattern produced by the manufacturing method of the present invention can be used as a mask to pattern the intermediate layer and / or the substrate. Known methods such as etching (dry etching, wet etching) can be used for pattern formation. For example, the resist pattern can be used as an etching mask to etch the intermediate layer, and the resulting intermediate layer pattern can be used as an etching mask to etch the substrate and form a pattern on the substrate. Alternatively, the resist pattern can be used as an etching mask to etch the layer below the photoresist layer (e.g., the intermediate layer) while simultaneously etching the substrate. Wiring can then be formed on the substrate using the formed pattern. These layers can preferably be removed by dry etching with O2, CF4, CHF3, Cl2, or BCl3, with O2 or CF4 being preferred.

[0053] Then, if necessary, the process: (7) Forming wiring on the processed substrate The device is formed by performing these steps. Further processing can be carried out using known methods. After device formation, the substrate can be cut into chips as needed, connected to lead frames, and packaged in resin. A preferred example of the device is a semiconductor device.

[0054] The present invention will be described below using various examples. However, the embodiments of the present invention are not limited to these examples.

[0055] <Examples 101-115, Comparative Examples 102, 103> In water (deionized water), (A) ethanesulfonic acid as a sulfonyl group-containing compound and (B) ammonia as a nitrogen-containing compound are added in amounts of 0.2% by mass and 0.5% by mass, respectively, and dissolved. This is filtered (pore size = 10 nm) to prepare the replacement solution of Example 101. The substitution solutions for Examples 101 to 115, Comparative Examples 102 and 103 were prepared in the same manner as in Example 101, except that (A) the sulfonyl group-containing compound, (B) the nitrogen-containing compound, and (D) the polymer were of the types and concentrations listed in Table 1. [Table 1] In the table, A1: Ethanesulfonic acid, A2: Methanesulfonic acid, A3: Decansulfonic acid, A4: Sulfuric acid, A5: Trifluoromethanesulfonic acid, A6: Bis(trifluoromethanesulfonyl)amide, A7: A mixture of alkyl sulfonic acid compounds with 13 to 18 carbon atoms. B1: Ammonia, B2: Triethylamine, B3:2-aminoethanol, B4: Diethanolamine, B5: N-(2-aminoethylamino)ethanol, D1: Polyacrylic acid represented by the following structural formula, [ka] D2: Polyvinyl sulfonic acid represented by the following structural formula, [ka] D3: A vinyl ether alkylate homopolymer represented by the following structural formula. [ka] D4: Poly(2-acrylamido-2-methyl-1-propanesulfonic acid) [ka]

[0056] <Evaluation of the effect of preventing tipping over> An anti-reflective underlayer composition (AZ Kr-F17B, manufactured by Merck Performance Materials K.K. (hereinafter referred to as MPM)) is applied to a silicon substrate by spin coating, and heated on a hot plate at 180°C for 60 seconds to obtain an 80 nm thick underlayer anti-reflective film. A PHS-acrylate-based chemically amplified resist (DX6270P, manufactured by MPM) is applied on top of this, and heated on a hot plate at 120°C for 90 seconds to obtain a 620 nm thick resist film. This substrate is exposed using a KrF exposure apparatus (FPA3000 EX5, manufactured by Canon) through a mask (250 nm line / space 1:1). The exposure dose at this time is 25 mJ / cm². 2 ~40 mJ / cm² 2 The mixture is then varied to change the resulting line width. After that, post-exposure heating (PEB) is performed on a hot plate at 100°C for 60 seconds, and a 2.38% TMAH aqueous developer solution is poured in and held for 60 seconds (paddle). With the developer solution paddled, water is poured in and the substrate is rotated to replace the developer solution with water, and the substrate is stopped with the water paddled and left to stand for 90 seconds. After that, with the substrate still paddled with water, the replacement solution from Example 101 prepared above is poured in to replace the water with the replacement solution, and the substrate is stopped with the replacement solution paddled and left to stand for 30 seconds. After that, the substrate is dried by high-speed rotation for 30 seconds, and then water is poured in and washed for another 30 seconds. Finally, after the substrate is dried by high-speed rotation, the resist pattern is observed using a length measuring SEM CG4000 (Hitachi High-Technologies Corporation) to see if it is tilted or not. The same procedure was carried out using the displacement solutions from Examples 102-115 and Comparative Examples 102 and 103, respectively. Comparative Example 101 is performed in the same manner as in Example 101, by paddled with developer, then water is added, washed for 30 seconds, and the substrate is dried by high-speed rotation. In other words, Comparative Example 101 does not involve treatment with a displacement solution. At this point, when the line width becomes narrower than 188 nm, the deformation of the resist pattern is observed.

[0057] The evaluation criteria are as follows. The results obtained are shown in Table 1. A: When the line width is between 150nm and 178nm, no distortion of the resist pattern is observed. B: When the line width is between 178nm and 188nm, distortion of the resist pattern is observed. C: When the line width is between 188nm and 220nm, distortion of the resist pattern is observed.

[0058] <Evaluation of defect suppression effect> A PHS-acrylate-based chemically amplified resist for EUV is applied to a silicon substrate by spin coating and heated on a hot plate at 110°C for 60 seconds to obtain a resist film with a thickness of 45 nm. A 2.38% by mass aqueous TMAH developer solution is poured in and held for 30 seconds. With the developer solution paddled, water is poured in and the substrate is rotated to replace the developer solution with water, and the substrate is stopped for 90 seconds with the water paddled. Then, with the substrate still paddled with water, the replacement solution from Example 101 prepared above is poured in to replace the water with the replacement solution, and the substrate is stopped for 30 seconds with the replacement solution paddled. After that, the substrate is dried by high-speed rotation for 30 seconds, and then washed with water for another 30 seconds. Finally, the substrate is dried by high-speed rotation. The same procedure was carried out using the displacement solutions from Examples 102-115 and Comparative Examples 102 and 103, respectively. Comparative Example 101 is similar to Example 101 in that after paddled with the developer, water is added, washed for 30 seconds, and the substrate is dried by high-speed rotation. In other words, no treatment with displacement solution is performed.

[0059] The number of defects in each wafer was observed using the LS9110 wafer surface inspection system (manufactured by Hitachi High-Technologies Corporation) and evaluated as follows. The results obtained are shown in Table 1. A: The number of defects is less than 25% compared to Comparative Example 101. B: The number of defects is 25% or more but less than 50% compared to Comparative Example 101. C: The number of defects is 50% or more but less than 150% compared to Comparative Example 101. D: The number of defects is 150% or more compared to Comparative Example 101.

[0060] <Examples 201-208> The substitution solutions for Examples 201 to 208 were prepared in the same manner as in Example 101, except that (A) the sulfonyl group-containing compound, (B) the nitrogen-containing compound, and (D) the polymer were of the types and concentrations listed in Table 2. [Table 2]

[0061] <Evaluation of Limit Pattern Size 1> A silicon substrate is treated with hexamethyldisilazane (HMDS) at 90°C for 30 seconds. A PHS-acrylate-based chemically amplified resist for EUV is then applied by spin coating and heated on a hot plate at 110°C for 60 seconds to obtain a resist film with a thickness of 45 nm. This substrate is exposed using an EUV lithography system (NXE:3300B, ASML) through a mask (18 nm line / space 1:1). The exposure amount is varied to change the resulting line width. Afterwards, post-exposure heating (PEB) is performed on a hot plate at 100°C for 60 seconds, and a 2.38 mass% TMAH aqueous developer solution is poured in and held for 30 seconds (paddle). While the developer is paddled, water is started to flow, and the substrate is rotated to replace the developer with water. The substrate is then stopped while paddled with water and allowed to stand for 90 seconds. Next, with the substrate paddled with water, the displacement solution from Example 201 is poured in to replace the water with the displacement solution. The substrate is then stopped while paddled with the displacement solution and left to stand for 30 seconds. After that, it is dried by high-speed rotation for 30 seconds, rinsed with a surfactant-containing rinse solution (AZ SPC-708, MPM) for 30 seconds, and then dried by high-speed rotation. The formed resist pattern is observed using a length-measuring SEM CG4000 to check the line width and whether or not the pattern is distorted. The minimum line size for which no pattern distortion was observed is defined as the limit pattern size. Similarly, the limit pattern size is determined using the displacement solutions from Examples 202 to 208. Comparative Example 201 was obtained using the same procedure as above, except that the displacement solution was not poured in.

[0062] The processes are evaluated using the following methods. The resist films formed by each of the methods described below will be designated as Comparative Example 301. Samples obtained by treating the resist film of Comparative Example 301 with processes A to E will be designated as Comparative Example 302, Comparative Example 303, Example 301, Example 302, and Example 303. [Formation of resist film] A silicon substrate is treated with HMDS at 90°C for 30 seconds. An EUV-compatible PHS-acrylate chemically amplified resist is then applied by spin coating and heated on a hot plate at 110°C for 60 seconds to obtain a resist film with a thickness of 40 nm. [Process A] After pouring a 2.38% by mass TMAH aqueous developer solution onto the substrate, hold it there for 30 seconds. With the developer paddled on the substrate, begin flowing water and rotate to replace the developer with water. Stop while the substrate is still paddled with water and let it stand for 90 seconds. Next, rinse with water for 30 seconds, then rotate at high speed to dry the substrate. [Process B] After pouring a 2.38% by mass TMAH aqueous developer solution onto the substrate, hold it there for 30 seconds. With the developer paddled on the substrate, begin pouring water over it and rotate to replace the developer with water. Stop the rotation with the substrate paddled with water and let it stand for 90 seconds. Next, rinse with a surfactant-containing rinse solution (AZ SPC-708, MPM) for 30 seconds, then rotate at high speed to dry the substrate. [Process C] After pouring a 2.38% by mass TMAH aqueous developer solution onto the substrate, hold it for 30 seconds. With the developer solution paddled on the substrate, begin pouring water and rotate to replace the developer solution with water. Stop while the substrate is paddled with water and let it stand for 90 seconds. Next, pour in the replacement solution from Example 109 to replace the water with the replacement solution, and let it stand for 30 seconds while the substrate is paddled with the replacement solution. Then, rotate at high speed for 30 seconds to dry the substrate. After washing the substrate with water for 30 seconds, rotate at high speed to dry the substrate. [Process D] After pouring a 2.38 mass% aqueous TMAH developer solution onto a substrate, hold for 30 seconds. Start flowing water while the developer solution is padded on the substrate, replace the developer solution with water while rotating, stop while the water is padded, and leave to stand for 90 seconds. Next, pour the replacement solution of Example 109 to replace water with the replacement solution, then leave to stand for 30 seconds while the replacement solution is padded. Thereafter, perform high-speed rotation treatment for 30 seconds to dry the substrate. This substrate is washed for 30 seconds while pouring a surfactant-containing rinse solution (AZ SPC-708, MPM), then subjected to high-speed rotation treatment to dry the substrate. [Process E] After pouring a 2.38 mass% aqueous TMAH developer solution onto a substrate, hold for 30 seconds. Start flowing water while the developer solution is padded on the substrate, replace the developer solution with water while rotating, stop while the water is padded, and leave to stand for 90 seconds. Next, pour the replacement solution of Example 109 to replace water with the replacement solution, then leave to stand for 30 seconds while the replacement solution is padded. Thereafter, perform high-speed rotation treatment for 30 seconds to dry the substrate.

[0063] <TMAH intensity> The resist film obtained by the above resist film formation is designated as Comparative Example 301. Using a time-of-flight secondary ion mass spectrometer TOF-SIMS (TOF.SIMS5, ION-TOF), measure the residual amount of TMAH by argon sputtering from the surface to a depth of 2 nm of the resist film of Comparative Example 302 (the resist film obtained after performing Process A on the resist film of Comparative Example 301), and set this TMAH intensity to 1.0 (reference). For the resist film of Comparative Example 301, and the resist films obtained after performing Processes B to E respectively on the resist film of Comparative Example 301, measure the residual amount of TMAH in the same manner, and evaluate the TMAH intensity relative to the reference. The obtained results are as shown in Table 3. It is confirmed that by using the replacement solution according to the present invention, the amount of TMAH remaining in the resist film is reduced.

Table 3

[0064] <Evaluation of Limit Pattern Size 2> A silicon substrate is treated with HMDS at 90°C for 30 seconds. A PHS-acrylate-based chemically amplified resist for EUV is then applied by spin coating and heated on a hot plate at 110°C for 60 seconds to obtain a resist film with a thickness of 45 nm. This substrate is exposed using an EUV lithography system (NXE:3300B, ASML) through a mask (18 nm line / space 1:1). The exposure amount is varied to change the resulting line width. Post-exposure heating (PEB) is then performed on a hot plate at 100°C for 60 seconds. Processes A to D are then performed for each (Comparative Example 302, Comparative Example 303, Example 301 and Example 302).

[0065] The formed resist patterns were observed for line width and pattern deformation using a length-measuring SEM CG4000. The smallest line size in which no pattern deformation was observed was defined as the limit pattern size. The results are shown in Table 3.

[0066] <Evaluation of defect reduction rate> A resist film is obtained using the same procedure as in Evaluation 2 of the Limit Pattern Size described above, except that the exposure amount is not changed. Processes A to D are then performed on this resist film to form resist patterns (Comparative Example 302, Comparative Example 303, Example 301 and Example 302). The number of defects on the formed resist patterns is measured using a defect inspection device (UVision4, Applied Materials). The defect reduction rate for processes B to D is calculated based on the number of defects when process A is performed. A higher defect reduction rate indicates that defects are suppressed. The results obtained are shown in Table 3.

[0067] <Evaluation of contact angle and contact angle uniformity> A silicon substrate is treated with HMDS at 90°C for 30 seconds. A PHS-acrylate-based chemically amplified resist for EUV is then applied by spin coating and heated on a hot plate at 110°C for 60 seconds to obtain a resist film with a thickness of 40 nm (no treatment, Comparative Example 301). The resist film obtained in the same manner is treated with process A or process C (Comparative Example 302, Example 301). DIW is dropped onto the upper surface of the resist film and the contact angle is measured. Measurements are taken at 100 locations on the same sample to obtain 3 sigma. The results are shown in Table 3. Although not bound by theory, it is considered possible to restore uniformity by treating the film surface with the replacement solution of the present invention as a surface modifier, as TMAH solution treatment causes an uneven distribution of the remaining TMAH on the film surface. Some aspects of the present invention are shown below. [Aspect 1] (A) Sulfonyl group-containing compound, (B) Nitrogen-containing compounds, and (C) Solvent Resist pattern replacement solution comprising: Here, (A) A sulfonyl group-containing compound is represented by formula (a), [ka] R 11 C 1-20 Alkyl, C where some or all of the hydrogen atoms are substituted with halogens or -OH groups. 1-20 alkyl, unsubstituted, or R 13 C replaced by 6-10 It is an aryl, -OH, or nitrogen group, with H ionically bonded to the nitrogen. + NH 4 + You can change it to this, R 12 is -OH, C 1-15 Alkyl, or C in which some or all of the hydrogen atoms are substituted with halogens 1-15 It is alkyl, R 13 C 1-5 Alkyl, or C in which some or all of the hydrogen atoms are substituted with halogens 1-5 It is alkyl, R 11 、R 12 or R 13 The alkyl groups in this combination may form a ring, and two or more of these groups may form a ring by bonding with each other. n 11 = 1, 2 or 3; and (C) The solvent consists of water. [Aspect 2] (B) Resist pattern replacement solution according to embodiment 1, wherein the nitrogen-containing compound is (B1) a monoamine compound, (B2) a diamine compound, or (B3) a heteroaryl compound containing 1 to 3 nitrogen atoms: Here, (B1) Monoamine compounds are represented by formula (b1),

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Claims

1. (A) Sulfonyl group-containing compounds, (B) nitrogen-containing compound, (C) Solvent, and (D) Polymer Resist pattern replacement solution comprising: Here, (A) A sulfonyl group-containing compound is represented by formula (a-1), R 14 -SO 3 H (a-1) R14 is C １－２０ Alkyl; and (C) The solvent consists of water, (D) The polymer has sulfo or carboxy in its repeating units. Based on the total mass of the resist pattern substitution solution, (A) the content of the sulfonyl group-containing compound is 0.1 to 1% by mass. Based on the total mass of the resist pattern displacement solution, (B) the nitrogen-containing compound content is 0.1 to 1% by mass. Based on the total mass of the resist pattern substitution solution, the content of (D) polymer is 1 to 8% by mass.

2. The resist pattern replacement solution according to Claim 1, wherein (B) the nitrogen-containing compound is (B1) a monoamine compound, (B2) a diamine compound, or (B3) a heteroaryl having 1 to 3 nitrogen atoms: Here, (B1) Monoamine compounds are represented by formula (b1), 【Chemistry 1】 Here, R21, R22, and R23 are each independently H, C1-5 alkyl, or C1-5 alkanol. The alkyl groups in R21, R22, and R23 may form rings, two or more of these may be bonded to each other, and the -CH2- portion of the alkyl groups in R21, R22, and R23 may be substituted with -O-; (B2) Diamine compounds are represented by formula (b2), 【Chemistry 2】 Here, R31, R32, R33, and R34 are each independently H, C1-5 alkyl, or C1-5 alkanol. The alkyl groups in R31, R32, R33, and R34 may form rings, and two or more of these may be bonded to each other, and the -CH2- portion of the alkyl groups in R31, R32, R33, and R34 may be substituted with -O-. L 31 is a C 1-5 alkylene, and the -CH 2- portion of the alkylene may be substituted with -O-.

3. The content of (C) solvent is 80 to 99.98% by mass, based on the total mass of the resist pattern substitution solution; or The resist pattern displacement solution according to claim 1 or 2, wherein the amount of water contained in the solvent (C) is 80 to 99.94% by mass, based on the total mass of the resist pattern displacement solution.

4. The resist pattern substitution solution according to any one of claims 1 to 3, further comprising (E) a surfactant.

5. The resist pattern replacement solution according to any one of claims 1 to 4, further comprising (F) additive: Here, (F) additive comprises an acid, a base, a surfactant other than (E) surfactant, a bactericide, an antimicrobial agent, a preservative, an antifungal agent, or a combination thereof; however, if the resist pattern displacement solution contains a surfactant other than (E) surfactant, then the resist pattern displacement solution also contains (E) surfactant; Preferably, the content of additive (F) is 0.0005 to 20% by mass, based on the resist pattern substitution solution.

6. The resist pattern replacement liquid according to any one of claims 1 to 5, characterized in that the resist pattern replacement liquid is applied between resist patterns to replace the liquid present between resist patterns.

7. Use of the resist pattern replacement solution according to any one of claims 1 to 6 in the manufacture of a resist pattern.

8. Use of the resist pattern replacement solution according to any one of claims 1 to 6 in the manufacture of a processed substrate.

9. Use of the resist pattern substitution solution according to any one of claims 1 to 6 in the manufacture of a device.

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