Replacement liquid of liquid filling between resist patterns, and method for producing resist patterns 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 an inter-resist pattern replacement liquid and a method for producing a resist pattern using the same.The present invention also relates to a method for producing a processed substrate and a method for producing a device. [Background technology]

[0002] In recent years, the need for higher integration of LSIs has increased, resulting in a demand for finer resist patterns. To meet these needs, lithography processes using short-wavelength light, such as KrF excimer lasers (248 nm), ArF excimer lasers (193 nm), extreme ultraviolet (EUV; 13 nm), X-rays, and electron beams, are becoming more common. To meet this demand for finer resist patterns, photosensitive resin compositions used as resists in fine processing are also required to have high resolution. However, as miniaturization progresses, the resist pattern tends to collapse, the number of defects increases, and pattern roughness tends to worsen.

[0003] Resist pattern collapse is also thought to occur when the pattern is washed with water (deionized water) after development due to the negative pressure generated between the patterns caused by the surface tension of the water. To prevent resist pattern collapse, there is a method of washing with a rinse solution containing specific components instead of conventional water (see, for example, Patent Document 1). Another method of improving resist surface roughness is to apply a composition containing specific components to the dried resist pattern (see, 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 Summary of the Invention [Problem to be solved by the invention]

[0005] The present inventors have recognized that there are one or more problems that still require improvement, such as the following: Prevents resist pattern collapse in fine resist patterns; reduces defects in fine resist patterns; suppresses variations in the surface energy of the resist film; reduces components derived from the developer remaining in the resist pattern film; suppresses swelling of the resist pattern; reduces the frequency of water droplets occurring in the process of drying the resist pattern; increases the hardness and / or elastic modulus of the resist pattern; suppresses variations in the shape of the resist pattern. [Means for solving the problem]

[0006] The resist pattern replacement liquid according to the present invention comprises: (A) a sulfonyl group-containing compound, (B) nitrogen-containing compounds, and (C) Solvent comprising where: (A) The sulfonyl group-containing compound is represented by formula (a): [ka] R 11 is C 1-20 Alkyl, C in which some or all of the hydrogen atoms are replaced by halogen or -OH 1-20 Alkyl, unsubstituted or R 13 C replaced with 6-10 Aryl, -OH, or nitrogen, and H ionically bonded to nitrogen + is NH4 + You can also change it to R 12 -OH, C 1-15 Alkyl or C in which some or all of the hydrogen atoms are replaced by halogen 1-15 is alkyl, R 13 is C 1-5Alkyl or C in which some or all of the hydrogen atoms are replaced by halogen 1-5 is alkyl, R 11 , R 12 or R 13 The alkyl in may form a ring, or two or more of these may be bonded to each other to form a ring, n 11 = 1, 2, or 3; and (C) The solvent comprises water.

[0007] 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) applying a developer to the exposed photosensitive resin layer to form a resist pattern; (4) applying the above-described inter-resist pattern replacement liquid to the resist pattern to replace the liquid present between the resist patterns; and (5) The inter-resist pattern replacement liquid is removed.

[0008] The method for producing a processed substrate according to the present invention comprises the following steps: producing a resist pattern by the above method; and (6) Processing is performed using the resist pattern as a mask.

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

[0010] By using the resist pattern replacement liquid according to the present invention, one or more of the following effects can be expected. It is possible to prevent resist pattern collapse in fine resist patterns; it is possible to reduce defects in fine resist patterns; it is possible to suppress variations in the surface energy of the resist film; it is possible to reduce components derived from the developer remaining in the resist pattern film; it is possible to suppress swelling of the resist pattern; it is possible to reduce the frequency of water droplets occurring in the process of drying the resist pattern; it is possible to increase the hardness and / or elastic modulus of the resist pattern; and it is possible to suppress variations in the shape of the resist pattern. DETAILED DESCRIPTION OF THE INVENTION

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

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

[0013] <Resist pattern replacement liquid> The inter-resist pattern replacement liquid (hereinafter, sometimes referred to as replacement liquid) according to the present invention comprises (A) a sulfonyl group-containing compound, (B) a nitrogen-containing compound, and (C) a solvent. The inter-resist pattern replacement liquid is characterized in that it is applied between resist patterns to replace the liquid present between the resist patterns. In other words, the inter-resist pattern replacement liquid according to the present invention is applied between resist patterns in a wet state after development processing, and is different from the resist pattern treatment liquid that is applied to the resist pattern after drying after development processing.

[0014] (A) Sulfonyl group-containing compound The sulfonyl group-containing compound (A) used in the present invention is represented by formula (a). [ka] R 11 is C 1-20 Alkyl, C in which some or all of the hydrogen atoms are replaced by halogen (preferably fluorine) or -OH 1-20 Alkyl, unsubstituted or R 13 C replaced with 6-10aryl, -OH, or nitrogen, where nitrogen is n 11 When = 1, -NH2, n 11 When = 2, it means -NH-. H ionically bonded to nitrogen + is NH4 + For example, n 11 When = 2, H of -NH- + is NH4 + In a preferred embodiment of the present invention, H ionically bonded to nitrogen is + is NH4 + Here, the above C 1-20 Alkyl is n 11 When is 2 or 3, C 1-20 R means a divalent or trivalent saturated hydrocarbon group of the formula: 12 -OH, C 1-15 Alkyl or C in which some or all of the hydrogen atoms are replaced by halogen 1-15 It is alkyl. R 13 is C 1-5 Alkyl or C in which some or all of the hydrogen atoms are replaced by halogen 1-5 It is alkyl. R 11 , R 12 or R 13 The alkyl in the formula (I) may form a ring, or two or more of these may be bonded to each other to form a ring. n 11 n = 1, 2, or 3; preferably 1 or 2; more preferably 1. 11 =2 is another preferred embodiment. Without being bound by theory, it is believed that the presence of a sulfonyl group (more preferably a sulfonic acid or sulfonylimide skeleton) makes it possible to remove residual components of a developer (more preferably an alkaline aqueous solution, even more preferably an aqueous tetramethylammonium hydroxide (TMAH) solution) remaining on a resist pattern.

[0015] In one preferred embodiment, formula (a) is represented by formula (a-1). R 14-SO3H (a-1) where: R 14 is C 1-20 Alkyl, C in which some or all of the hydrogen atoms are replaced by fluorine or -OH 1-20 Alkyl, unsubstituted or R 13 C replaced with 6-10 aryl, or -OH; R 13 is 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) where: R 15 -OH, C 1-9 Alkyl or C in which some or all of the hydrogen atoms have been replaced by fluorine or -OH 1-9 It is alkyl. R 15 is preferably —OH, linear C 1-3 Alkyl, hydroxymethyl, hydroxyethyl, or C in which some or all of the hydrogen atoms are replaced by fluorine 1-8 alkyl; more preferably -OH, methyl, ethyl, hydroxymethyl, C in which all hydrogen atoms are replaced by fluorine atoms 1-4 Alkyl or C with some of the hydrogen replaced by fluorine 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) where: m is a number from 10 to 20. m is preferably a number from 11 to 19, more preferably a number from 12 to 18, and even more preferably a number from 13 to 18. Examples of these include decane sulfonic acid, 1-dodecane sulfonic acid, and 1-tetradecane sulfonic acid. For example, an alkylsulfonic acid represented by (a-1-2) having 11 to 19 carbon atoms (the above m=11 to 19) is one preferred embodiment of the sulfonyl group-containing compound (A) of the present invention.

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

[0020] In one preferred embodiment, formula (a) is represented by formula (a-2). [ka] where: L 11 is C 1-5 alkylene, or -NH-; preferably C 1-3 It is alkylene or -NH-; more preferably -NH-. H ionically bonded to nitrogen + is NH4 + In a preferred embodiment of the present invention, H ionically bonded to nitrogen + is NH4 + and will not be changed. Independently, R 17 and R 18 -OH, C 1-15 Alkyl or C in which some or all of the hydrogen atoms are replaced by fluorine 1-15 alkyl; preferably, C in which all of the -OH or hydrogen atoms are replaced by 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), which can be included in formula (a-2). 11 is -NH- and R 17 is fluoroethyl (C2), and R 18 is fluoromethyl (C1) and R 17 and R 18 The compound on the right below has H ionically bonded to the nitrogen of the compound on the left below. + NH4 + It is an ammonium salt modified as follows: [ka]

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

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

[0023] (B) Nitrogen-containing compounds The displacement liquid according to the present invention contains (B) a nitrogen-containing compound. (B) The nitrogen-containing compound plays a role in controlling the acidity of the displacement liquid according to the present invention. Without being bound by theory, it is believed that if (B) the nitrogen-containing compound is not contained, deprotection of the resist is induced by the acidic component (e.g., (A) the sulfonyl group-containing compound or (D) the polymer), resulting in pattern collapse. (B) The nitrogen-containing compound is (B1) a monoamine compound, (B2) a diamine compound, or (B3) a heteroaryl containing 1 to 3 nitrogen atoms.

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

[0025] (B2) Diamine compound The diamine compound (B2) is represented by formula (b2). [ka] where: R 31 , R 32 , R 33 and R 34 are independently H, C 1-5 Alkyl, or C 1-5 is an alkanol, R 31 , R 32 , R 33 and R 34 The alkyl in may form a ring, and two or more of them may be bonded to each other, and R 31 , R 32 , R 33 and R 34 The —CH2— moiety of the alkyl in L 31 is C 1-5 It is alkylene, and the -CH2- portion of the alkylene may be substituted with -O-. Examples of the (B2) diamine compound 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 containing 1 to 3 nitrogen atoms The heteroaryl containing 1 to 3 nitrogen atoms is preferably a five- or six-membered ring, and examples thereof include pyridine, imidazole, and triazine. The number of nitrogen atoms contained is preferably 1 or 2, and more preferably 1.

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

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

[0029] (C) Solvent The displacement liquid according to the present invention comprises a (C) solvent. The (C) solvent comprises water. The water is preferably deionized water. For use in fine resist patterns, the (C) solvent preferably has a low impurity content. A preferred (C) solvent has an impurity content of 1 ppm or less; more preferably 100 ppb or less; and even more preferably 10 ppb or less. Filtering the liquid for use in fine processes is also a preferred embodiment of the present invention. The content of water based on the total mass of (C) solvent 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 a preferred embodiment of the present invention, (C) solvent consists essentially of water. However, an embodiment in which an additive is contained in the replacement liquid of the present invention in a state of being dissolved and / or dispersed in a solvent other than water (for example, a surfactant) is also acceptable as a preferred embodiment of the present invention.

[0030] Specific examples of the solvent (C) 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 solvents are preferred in terms of the storage stability of the solution. Two or more of these solvents can also be used as a mixture.

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

[0032] The replacement fluid of the present invention essentially contains the above-described components (A) to (C), but may contain additional compounds as necessary. These will be described in detail below. The total amount of components other than (A) to (C) (if multiple components are present) in the entire composition is 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 replacement fluid. A preferred embodiment of the present invention is one in which the replacement fluid of the present invention does not contain any components other than (A) to (C) (0% by mass).

[0033] (D) Polymer The replacement liquid according to the present invention may further contain (D) a polymer. The polymer (D) is preferably a water-soluble polymer from the viewpoint of affinity with the displacement liquid. Among 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. The polymer (D) further preferably has sulfo (-SO3H) and / or carboxy (-COOH) in the repeating unit. Examples of the (D) polymer include polyacrylic acid, polymethacrylic acid, polymaleic acid, polyvinyl sulfonic acid, polystyrene sulfonic acid, fluorinated vinyl ether alkyl acid polymers, poly2-acrylamido-2-methyl-1-propanesulfonic acid, polytrifluoromethylacrylic acid, salts thereof, and copolymers of any of these. Furthermore, as the (D) polymer, polyacrylamide or poly(trifluoromethyl)-4-penten-2-ol can also be used.

[0034] By including the (D) polymer, the effect of preventing collapse and the effect of suppressing defects can be improved.

[0035] The mass average molecular weight of the (D) 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 mass average molecular weight in terms of polystyrene, and can be measured by gel permeation chromatography using polystyrene as the standard.

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

[0037] (E) Surfactant The replacement liquid according to the present invention may further contain a surfactant (E). The surfactant (E) is a component different from the components (A) to (D). By including a surfactant, the coating properties can be improved. In the present invention, the term "surfactant (E)" refers to a compound having the above-described function. The compound may be dissolved or dispersed in a solvent and contained in the composition (liquid). However, it is preferable that such a solvent is contained in the composition as the solvent (C) or other component. Hereinafter, the same applies to various additives that may be contained in the composition. The surfactants that can be used in the present invention include anionic surfactants, cationic surfactants, and nonionic surfactants. More specifically, lauryl pyridinium chloride, lauryl methyl ammonium chloride, polyoxyethylene octyl ether, polyoxyethylene lauryl ether, and polyoxyethylene acetylenic glycol ether, fluorine-containing surfactants (e.g., Fluorad (trade name, Sumitomo 3M), Megafac (trade name, DIC), Sulfuron (trade name, Asahi Glass)), and organic siloxane surfactants (e.g., KP341 (trade name, Shin-Etsu Chemical Co., Ltd.)) can be mentioned.

[0038] The content of the (E) surfactant is preferably 0.01 to 5 mass %, more preferably 0.03 to 1 mass %, based on the total mass of the replacement liquid according to the present invention. In one preferred embodiment, the replacement liquid does not contain the (E) surfactant (0.0 mass %).

[0039] (F) Additives The displacement fluid used in the present invention may further contain an additive (F). The additive (F) is a component different from the components (A) to (E). The additive (F) preferably contains an acid, a base, a surfactant other than the surfactant (E), a bactericide, an antibacterial agent, a preservative, an antifungal agent, or a combination thereof; more preferably contains an acid, a base, a bactericide, an antibacterial agent, a preservative, or an antifungal agent. The content of the (F) additive is preferably 0.0005 to 20 mass %, more preferably 0.0005 to 1 mass %, based on the total mass of the resist pattern replacement liquid. In one preferred embodiment, the (F) additive is not included (0.0 mass %).

[0040] <Method of manufacturing a resist pattern> 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) applying a developer to the exposed photosensitive resin layer to form a resist pattern; (4) applying the resist pattern inter-pattern replacement liquid of the present invention to the resist pattern to replace the liquid present between the resist patterns; and (5) The inter-resist pattern replacement liquid is removed. For clarity, the numbers in parentheses indicate the order, e.g., step (4) is performed before step (5).

[0041] Details are explained below. The photosensitive resin composition is applied by an appropriate method onto a substrate (e.g., a silicon / silicon dioxide-coated substrate, a silicon nitride substrate, a silicon wafer substrate, a glass substrate, an ITO substrate, or the like). In the present invention, "above" includes a case where the composition is formed directly onto the substrate and a case where the composition is formed via another layer. For example, a planarizing film or a resist underlayer film may be formed directly onto the substrate, and the photosensitive resin composition may be applied directly onto the planarizing film or resist underlayer film. The application method is not particularly limited, and examples include coating methods using a spinner or coater. After coating, the photosensitive resin layer is formed by heating, if necessary. Heating is performed, for example, using 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 a hot plate. The heating time is preferably 30 to 900 seconds, more preferably 60 to 300 seconds. Heating is preferably performed in air or a nitrogen gas atmosphere. The thickness of the photosensitive resin layer is selected depending on the purpose, and the thickness of the photosensitive resin layer can be made greater than 1 μm.

[0042] In the resist pattern manufacturing method according to the present invention, the presence of films or layers other than the photosensitive resin layer is also permitted. An intermediate layer may be interposed between the substrate and the photosensitive resin layer without direct contact. The intermediate layer is a layer formed between the substrate and the photosensitive resin layer and is also called an underlayer film. Examples of underlayer films include substrate modification films, planarization films, bottom antireflective coatings (BARCs), inorganic hard mask intermediate layers (silicon oxide films, silicon nitride films, and silicon oxide nitride films), and adhesion films. The intermediate layer may be composed of one layer or multiple layers. A top antireflective coating (TARC) may also be formed on the photosensitive resin layer.

[0043] The photosensitive resin layer is exposed to radiation through a predetermined mask. When other layers are included (such as a TARC layer), they may be exposed as well. 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 laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), and extreme ultraviolet (wavelength 13.5 nm) can be used. These wavelengths allow a ±1% range. After exposure, post-exposure bake (PEB) can be performed as needed. The PEB temperature is 70 to 150°C, preferably 80 to 120°C, and the heating time is 30 to 300 seconds, preferably 30 to 120 seconds. Heating is preferably performed in air or a nitrogen gas atmosphere.

[0044] Next, a developer is applied to the exposed photosensitive resin layer to form a resist pattern. Conventional methods used for developing photoresists, such as paddle development, immersion development, and swing immersion development, can be used as the development method. Preferably, the development method is paddle development. The developer used may be an aqueous alkali solution containing an inorganic alkali such as sodium hydroxide, potassium hydroxide, sodium carbonate, or sodium silicate; an organic amine such as ammonia, ethylamine, propylamine, diethylamine, diethylaminoethanol, or triethylamine; or a quaternary amine such as TMAH. A 2.38% by mass (±1% tolerance) aqueous TMAH solution is preferably used. Furthermore, 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 appropriately selected from the range of generally 10 to 300 seconds, preferably 20 to 60 seconds.

[0045] With the developer remaining between the resist patterns, if necessary, further process: (3.1) Applying a cleaning solution to the resist pattern to clean the resist pattern The cleaning liquid used here may be one used in a known method, such as water (deionized water) or a known rinse liquid. When the developer or the above-mentioned cleaning liquid remains between the resist patterns, the substitute liquid according to the present invention is applied to the resist pattern to substitute for 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 (for example, alkaline components, TMAH) may remain in the resist pattern film. Without being bound by theory, the inventors considered the following. Residual components derived from the developer are difficult to remove with the above-mentioned cleaning solutions (water and rinse solutions). It is believed that by applying the displacement solution of the present invention to the resist pattern, the sulfonyl group-containing compound contained in the displacement solution of the present invention can remove residual components derived from the developer from the resist pattern film. As a function of this, attraction due to neutralization energy may also occur. In other words, steps (4) and / or (5) reduce residual components derived from the developer from the resist pattern. Residual components derived from the developer present in the resist pattern film may cause the resist pattern to swell, and the uneven presence of alkaline components in the resist pattern may result in uneven surface energy within the resist pattern. Uneven surface energy of the resist pattern may trigger the formation of water droplets during drying of the pattern, leading to pattern collapse. The application of the displacement liquid of the present invention reduces residual components derived from the developer, thereby suppressing swelling of the resist pattern, increasing the hardness of the resist pattern, and further homogenizing the surface energy of the resist pattern, thereby suppressing resist pattern collapse. Therefore, it is more preferable not to dry the resist pattern before applying the displacement liquid of the present invention. In other words, it is preferable not to dry the resist pattern between steps (3) and (4). In a preferred embodiment of the present invention, the displacement liquid of the present invention can also be considered a resist film surface modifier containing the above-mentioned components (A), (B), (C), etc. The resist film referred to here is not limited to a patterned one, but a patterned resist film is more preferred. The resist pattern obtained in step (5) is believed to have a higher hardness and / or elastic modulus than the resist pattern obtained in steps (1) through (3).

[0047] The following stresses are known to act on the resist wall during drying. As equation (8) of Namatsu et al. Appl. Phys. Lett. 1995 (66) p. 2655-2657, σ max =6γcosθ / Dx(H / W) 2 As described above, the stress acting 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 (for example, SEM photographs). As can be seen from the above equation, a shorter D or a shorter W will cause more stress.

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

[0049] The method for applying the cleaning solution or the replacement solution according to the present invention is not particularly limited, but the time for contacting the resist pattern, i.e., the treatment time, is preferably 1 second or more. The treatment temperature may also be any desired temperature. The contact method may also be any desired method, such as immersing the substrate in the solution or dropping the solution onto the surface of a rotating substrate.

[0050] In a preferred embodiment of the resist pattern production method of the present invention, the developer is replaced with water, the water is replaced with the replacement liquid according to the present invention, the replacement liquid is replaced with a cleaning liquid, and then the substrate is dried by a high-speed rotation process.

[0051] Resist patterns produced by the method of the present invention are suppressed from generating defects such as bridges, and also suppress resist pattern collapse. In this specification, a bridge is a type of defect, which refers to the presence of an unintended structure in the grooves of a resist pattern. Possible causes include connections between resist pattern walls, or foreign matter that should be washed away becoming trapped and remaining in the grooves. If the intended grooves are filled with bridges, it becomes impossible to design the intended circuit in subsequent processes such as etching. The mechanism by which defects such as bridges are suppressed when using the replacement liquid of the present invention is not yet elucidated, and it was unexpected that such an effect could be achieved.

[0052] <Methods of manufacturing processed substrates and devices> After forming the resist pattern as described above, the process: (6) Processing is performed using the resist pattern as a mask. to form a processed substrate according to the present invention. The resist pattern produced by the production method of the present invention can be used as a mask to pattern the intermediate layer and / or the substrate. Known techniques such as etching (dry etching, wet etching) can be used to form the pattern. For example, the intermediate layer can be etched using the resist pattern as an etching mask, and the substrate can be etched using the resulting intermediate layer pattern as an etching mask to form a pattern on the substrate. Alternatively, the resist pattern can be used as an etching mask to etch layers below the photoresist layer (e.g., the intermediate layer) while simultaneously etching the 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.

[0053] Then, if necessary, perform the following steps: (7) Forming wiring on the processed substrate A device is formed by the above steps. These further processing steps can be carried out by applying known methods. After the device is formed, the substrate can be cut into chips, connected to a lead frame, and packaged with resin, as needed. A suitable example of the device is a semiconductor device.

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

[0055] <Examples 101 to 115, Comparative Examples 102 and 103> (A) Ethanesulfonic acid as a sulfonyl group-containing compound and (B) ammonia as a nitrogen-containing compound are added to water (deionized water) so that the concentrations are 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 replacement solutions of Examples 101 to 115 and Comparative Examples 102 and 103 were prepared in the same manner as in Example 101, except that the types and concentrations of (A) the sulfonyl group-containing compound, (B) the nitrogen-containing compound, and (D) the polymer were each set forth in Table 1. [Table 1] In the table, A1: ethanesulfonic acid, A2: methanesulfonic acid, A3: decane sulfonic acid, A4: Sulfuric acid, A5: Trifluoromethanesulfonic acid, A6: bis(trifluoromethanesulfonyl)amide, A7: a mixture of alkylsulfonic acid compounds having 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: Fluorinated vinyl ether alkyl acid homopolymer represented by the following structural formula [ka] D4: Poly(2-acrylamido-2-methyl-1-propanesulfonic acid) [ka]

[0056] <Evaluation of fall prevention effect> A base anti-reflective coating composition (AZ Kr-F17B, manufactured by Merck Performance Materials Co., Ltd. (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 a bottom anti-reflective coating with a thickness of 80 nm. A PHS-acrylate 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 resist film with a thickness of 620 nm. This substrate is exposed through a mask (250 nm line / space 1:1) using a KrF exposure system (FPA3000 EX5, manufactured by Canon). The exposure dose is 25 mJ / cm. 2 ~40mJ / cm 2 The temperature is changed to change the resulting line width. Then, post-exposure baking (PEB) is performed on a hot plate at 100°C for 60 seconds, and a 2.38% by mass TMAH aqueous developer is poured in and held for 60 seconds (puddling). While the developer is puddling, water is started to flow, and while rotating the substrate, the developer is replaced with water. The process is stopped while the substrate is puddling with water, and the substrate is left standing for 90 seconds. Then, while the substrate is puddling with water, the replacement solution prepared in Example 101 above is poured in, and the water is replaced with the replacement solution. The process is stopped while the substrate is puddling with the replacement solution, and the substrate is left standing for 30 seconds. The substrate is then dried by high-speed rotation for 30 seconds, and then water is poured in and washed for 30 seconds. Finally, the substrate is dried by high-speed rotation, and the resist pattern is observed for collapse using a critical dimension SEM CG4000 (manufactured by Hitachi High-Technologies Corporation). The same procedure was carried out using the replacement liquids of Examples 102 to 115 and Comparative Examples 102 and 103, respectively. In Comparative Example 101, the developer was puddled in the same manner as in Example 101, followed by pouring water in, washing for 30 seconds, and drying the substrate by high-speed rotation. In other words, in Comparative Example 101, treatment with a replacement liquid was not performed. In this case, when the line width became narrower than 188 nm, the resist pattern collapsed.

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

[0058] <Evaluation of defect suppression effect> A PHS-acrylate chemically amplified resist for EUV was spin-coated onto a silicon substrate and heated on a hot plate at 110°C for 60 seconds to obtain a 45 nm thick resist film. A 2.38% by weight TMAH aqueous solution was poured into the developer and then held for 30 seconds. While the developer was puddling, water was started to flow, and the developer was replaced with water while rotating the substrate. The substrate was then left puddling with water for 90 seconds. The replacement solution prepared in Example 101 was then poured into the puddling with water, and the water was replaced with the replacement solution. The replacement solution was then left puddling with the replacement solution for 30 seconds. The substrate was then dried by high-speed spinning for 30 seconds, and then washed with water for another 30 seconds. Finally, the substrate was dried by high-speed spinning. The same procedure was carried out using the replacement liquids of Examples 102 to 115 and Comparative Examples 102 and 103, respectively. In Comparative Example 101, the developer was puddled in the same manner as in Example 101, and then water was poured in, the substrate was washed for 30 seconds, and the substrate was dried by high-speed rotation treatment. In other words, treatment with a substitute liquid was not performed.

[0059] The number of defects in each sample was observed using a wafer surface inspection device LS9110 (manufactured by Hitachi High-Technologies Corporation) and evaluated as follows. The results 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 and less than 50% compared to Comparative Example 101. C: The number of defects is 50% or more and 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 to 208> The replacement solutions of Examples 201 to 208 are prepared in the same manner as in Example 101, except that the types and concentrations of (A) the sulfonyl group-containing compound, (B) the nitrogen-containing compound, and (D) the polymer are respectively as shown in Table 2. [Table 2]

[0061] <Evaluation of limiting pattern size 1> A silicon substrate is treated with hexamethyldisilazane (HMDS) at 90°C for 30 seconds. An EUV PHS-acrylate chemically amplified resist is then spin-coated and heated on a hotplate at 110°C for 60 seconds to obtain a 45nm thick resist film. The substrate is then exposed to light through a mask (18nm line / space 1:1) using an EUV exposure system (NXE:3300B, ASML). The exposure dose is varied to vary the resulting line width. A post-exposure bake (PEB) is then performed on a hotplate at 100°C for 60 seconds. A 2.38% by weight aqueous TMAH developer is then poured in and held for 30 seconds (puddling). While the developer is puddling, water is started, and the developer is replaced with water while the substrate is rotating. The puddling is stopped and the substrate is left to stand for 90 seconds. Then, while the substrate is being puddled with water, the replacement liquid of Example 201 is poured in to replace the water with the replacement liquid, and the substrate is stopped while being puddled with the replacement liquid and left to stand for 30 seconds. After that, the substrate is dried by high-speed rotation for 30 seconds, rinsed with a surfactant-containing rinse liquid (AZ SPC-708, MPM) for 30 seconds, and then dried by high-speed rotation. The formed resist pattern is observed for line width and the presence or absence of pattern collapse using a critical dimension SEM CG4000. The minimum line size at which pattern collapse is not confirmed is defined as the limiting pattern size. Similarly, the critical pattern size is determined using the replacement liquids of Examples 202 to 208, respectively. Comparative Example 201 shows the results obtained by carrying out the same procedure as above, except that the replacement liquid was not poured in.

[0062] The processes were evaluated using the following methods. A resist film formed by each of the methods described below was designated Comparative Example 301. Samples obtained by treating the resist film of Comparative Example 301 with Processes A to E were designated Comparative Example 302, Comparative Example 303, Example 301, Example 302, and Example 303. [Resist film formation] A silicon substrate is treated with HMDS at 90°C for 30 seconds, and then a PHS-acrylate chemically amplified resist for EUV is applied onto it by spin coating and heated on a hot plate at 110°C for 60 seconds to obtain a 40nm thick resist film. [Process A] After pouring a 2.38% by weight TMAH aqueous developer onto the substrate, hold the substrate for 30 seconds. While the developer is puddling on the substrate, start pouring water. While rotating, replace the developer with water. Stop puddling with water and let stand for 90 seconds. Next, rinse with water for 30 seconds, then spin at high speed to dry the substrate. [Process B] A 2.38% by weight TMAH aqueous developer solution was poured onto the substrate and then held for 30 seconds. While the developer was puddling on the substrate, water was started to flow, and while rotating, the developer was replaced with water. The puddling was stopped with water, and the substrate was left to stand for 90 seconds. Next, a surfactant-containing rinse solution (AZ SPC-708, MPM) was poured in and the substrate was washed for 30 seconds, after which it was spun at high speed and dried. [Process C] A 2.38% by mass TMAH aqueous developer solution is poured onto the substrate, and then the substrate is left for 30 seconds. While the developer is puddling on the substrate, water is started to flow, and while rotating, the developer is replaced with water. The flow is stopped while the developer is puddling with water, and the substrate is left standing for 90 seconds. Next, the replacement solution of Example 109 is poured in to replace the water with the replacement solution, and the substrate is left standing for 30 seconds while the replacement solution is puddling. The substrate is then spun at high speed for 30 seconds to dry. The substrate is washed for 30 seconds while water is poured onto it, and then spun at high speed to dry the substrate. [Process D] After flowing a 2.38 mass% TMAH aqueous solution as a developer onto the substrate, it is held for 30 seconds. While the developer is being paddled on the substrate, water is started to flow, and while rotating, the developer is replaced with water. It is stopped in a state of being paddled with water and left standing for 90 seconds. Next, after flowing the replacement liquid of Example 109 to replace the water with the replacement liquid, it is left standing for 30 seconds in a state of being paddled with the replacement liquid. Then, it is subjected to a high-speed rotation treatment for 30 seconds to dry the substrate. After washing for 30 seconds while flowing a rinse liquid containing a surfactant (AZ SPC-708, MPM) onto this substrate, it is subjected to a high-speed rotation treatment to dry the substrate. [Process E] After flowing a 2.38 mass% TMAH aqueous solution as a developer onto the substrate, it is held for 30 seconds. While the developer is being paddled on the substrate, water is started to flow, and while rotating, the developer is replaced with water. It is stopped in a state of being paddled with water and left standing for 90 seconds. Next, after flowing the replacement liquid of Example 109 to replace the water with the replacement liquid, it is left standing for 30 seconds in a state of being paddled with the replacement liquid. Then, it is subjected to a high-speed rotation treatment for 30 seconds to dry the substrate.

[0063] <TMAH Strength> The resist film obtained by forming the resist film described above is taken as Comparative Example 301. Using a time-of-flight secondary ion mass spectrometer TOF-SIMS (TOF.SIMS5, ION-TOF), the remaining amount of TMAH is measured by argon sputtering from the surface to a depth of 2 nm of the resist film of Comparative Example 302 (the resist film after performing Process A on the resist film of Comparative Example 301), and this TMAH strength is set to 1.0 (reference). For the resist film of Comparative Example 301 and the resist films after performing Processes B to E on the resist film of Comparative Example 301, the remaining amount of TMAH is similarly measured, and the TMAH strength with respect to the reference is evaluated. The results obtained are as shown in Table 3. It is confirmed that by using the replacement liquid according to the present invention, the amount of TMAH remaining in the resist film is reduced.

Table 3

[0064] <Evaluation of limiting pattern size 2> A silicon substrate is treated with HMDS at 90°C for 30 seconds. An EUV PHS-acrylate chemically amplified resist is then spin-coated onto the substrate and heated on a hot plate at 110°C for 60 seconds to obtain a 45 nm thick resist film. This substrate is then exposed to light through a mask (18 nm line / space 1:1) using an EUV exposure system (NXE:3300B, manufactured by ASML). The exposure dose is varied to vary the resulting line width. A post-exposure bake (PEB) is then performed on a hot plate at 100°C for 60 seconds. Processes A to D are then performed (Comparative Example 302, Comparative Example 303, Example 301, and Example 302).

[0065] The formed resist patterns were each observed for line width and the presence or absence of pattern collapse using a critical dimension SEM CG4000. The minimum line size at which pattern collapse was not confirmed was defined as the limiting pattern size. The results obtained 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 critical pattern size, except that the exposure dose is not changed. Processes A to D are 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 pattern is measured using a defect inspection system (UVision 4, manufactured by Applied Materials). The defect reduction rate when processes B to D are performed is calculated based on the number of defects when process A is performed. Note that a higher defect reduction rate indicates greater defect suppression. The results obtained are as shown in Table 3.

[0067] <Evaluation of contact angle and contact angle uniformity> A silicon substrate was treated with HMDS at 90°C for 30 seconds. An EUV PHS-acrylate chemically amplified resist was then applied thereon by spin coating and heated on a hot plate at 110°C for 60 seconds, yielding a 40 nm thick resist film (no treatment, Comparative Example 301). The resist film obtained in the same manner was treated with Process A or Process C (Comparative Example 302, Example 301). DIW was dropped onto the top surface of the resist film, and the contact angle was measured. Measurements were made at 100 locations on the same sample to obtain a 3 sigma. The results are shown in Table 3. Without being bound by theory, it is believed that TMAH solution treatment causes a bias in the amount of TMAH remaining on the film surface, and that treatment with the replacement solution of the present invention as a surface modifier can restore uniformity.

Claims

1. (A) a sulfonyl group-containing compound, (B) nitrogen-containing compound, (C) a solvent, and (D) Polymer A resist pattern replacement solution comprising: where: (A) The sulfonyl group-containing compound is represented by formula (a-1), R 14 -SO 3 H (a-1) R14 is C １－２０ is alkyl; and (C) the solvent comprises water; (D) the polymer has sulfo or carboxy in the repeating unit, the content of the sulfonyl group-containing compound (A) is 0.1 to 1 mass % based on the total mass of the resist pattern replacement liquid, the content of the nitrogen-containing compound (B) is 0.1 to 1 mass % based on the total mass of the resist pattern replacement liquid, The content of the (D) polymer is 1 to 8 mass % based on the total mass of the resist pattern replacement liquid.

2. The resist pattern replacement solution according to claim 1, wherein the nitrogen-containing compound (B) is (B1) a monoamine compound, (B2) a diamine compound, or (B3) a heteroaryl containing 1 to 3 nitrogen atoms. where: (B1) The monoamine compound is represented by formula (b1), 【Chemical 1】 where: R 21 , R 22 and R 23 are each independently H, C 1-5 alkyl, or C 1-5 alkanol; The alkyls in R 21 , R 22 and R 23 may form a ring, or two or more of them may be bonded to each other, and the —CH 2 — moiety of the alkyl in R 21 , R 22 and R 23 may be substituted with —O—; The diamine compound (B2) is represented by formula (b2): 【Chemistry 2】 where: R 31 , R 32 , R 33 and R 34 are each independently H, C 1-5 alkyl, or C 1-5 alkanol; The alkyls in R 31 , R 32 , R 33 and R 34 may form a ring, or two or more of them may be bonded to each other, and the —CH 2 — moiety of the alkyl in R 31 , R 32 , R 33 and R 34 may be substituted with —O—; L 31 is C 1-5 alkylene, and the —CH 2 — portion of the alkylene may be substituted with —O—.

3. The content of the solvent (C) is 80 to 99.98 mass% based on the total mass of the resist pattern replacement liquid; or 3. The inter-resist pattern replacement liquid according to claim 1, wherein the water content of the solvent (C) is 80 to 99.94 mass % based on the total mass of the inter-resist pattern replacement liquid.

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

5. The resist pattern replacement liquid according to any one of claims 1 to 4, further comprising (F) an additive: Here, the (F) additive comprises an acid, a base, a surfactant other than the (E) surfactant, a bactericide, an antibacterial agent, an antiseptic, an antifungal agent, or a combination thereof; provided that when the inter-resist pattern replacement liquid comprises a surfactant other than the (E) surfactant, the inter-resist pattern replacement liquid also comprises the (E) surfactant; Preferably, the content of the additive (F) is 0.0005 to 20 mass % based on the resist pattern replacement liquid.

6. A resist pattern replacement liquid described in 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 the resist patterns.

7. Use of the resist pattern replacement liquid described in any one of claims 1 to 6 in the production of a resist pattern.

8. Use of the resist pattern replacement liquid described in any one of claims 1 to 6 in the production of processed substrates.

9. Use of the resist pattern replacement liquid described in any one of claims 1 to 6 in the manufacture of a device.

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