Substrate processing liquid

Abstract

To provide a substrate processing liquid with improved suppression of pattern collapse.SOLUTION: A substrate processing liquid contains a solidifying component and satisfies at least one of the following conditions (i) or (ii). (i) The solidifying component is a plastic crystalline compound having a melting point of 20°C or higher and 200°C or lower at atmospheric pressure. (ii) The substrate processing liquid further contains a surface modifying component.SELECTED DRAWING: None

Description

[Technical Field]

[0001] An embodiment of the present invention relates to a substrate processing liquid. [Background technology]

[0002] In the manufacture of devices (electronic components) such as semiconductor devices and liquid crystal displays, a process is known in which a fine concave-convex pattern is formed on a wafer surface by film deposition, lithography, etching, or the like, and then the wafer surface is cleaned. Due to the need for higher integration of LSIs, there is a trend toward miniaturization of elements, resulting in a need for such concave-convex patterns to have narrower widths and higher aspect ratios. Known techniques for cleaning wafer surfaces with concave-convex patterns include supplying cleaning solutions such as ion-exchanged water (DIW) or organic solvents to remove contaminants. However, when the concave-convex pattern is very fine, there is a problem in that the pattern collapses during the drying process after contaminant removal due to the surface tension and capillary action of the cleaning solution.

[0003] In light of this situation, there have been attempts to clean patterns while preventing pattern collapse by replacing cleaning solutions, etc., in cleaning processes with a filling treatment agent containing a sublimable substance and then sublimating the sublimable substance. Patent Document 1 discusses a technique in which a substrate processing solution containing plastic crystals is supplied to a substrate and cooled to semi-solidify, forming a plastic crystal layer, which is then removed by vaporization, thereby removing the liquid adhering to the substrate surface while preventing pattern collapse. Patent Document 2 discusses a technique in which cyclohexanone oxime is added to a substrate processing solution as a sublimable substance, removing the liquid adhering to the substrate surface while preventing pattern collapse. Patent Document 3 provides a pattern formation method using a gap-filling compound. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 2019-62004 [Patent Document 2] Patent Publication No. 2021-10002 [Patent Document 3] International Publication No. 2017 / 174476 [Non-patent literature]

[0005] [Non-Patent Document 1] Toshiba Review, Vol. 59, No. 8 (2004), pp. 22-25 Summary of the Invention [Problem to be solved by the invention]

[0006] The inventors have found that there are still one or more problems that require improvement. These include, for example: Substrate patterns cannot be cleaned; Pattern collapse occurs during substrate pattern cleaning; Fine substrate patterns cannot be filled; Films cannot be formed on fine substrate patterns; Films cannot be formed without cooling; Reduced pressure is required to remove films; The solvent cannot be vaporized first, and then the solidified components cannot be vaporized in stages; A large amount of solidified components remains on the substrate pattern after removal; The solubility of the solidified components in the solvent is low; The process for removing films from the substrate pattern cleaning process is complicated; Other layers and components near the substrate pattern are damaged during substrate pattern cleaning; Low yield; Low stability of the substrate processing solution; A large amount of residual film remains after the film formed from the substrate processing solution is removed; Cracks occur in the film formed from the substrate processing solution; Increasing the thickness of the film formed from the substrate processing solution causes pattern collapse.

[0007] In view of the above-mentioned problems, one object of one embodiment of the present invention is to provide a substrate processing liquid that is more effectively able to suppress pattern collapse. [Means for solving the problem]

[0008] A substrate processing solution according to one embodiment of the present invention contains a solidifying component and satisfies at least one of the following conditions (i) and (ii): (i) The solidifying component is a plastic crystalline compound having a melting point of 20° C. or higher and 200° C. or lower at normal pressure. (ii) The substrate processing solution further contains a surface modifying component represented by general formula (I). [ka] (In general formula (I), each X is independently any one of the group consisting of a tertiary amine, a secondary amine, a primary amine, -OH, -SO2-NH-SO2-, -CO-NH2, -COOH, -CHO, -SO3H, -CO-NH-CO-, and -CO-NH-SO2-; each Y is independently H, C 1~10 Fluoroalkyl having C 5~20 and at least one of the Y's is C 1~10 Fluoroalkyl or C 5~20 is a fluoroaryl having n 11 is 1, 2, or 3, and m 11 is 1, 2, or 3, and n 11 and m 11 At least one of is 1.)

[0009] The substrate processing solution may not be cooled in a temperature range from a temperature 5° C. lower than the freezing point of the solidifying component to a temperature lower than the freezing point of the solidifying component.

[0010] The molecular weight of the solidifying component may be 58 or more and 200 or less.

[0011] The content of the solidifying component may be 1% by mass or more and 30% by mass or less.

[0012] The content of the surface modifying component may be 0.01% by mass or more and 1.0% by mass or less.

[0013] The substrate processing solution may further contain a solvent, and the solvent may contain an organic solvent including at least one selected from the group consisting of alcohols, alkanes, ethers, lactate esters, acetate esters, aromatic hydrocarbons, ketones, amides, and lactones, and / or water.

[0014] The substrate processing solution may be characterized in that the substrate pattern on the substrate is cleaned with the cleaning solution and used to replace the cleaning solution remaining on the substrate.

[0015] In one embodiment of the present invention, a film may be formed from the substrate processing liquid, and the film may be removed from the substrate pattern by vaporizing a solidified component. Vaporization is preferably sublimation. When removing the film formed from the substrate processing liquid, at least one step selected from the group consisting of heating the substrate, blowing a gas onto the substrate, and rotating the substrate may be performed.

[0016] A substrate processing liquid according to one embodiment of the present invention is applied to a pattern on a substrate to form a film, and is characterized in that the thickness T of the film and the height H of the pattern satisfy the relational expression 1H≦T≦5H. [Effects of the Invention]

[0017] By using the substrate processing solution according to one embodiment of the present invention, one or more of the following effects can be expected.

[0018] Substrate patterns can be cleaned. Pattern collapse can be prevented during substrate pattern cleaning. Fine substrate patterns can be filled. A film can be formed on a fine substrate pattern. A film can be formed without cooling. A film can be removed without reducing pressure. Pattern collapse can be prevented by first evaporating the solvent and then gradually evaporating the solidified components. The amount of solidified components remaining on the substrate pattern after removal can be reduced. A substrate processing solution can be obtained in which the solidified components have good solubility in the solvent. The number of steps for removing a film can be reduced from the substrate pattern cleaning process. Damage to other layers and components near the substrate pattern can be reduced. Good yield. The substrate processing solution has excellent stability. A plastic crystalline phase can be formed from the substrate processing solution. The amount of film remaining after removal of a film formed from the substrate processing solution can be reduced. A highly tenacious film can be formed from the substrate processing solution. Cracks in a film formed from the substrate processing solution can be reduced. Pattern collapse does not occur even when a thick film is formed from the substrate processing solution. [Brief explanation of the drawings]

[0019] [Figure 1] 1A to 1C are schematic cross-sectional views illustrating a method for forming a substrate pattern using a substrate processing liquid according to an embodiment of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0020] The substrate processing solution according to one embodiment of the present invention will be described below. [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°C means 20°C. The additive refers to the compound itself that has that function (for example, in the case of a base generator, the compound itself that generates a base). In some embodiments, the compound is dissolved or dispersed in a solvent and added to the composition. Such a solvent is preferably contained in the substrate processing solution as a solvent (C) or other additive (E) described below.

[0021] [1. Composition of substrate processing solution] A substrate processing solution according to one embodiment of the present invention comprises a solidifying component (A), a surface-modifying component (B), a solvent (C), a vaporizable component (D), and other additives (E). The surface-modifying component (B), the vaporizable component (D), and other additives (E) may be included in the substrate processing solution as needed. The substrate processing solution is preferably a pattern-filling substrate processing solution, and is used in a substrate pattern cleaning process.

[0022] Here, the term "substrate pattern" as used herein includes a pattern formed by processing the surface of a substrate. The term "substrate pattern" preferably does not include a pattern formed from another film or layer on the substrate. For example, a resist pattern formed solely from an organic material on a bare wafer is preferably not included in the term "substrate pattern." However, a pattern obtained by depositing a metal film on the surface of a substrate and then processing the metal film is included in the term "substrate pattern." The surface of the substrate before processing may be treated with oxygen or nitrogen. Resist patterns containing non-organic materials may or may not be included in the substrate pattern of the present invention (more preferably, they are not included). Resist patterns containing non-organic materials can be formed by using a resist composition containing a solidifying component (preferably a matrix, more preferably a resin) containing Si or Sn, etc., as the resist composition. Resist patterns formed using such resist compositions are considered to be suitable for use with the substrate processing solution of the present invention due to their high hardness. The substrate processing liquid means a composition that is filled into gaps in a substrate pattern (overflow is permitted), and more preferably, a film is formed thereafter. Each component of the substrate processing solution will be described below.

[0023] [1-1. Solidification component (A)] The substrate processing liquid according to one embodiment of the present invention contains a solidifying component, and in one aspect thereof, (i) the solidifying component is preferably a plastic crystalline compound having a melting point of 20° C. or more and 200° C. or less at room temperature. A substrate processing solution according to one embodiment of the present invention is filled into a substrate pattern to form a film. The solvent (C) evaporates first, and the solidification component (A) forms a film. The film is then removed by the evaporation of the solidification component (A). A preferred mode of vaporization is sublimation. Preferably, sublimation refers to a direct change of a portion of the solidification component (A) from a solid phase to a gas phase. More preferably, sublimation refers to a direct change of substantially all of the solidification component (A) from a solid phase to a gas phase. In another embodiment of the solidification component (A), the solidification component (A) is a substance that has a sublimation point at room temperature at which it changes from a solid phase to a gas phase without passing through a liquid phase. In another preferred embodiment, the solidification component (A) may be a substance that changes from a solid phase to a liquid phase to a gas phase when heated at atmospheric pressure, has a melting point, and slowly sublimes below the melting point.

[0024] When removing a film formed by a substrate processing solution, the substrate may be heated. Heating here refers to heating to a temperature of preferably 40°C or higher, even more preferably 50°C or higher, and even more preferably 60°C or higher. The upper limit is preferably 200°C or lower, even more preferably 170°C or lower, and even more preferably 150°C or lower. Another advantage of the present invention is that a cooling step, as described in Patent Document 1, is not required when removing the film. In another embodiment, the film may be removed by spraying a gas or by rotating the substrate. Examples of the gas include air, Ar, and nitrogen gas, and examples of gases with reduced humidity and oxygen concentration include the use of such gases. It is also a preferred embodiment of the present invention that the film is removed without reducing pressure (specifically, to 80 kPa or lower).

[0025] From the viewpoint of cleaning the substrate pattern and reducing the amount of solidification component (A) remaining on the substrate pattern, it is desirable that the solidification component (A) be a substance that is easily vaporized. In order to further reduce the amount of the solidification component (A) remaining, which has such properties, a heating step can be added. In one embodiment of the present invention, when removing the film formed from the substrate processing solution, heating can be performed under the conditions of 35 to 150°C (preferably 35 to 120°C, more preferably 40 to 110°C, and particularly preferably 40 to 100°C) for 10 to 180 seconds (preferably 10 to 120 seconds, and more preferably 10 to 90 seconds).

[0026] In one embodiment of the present invention, the substrate processing solution is preferably cooled to a temperature that is at least 5°C lower than the freezing point of the solidifying component (A), but not to a temperature that is lower than the freezing point of the solidifying component (A). The solidifying component (A) is preferably a substance having such a freezing point. For example, the melting point of the solidifying component (A) at normal pressure is 20 to 200°C, preferably 25 to 190°C, more preferably 30 to 180°C, and even more preferably 30 to 100°C. In this case, the film formed from the substrate processing solution is solid at room temperature (25°C), and therefore does not require a cooling device or the like, making it easy to handle. Without being bound by theory, cooling the substrate processing solution at a temperature that is at least 5°C lower than the freezing point of the solidifying component (A) but not higher than the freezing point of the solidifying component (A) increases the number of processes in the substrate processing, which increases costs and time. Furthermore, there is a risk of condensation from the gas in the system, which can cause patterns to collapse or defects to form on the wafer, which is undesirable.

[0027] The concentration of the solidifying component (A) is 1 to 50 mass % (preferably 1 to 30 mass %, more preferably 2 to 20 mass %) based on the substrate processing solution. The concentration of the solidifying component (A) is not particularly limited, but if the amount of the solidifying component (A) is too small, it becomes difficult to form a film and the effect of suppressing pattern collapse becomes small, so the concentration is preferably in the above range.

[0028] The molecular weight of the solidifying component (A) is 58 to 200 (preferably 70 to 180). There are no particular limitations on the molecular weight of the solidifying component (A), but if the molecular weight is too large, energy is required for vaporization, so it is preferable that the molecular weight is within the above range. When the solidifying component contained in the substrate processing solution according to one embodiment of the present invention does not satisfy the above condition (i) but satisfies the above condition (ii), it is preferable that the solidifying component (A) is the vaporizing component (D). Specifically, the vaporizing component (D) functions as a solidifying component and is removed by vaporization, and the vaporizing component (D) is contained in the substrate processing solution together with the surface modifying component (B).

[0029] The solidifying component (A) is preferably a plastic crystal, more preferably a plastic molecular crystal. A plastic crystal is a substance with soft properties, and has a plastic crystalline phase as an intermediate phase between a crystalline phase and a liquid phase. Specifically, the structure of the solidifying component (A) is as follows. However, the solidifying component (A) is not limited to the following structure. [ka]

[0030] [1-2. Surface modification component (B)] The substrate processing solution according to one embodiment of the present invention may contain a surface-modifying component (B). The surface-modifying component (B) is a compound capable of physical adsorption to the surface of a substrate. The surface-modifying component (B) is preferably highly volatile. Specifically, the surface-modifying component (B) preferably evaporates when the solidifying component (A) evaporates, or around the time of evaporation, but is not limited to this. The content of the surface-modifying component (B) in the substrate processing solution is 0.01 to 1.0 mass %, preferably 0.02 to 0.2 mass %, and more preferably 0.03 to 0.2 mass %, based on the substrate processing solution. Note that, in one embodiment of the present invention, the substrate processing solution may not contain the surface-modifying component (B) (0 mass %).

[0031] In one embodiment of the present invention, the substrate processing solution contains, in addition to a solidifying component, (ii) a surface modifying component represented by general formula (I), which will be described later. The surface-modifying component (B) is preferably a repelling agent. Without being bound by theory, it is believed that in one embodiment of the present invention, the surface-modifying component (B) is adsorbed to the surface of the pattern, causing repulsion between the patterns, thereby further preventing the patterns from collapsing.

[0032] Silicon coupling agents are commonly used as surface modifiers, but because they react with water and alcohol, they cannot be used as solvents. Furthermore, silicon coupling agents form chemical bonds with the substrate surface, a process known as chemisorption. Therefore, removal of the silicon coupling agent requires a process such as ashing to sever the bonds. Without being bound by theory, the surface-modifying component (B) contained in the substrate processing solution is physically adsorbed, allowing the use of many different solvents, such as the solvent (C) described below. Furthermore, the surface-modifying component (B) can be removed during the vaporization of the solidifying component (A), eliminating the need for a process to remove only the surface-modifying component (B).

[0033] For example, the surface modifying component (B) is a compound represented by general formula (I). [ka] In general formula (I), each X is independently any one of the group consisting of a tertiary amine, a secondary amine, a primary amine, -OH, -SO2-NH-SO2-, -CO-NH2, -COOH, -CHO, -S03H, -CO-NH-CO-, and -CO-NH-SO2-. Each X is independently preferably a tertiary amine, a primary amine, -OH, -SO2-NH-SO2-, -CO-NH2, -COOH, -CHO, -S03H, -CO-NH-CO-, or -CO-NH-SO2-, more preferably a tertiary amine, -OH, or -SO2-NH-SO2-, and even more preferably -OH. In the general formula (I), each Y is independently H, C 1~10 Fluoroalkyl having C 5~20 and at least one of the Y's is C 1~10 Fluoroalkyl or C 5~20 The fluoroaryl has the formula: wherein the fluoroalkyl is one in which some or all of the H's in the alkyl are substituted with fluoro (preferably, all of the H's in the alkyl are substituted with fluoro). The fluoroaryl is one in which some or all of the H's in the aryl are substituted with fluoro (preferably, all of the H's in the alkyl are substituted with fluoro). A preferred example of fluoro is F or Cl (a more preferred example is F). Each Y is independently preferably H, C 1~9 or C6 fluoroaryl, more preferably C 2~4 is a fluoroalkyl having the formula: Also, n 11 is 1, 2, or 3, and m 11 is 1, 2, or 3, and n 11 and m 11 At least one of is 1. Preferably, n 11 is 1 and m 11 is 1, 2 or 3, and more preferably n 11 and m 11 is 1.

[0034] The tertiary amine, secondary amine, and primary amine are as follows: [ka]

[0035] In addition, X may be a polar functional group. In one compound represented by general formula (I), the sum of the valences of X is equal to the valence of Y. For example, n 11 When =1, X is m 11 It is a polar functional group with valence, and depending on the selected X, m 11 The number of is determined.

[0036] Specifically, the structure of the surface modifying component (B) is as follows: However, the surface modifying component (B) is not limited to the structure below. [ka] [ka]

[0037] [1-3. Solvent (C)] A substrate processing solution according to one embodiment of the present invention contains a solvent (C). The solvent (C) is preferably volatile and capable of dissolving at least a portion of the solidification component (A). The boiling point of the solvent (C) at 1 atmosphere is 50 to 200°C, preferably 60 to 170°C, and more preferably 70 to 150°C. The solvent (C) is preferably a solvent that is vaporized by spin drying. The content of the solvent (C) is 30 to 99 mass %, preferably 50 to 95 mass %, more preferably 80 to 95 mass %, and particularly preferably 85 to 95 mass %, based on the mass of the substrate processing solution.

[0038] For example, water and / or an organic solvent can be used as the solvent (C). The solvent (C) may be a mixture of water and an organic solvent. The water is preferably pure water (ion-exchanged water: DIW). In one embodiment of the present invention, the solvent (C) is water. When the solvent (C) is water, the amount of organic solvent used can be reduced, which is considered to be advantageous in terms of the process. When the solvent (C) is a mixture of water and an organic solvent, the volume ratio is 1:99 to 99:1, preferably 10:90 to 90:10, more preferably 20:80 to 80:20, and even more preferably 40:60 to 60:40.

[0039] For example, the organic solvent may be an alcohol such as methanol (MeOH), ethanol (EtOH), 1-propanol, isopropanol (IPA), 1-butanol, or benzyl alcohol; an alkanes such as hexane, heptane, or octane; an ether such as ethyl butyl ether, dibutyl ether, tetrahydrofuran (THF), or anisole; a lactate ester such as methyl lactate or ethyl lactate (EL); an acetate ester such as ethyl acetate or butyl acetate; an aromatic hydrocarbon such as benzene, toluene, or xylene; a ketone such as acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-heptanone, cyclopentanone, or cyclohexanone; an amide such as N,N-dimethylacetamide or N-methylpyrrolidone; or a lactone such as γ-butyrolactone. In addition to the above, other ethers that can be used include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether, ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate, propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether (PGME) and propylene glycol monoethyl ether (PGEE), and propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monoethyl ether acetate. These organic solvents can be used alone or in combination of two or more.

[0040] Here, a preferred embodiment of the organic solvent contained in the substrate processing solution will be specifically described.

[0041] The organic solvent contained in solvent (C) is one or more selected from the group consisting of MeOH, EtOH, 1-propanol, IPA, 1-butanol, THF, PGEE, PGME, PGMEA, benzene, acetone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, ethyl acetate, butyl acetate, EL, dibutyl ether, anisole, and benzyl alcohol. Furthermore, the organic solvent contained in solvent (C) is preferably one or more selected from the group consisting of MeOH, EtOH, IPA, PGEE, and acetone. Furthermore, the organic solvent contained in solvent (C) is more preferably one or more selected from the group consisting of MeOH, EtOH, IPA, and PGEE. When two organic solvents are used in combination, the mass ratio is 1:99 to 99:1, preferably 10:90 to 90:10, more preferably 20:80 to 80:20, and even more preferably 40:60 to 60:40.

[0042] [1-4. Vaporized Components (D)] The substrate processing liquid according to one embodiment of the present invention may further contain a vaporizable component (D). The vaporizable component (D) is a component that remains as a solidifiable component in a film formed from the substrate processing liquid and can be vaporized. The vaporizable component (D) is preferably a component other than a plastic crystalline compound having a melting point of 20°C or higher and 200°C or lower at room temperature, and more preferably a component other than the solidifiable component (A). The content of the vaporizable component (D) in the substrate processing liquid is 0 to 20% by mass relative to the substrate processing liquid. The upper limit of the content is preferably 15% by mass, more preferably 10% by mass, even more preferably 5% by mass, and still more preferably 2% by mass. The lower limit of the content is preferably 0% by mass, more preferably 0.1% by mass, and even more preferably 0.5% by mass. A preferred embodiment of the present invention is one in which the vaporizable component (D) is not contained (0% by mass). When the solidifying component contained in the substrate processing solution according to one embodiment of the present invention does not satisfy the above condition (i) but satisfies the above condition (ii), and the solidifying component (A) is the vaporizing component (D), the above description of the solidifying component (A) takes precedence over the content of the solidifying component.

[0043] For example, the vaporized component (D) is a compound such as a saturated hydrocarbon ring, specifically a compound represented by the general formula (II). [ka] Cy 11 and Cy 12 are each independently a saturated or unsaturated hydrocarbon ring or heterocyclic ring. 11 and Cy 12 are both saturated or unsaturated hydrocarbon rings or heterocyclic rings, and more preferably Cy 11 and Cy 12 are both saturated hydrocarbon rings or heterocyclic rings. The heterocyclic rings referred to here are C n1 may be substituted to form a heterocycle. C n1 are carbons, and n1 is an integer between 10 and 19 (i.e., C 10 , C 11 , C 19 ). C n1 The remaining bond is bonded to H. C n1 are each independently -C n1 R n1 -, -C n1 R n1 R n1 -, -C n1 (OH)-, -C n1 (=O)-, -N n1 H- and / or -N n1 R n1 - may be replaced with at least one C n1 is replaced by at least one of the above. Naturally absent elements are excluded from this proviso. For example, n 11 =n 12 When =0, C 10 ~C 14 At least one of the adjacent C n1 are preferably not substituted at the same time. R n1 and R n1 are each independently C 1~5Alkyl (preferably C 1~4 , more preferably C 1~3 ), -NH2 and / or C 1~5 Aminoalkyl (preferably C 1~4 , more preferably C 1~3 , more preferably C1), and R n1 and / or R n1 is another R n1 , R n1 and / or C n1 may be bonded to form a ring. n1 and R n1 Other R n1 , R n1 and / or C n1 and form a ring. n 11 , n 12 and n 13 are each independently 0 or 1. Preferably, n 11 = 0. Preferably, n 12 = 1. Preferably, n 13 =1.

[0044] The vaporized component (D) may be two or more compounds. In this case, the vaporized component (D) may contain a compound represented by general formula (III) in addition to a compound represented by general formula (II). [ka] Cy 21 , Cy 22 , R n2 , R n2 , n 21 , n 22 and n 23 The definitions, examples and explanations are each independently Cy 11 , Cy 12 , R n1 , R n1 , n 11 , n 12 and n 13 is the same as: C n2 The definitions, examples and explanations are each independently C n1n2 is an integer between 20 and 29 (i.e., C 20 , C 21 , C 29 ) The examples and explanations for n2 (20-29) each independently correspond to n1 (10-19).

[0045] Although not limiting the scope of the present invention, specific examples of the vaporized component (D) include the following: each independently phthalic anhydride, caffeine, melamine, 1,4-benzoquinone, camphor, hexamethylenetetramine, hexahydro-1,3,5-trimethyl-1,3,5-triazine, 1-adamantanol, 1,4-diazabicyclo[2.2.2]octane, borneol, (-)-borneol, (±)-isoborneol, 1,2-cyclohexanedione, 1,3-cyclohexanedione, 1,4-cyclohexanedione, 3-methyl-1,2-cyclopentanedione, (±)-camphorquinone, (-)-camphorquinone, (+)-camphorquinone, and 1-adamantanamine.

[0046] Although the scope of the present invention is not limited thereto, specific examples of the vaporizable component (D) are represented by the following structures. [ka]

[0047] The vaporized component (D) may also be a low molecular weight compound having a carbon number of 2 to 25. In this case, the vaporized component (D) may be, for example, 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 3-methyl-1,3-butanediol, 3-phenyl-1,3-butanediol, 1,2-pentanediol, 1,3-pentanediol, 2,4-pentanediol, 1,5-pentanediol, 1,2-hexanediol, 2,4-pentanediol, 2,5-pentanediol, 2,6-pentanediol, 2,7-pentanediol, 2,8-pentanediol, 2,9-pentanediol, 2,10-pentanediol, 2,11-pentanediol, 2,12-pentanediol, 2,13-pentanediol, 2,14-pentanediol, 2,15-pentanediol, 2,16-pentanediol, 2,17-pentanediol, 2,18-pentanediol, 2,19-pentanediol, 2,20-pentanediol, 2,21-pentanediol, 2,22-pentanediol, 2,23-pentanediol, 2,24-pentanediol, 2,25-pentanediol, 2,26-pentanediol, 2,27-pentanediol, 2,28-pentanediol, 2,29-pentanediol, 2,30-pentanediol, 2,31-pentanediol, 2,32-pentanediol, 2,33-pentanediol, 2,34-pent ,5-hexanediol, 2,4-diethyl-1,5-pentanediol, 2,4-dimethyl-2,4-pentanediol, 3-methyl-1,5-pentanediol, diethylene glycol, diethanolamine, 1,3-cyclopentanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 4-methyl-1,2-cyclohexanediol, 4-methylcatechol, etc. Preferably, the vaporized component (D) is 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 3-methyl-1,3-butanediol, or 3-phenyl-1,3-butanediol.

[0048] The vaporizable component (D) may also be a polymer. In this case, the vaporizable component (D) may be, for example, polyethylene glycol, polypropylene glycol, polypropylene carbonate, polyethylene carbonate, polyethylene propylene glycol, polyacetal, etc. Preferably, the vaporizable component (D) is polyethylene glycol or polypropylene carbonate.

[0049] When the solidification component contained in the substrate processing solution according to one embodiment of the present invention does not satisfy the above condition (i) but satisfies the above condition (ii), and the solidification component (A) is the vaporization component (D), specific examples of the solidification component (A) are the same as the above specific examples of the vaporization component (D).

[0050] [1-5. Other additives (E)] The substrate processing solution according to one embodiment of the present invention may further contain another additive (E). The other additive (E) is a compound different from the components (A) to (D). The other additive (E) is preferably highly volatile. Specifically, the other additive (E) preferably evaporates when the solidifying component (A) evaporates, or around the time of evaporation, but is not limited to this. The content of the other additive (E) in the substrate processing solution is 0 to 20% by mass, preferably 0 to 10% by mass, and more preferably 0 to 5% by mass, relative to the solidifying component (A). Needless to say, one embodiment of the present invention also includes an embodiment in which the substrate processing solution does not contain the other additive (E) (0% by mass).

[0051] The other additives (E) will be specifically described below. An example of the other additive (E) is a surfactant. When the substrate processing solution contains a surfactant as the other additive (E), it can improve the coating properties on the substrate. The content of the surfactant in the substrate processing solution is 0 to 2 mass % relative to the solidifying component (A), preferably 0 to 1 mass %, and more preferably 0 to 0.5 mass %.

[0052] Any surfactant can be used. For example, an anionic surfactant, a cationic surfactant, or a nonionic surfactant can be used. More specifically, alkyl sulfonates, alkyl benzene sulfonic acids, alkyl benzene sulfonates, lauryl pyridinium chloride, lauryl methyl ammonium chloride, polyoxyethylene octyl ether, polyoxyethylene lauryl ether, or polyoxyethylene acetylenic glycol ether is preferably used as the surfactant. Nonionic surfactants include nonionic alkyl ether surfactants manufactured by Nippon Nyukazai Co., Ltd., and the like, which are commercially available.

[0053] Another example of the other additive (E) is an antibacterial agent, a bactericide, a preservative, or an antifungal agent. The inclusion of an antibacterial agent, a bactericide, a preservative, or an antifungal agent as the other additive (E) can prevent the growth of bacteria or fungi in the substrate processing solution and suppress deterioration of the substrate processing solution over time. The content of the antibacterial agent, bactericide, preservative, or antifungal agent in the substrate processing solution is 0 to 1% by mass, preferably 0 to 0.1% by mass, and more preferably 0 to 0.01% by mass, relative to the solidification component (A).

[0054] For example, alcohols such as phenoxyethanol or isothiazolone can be used as antibacterial agents, disinfectants, preservatives, or antifungal agents. Bestside (trade name) manufactured by Nippon Soda Co., Ltd. is commercially available as an antiseptic, antifungal agent, or disinfectant.

[0055] Another example of the other additive (E) is an acid or a base. The inclusion of an acid or a base as the other additive (E) can improve the properties of the substrate processing solution, such as by adjusting the pH of the substrate processing solution or the solubility of the components (A) to (D) contained in the substrate processing solution. The acid or base may be prepared according to the material of the substrate to which the substrate processing solution is applied, and added to the substrate processing solution. The content of the acid or base contained in the substrate processing solution is 0 to 1 mass %, preferably 0 to 0.5 mass %, and more preferably 0 to 0.2 mass %, relative to the solidification component (A).

[0056] The acid or base can be selected arbitrarily as long as it does not impair the effects of the present invention. For example, carboxylic acids, amines, or ammonium salts can be used as the acid or base. The carboxylic acids, amines, or ammonium salts herein include fatty acids, aromatic carboxylic acids, primary amines, secondary amines, tertiary amines, or ammonium compounds, which may be substituted with any substituent. More specifically, the acid or base can be formic acid, acetic acid, propionic acid, benzoic acid, phthalic acid, salicylic acid, lactic acid, malic acid, citric acid, oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid, aconitic acid, glutaric acid, adipic acid, monoethanolamine, diethanolamine, triethanolamine, triisopropanolamine, or tetramethylammonium.

[0057] [2. Use of substrate processing liquid] The use of a substrate processing liquid according to one embodiment of the present invention will be described with reference to FIGS. 1(A) to 1(E). 1(A) to 1(E) are schematic cross-sectional views illustrating a method for forming a substrate pattern using a substrate processing solution according to one embodiment of the present invention. FIGS. 1(A) to 1(E) sequentially illustrate steps in the method for forming a substrate pattern. The method for forming a substrate pattern can be arbitrarily selected from known methods such as dry etching. For example, Non-Patent Document 1 discloses an example of a method for forming a substrate pattern. Various pretreatments can be combined in forming a substrate pattern.

[0058] FIG. 1(A) shows a state in which a coated carbon film layer 12, a silicon-containing anti-reflective coating layer 13, and a resist pattern 14 are formed in this order on a substrate 11.

[0059] The substrate 11 may be a semiconductor wafer, a glass substrate for a liquid crystal display device, a glass substrate for an organic electroluminescence display device, a glass substrate for a plasma display device, a substrate for an optical disk, a substrate for a magnetic disk, a substrate for a magneto-optical disk, a glass substrate for a photomask, or a substrate for a solar cell. The substrate 11 may be an unprocessed substrate (e.g., a bare wafer) or a processed substrate (e.g., a patterned substrate). That is, the substrate 11 may have a conductive film, wiring, or a semiconductor element formed thereon. The substrate may have a structure in which multiple layers are stacked. The substrate 11 is preferably a semiconductor. The semiconductor may be composed of an oxide, a nitride, a metal, or a combination thereof. Therefore, the material of the substrate 11 is not particularly limited, but may be, for example, Si, Ge, SiGe, SiO2, TiO2, Al2O3, SiON, HfO2, Ta2O5, HfSiO4, YO3, GaN, TiN, TaN, Si3N4, NbN, Cu, Ta, W, Hf, or Al.

[0060] The coated carbon film layer 12 includes a coated carbon film (also called a coated carbon film or a spin-on carbon film). The coated carbon film layer 12 is formed by coating using a known method such as spin coating, followed by pre-baking. Alternatively, the coated carbon film layer 12 may be formed by deposition using a CVD (chemical vapor deposition) method or an ALD (atomic layer deposition) method.

[0061] The silicon-containing anti-reflective coating layer 13 includes a silicon-containing anti-reflective coating (also referred to as a Si-ARC film). The silicon-containing anti-reflective coating layer 13 is formed by applying a coating by a known method such as spin coating, followed by pre-baking. The formation of the silicon-containing anti-reflective coating layer 13 can improve the cross-sectional shape and exposure margin. When the silicon-containing anti-reflective coating layer 13 is used as an etching mask, the silicon-containing anti-reflective coating layer 13 preferably has etching resistance.

[0062] The resist pattern 14 can be formed by combining known methods. Methods for forming the resist pattern 14 are disclosed in, for example, Patent Document 3.

[0063] In etching the substrate 11, the silicon-containing antireflective coating layer 13 may be etched using the resist pattern 14 as a mask, and then the coated carbon film layer 12 and the substrate 11 may be etched using the silicon-containing antireflective coating layer 13 as a mask; alternatively, the silicon-containing antireflective coating layer 13 and the coated carbon film layer 12 may be etched using the resist pattern 14 as a mask, and then the substrate 11 may be etched using the silicon-containing antireflective coating layer 13 and the coated carbon film layer 12 as masks. Alternatively, the silicon-containing antireflective coating layer 13, the coated carbon film layer 12, and the substrate 11 may be successively etched using the resist pattern 14 as a mask. The etching may be wet etching or dry etching.

[0064] 1(B) shows a state in which substrate 11 has been dry-etched, resulting in a gap 15 being formed on the surface of substrate 11. The type of gas used for dry etching is not particularly limited, but a fluorocarbon-based gas is generally used. As shown in FIG. 1(B), residue (debris) 16 remains in gap 15 after dry etching.

[0065] 1(C) illustrates the state in which the etched substrate 11 is cleaned with a cleaning liquid 17. The cleaning method using the cleaning liquid 17 may be a known method, such as a coating method, a dropping method, an immersion method, or a combination thereof. By cleaning with the cleaning liquid 17, residues 18 are removed. The cleaning liquid 17 is preferably an organic solvent, more preferably IPA.

[0066] 1(D) shows a state in which the gap 15 is filled with the substrate processing liquid 19. Specifically, in FIG. 1(D), a film of the substrate processing liquid 19 is formed so as to cover the gap 15. The substrate processing liquid 19 is applied (including by dropping or immersion) while the cleaning liquid 17 remains in the gap 15. The method for applying the substrate processing liquid 19 is not particularly limited, and any application method can be used, such as a method of dropping and spreading the substrate processing liquid 19 on the surface of the substrate 11 while rotating the substrate 11 at 1 to 3,000 rpm, a method of dropping the substrate processing liquid 19 on the surface of a stationary substrate 11 and then rotating the substrate 11 at 1 to 3,000 rpm to spread the substrate processing liquid 19, a method of immersing the substrate 11 in the substrate processing liquid 19, or a method of supplying the substrate processing liquid 19 by spraying or spraying. Among these, a method in which the substrate processing liquid 19 is dropped onto the surface of the substrate 11 while the substrate 11 is being rotated at 1 to 3,000 rpm and then spread, or a method in which the substrate processing liquid 19 is dropped onto the surface of the stationary substrate 11 and then the substrate 11 is rotated at 1 to 3,000 rpm and then the substrate processing liquid 19 is spread, is preferred. At this time, at least a portion of the cleaning liquid 17 in the gap 15 is replaced, and the substrate processing liquid 19 fills the gap 15. To fully exert the effects of the present invention, it is preferable that the cleaning liquid 17 is sufficiently replaced by the substrate processing liquid 19.

[0067] The cleaning may be performed in multiple steps. For example, a cleaning liquid (such as an acid or alkali) that dissolves and removes inorganic substances may be applied, followed by a cleaning liquid (such as ion-exchanged water or an organic solvent) that is highly compatible with the substrate processing liquid 19. Even in this case, it is preferable that the cleaning liquid present in the gap 15 is sufficiently replaced with the substrate processing liquid 19.

[0068] After the above steps, substrate 11 may be rotated at a speed faster than 50 rpm and not more than 5000 rpm. This rotation removes excess organic solvent and water from substrate processing solution 19 from substrate 11, but at least a portion of solidifying component (A) remains. Because not all of the components of substrate processing solution 19 are removed from within gap 15, a film is formed, preventing pattern collapse.

[0069] The film thickness T of the film formed by the substrate processing solution 19 is, for example, 0.02 to 5 μm, preferably 0.05 to 4 μm, and more preferably 0.1 to 3 μm. The relationship between the film thickness T and the height H of the pattern 20 (described later) satisfies, for example, 1H≦T≦5H, preferably 1.2H≦T≦4H, and more preferably 1.5H≦T≦3H. A problem with films formed by conventional substrate processing solutions is that cracks occur as the film thickness increases. That is, conventional films have a high film thickness dependency and a narrow process window. Without being bound by theory, in one embodiment of the present invention, the film formed by the substrate processing solution 19 is a film formed by the solidifying component (A) having plasticity, and is therefore highly tough and unlikely to crack even in a thick film. Therefore, the film formed by the substrate processing solution 19 has a wide process window, and it is believed that pattern collapse can be prevented even in a thick film.

[0070] FIG. 1(E) illustrates a state in which a pattern 20 is formed after the substrate processing liquid 19 filling the gap 15 has been removed. The substrate processing liquid 19 can be removed by heating, air drying (spraying), rotation, leaving the substrate stationary, or a combination of these. Any method for removing the substrate processing liquid 19 may be used as long as it does not damage the shape of the pattern 20. When removing the substrate processing liquid 19 by heating, the heating time is not particularly limited, but is, for example, 0 to 180 seconds, preferably 10 to 120 seconds, and more preferably 10 to 90 seconds. The substrate processing liquid 19 can be removed by air drying by holding the pattern 20 in an airflow. The airflow may be either positive or negative pressure. Specifically, the airflow can be generated by spraying a gas. In this case, the gas to be sprayed is not particularly limited. While a gas such as air can be used, an inert gas such as argon gas or nitrogen gas is preferably used. The airflow velocity is not particularly limited, and appropriate conditions for removing the substrate processing liquid 19 are selected. In removing the substrate processing liquid 19, it is preferable that the humidity of the gas forming the atmosphere or airflow is low. For example, the humidity of the gas is 10% or less, preferably 5% or less, more preferably 1% or less, and particularly preferably 0.1% or less. In removing the substrate processing liquid 19 by rotation, the rotation speed and rotation time of the substrate are not particularly limited, but are, for example, 20 to 2000 rpm for 30 to 300 seconds.

[0071] 1(E), the line width of the pattern 20 is represented by x and the height by H. The aspect ratio of the pattern 20 is represented by H / x. The above-described method for forming a substrate pattern can be effectively applied within a range of the pattern height H, for example, 0.01 to 6 μm or less, preferably 0.05 to 5 μm, and more preferably 0.1 to 3 μm. The aspect ratio H / x is, for example, 5 to 25, and preferably 15 to 22.

[0072] In the method for forming a substrate pattern using a substrate processing solution according to one embodiment of the present invention, the collapse rate of the substrate pattern can be suppressed even for fine patterns. For example, a pillar pattern, in which the center of a cylindrical shape is thinner than the bottom and / or top, is prone to collapse, but even such a pillar pattern can be cleaned while suppressing the collapse rate of the substrate pattern by using the method for forming a substrate pattern described above.

[0073] A line-space pattern, which has a wall structure, is thought to be less prone to collapse than a pillar pattern, but the collapse rate can be further reduced by using the above-described method for forming a substrate pattern.

[0074] The above-described pattern 20 can be further processed to manufacture a device. The device can be, for example, a semiconductor element, a liquid crystal display element, an organic EL display element, a plasma display element, or a solar cell element. The device is preferably a semiconductor. These can be processed using 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. An example of this packaged product is a semiconductor. One embodiment of the present invention provides a method for manufacturing a device, comprising filling a substrate pattern with the substrate processing liquid described above to form a film, and then vaporizing and removing the film. [Example]

[0075] The substrate processing solution according to one embodiment of the present invention will be described in more detail below with reference to examples. However, the substrate processing solution according to one embodiment of the present invention is not limited to the following examples.

[0076] [Preparation of Example 1] As the solidification component (A), 2,2-dimethyl-1-propanol (S1) was added to the solvent (C), IPA, so that the amount was 10 mass % based on the prepared substrate processing solution. The container was capped and stirred overnight, and the solute was visually confirmed to have dissolved. The solution obtained above was filtered through a filter with a pore size of 0.1 μm to obtain the substrate processing solution (Example 1).

[0077] [Preparation of Examples 2 to 15 and Comparative Examples 1 and 2] Substrate processing solutions (Examples 2 to 15, Comparative Examples 1 and 2) were obtained in the same manner as in Example 1, except that the types and concentrations of the solidifying component (A), surface modifying component (B), and solvent (C) were changed as shown in Table 1. The concentration of the surface modifying component (B) is based on the concentration of the substrate processing solution after preparation.

[0078] [Table 1]

[0079] Here, in Table 1, S1 is 2,2-dimethyl-1-propanol, S2 is 2,2-dimethyl-1,3-propanediol, S3 is 2,2-dimethyl-1,3-propanediamine, S4 is 2,2-dimethylpropionic acid, S5 is DL-pantolactone, S6 is cyclohexanone oxime, and S7 is cyclohexane. Also, in Table 1, F1 is pentadecafluorotriethylamine, F2 is 2,2,3,4,4,4-hexafluoro-1-butanol, F3 is 2,2,3,3,3-pentafluoro-1-propanol, and F4 is bis(nonafluorobutanesulfonyl)imide.

[0080] [Evaluation of the formation of plastic crystalline phase] A wafer with a pillar pattern formed on it (hereinafter referred to as the patterned wafer) is mounted on an MS-A150 spin coater (Mikasa). 2 cc of the substrate processing solution is dropped onto the patterned wafer and spin-coated at 1,000 rpm for 20 seconds. The patterned wafer is a silicon wafer with a pillar pattern (provided by the Interunion Microelectronics Centre (IMEC)) formed on it, with the pillar pattern having a top diameter of approximately 30 nm, a bottom diameter of approximately 65 nm, and a height of approximately 600 nm. It is cut into approximately 3 cm squares for use. The formation of a plastic crystal phase due to the solidifying component (A) in the substrate processing solution is visually confirmed. The evaluation criteria are as follows. However, in Comparative Example 2, no solid film formation is confirmed, so no data can be obtained. A: A plastic crystal layer is formed. B: No plastic crystal layer is formed.

[0081] [Crack evaluation] The same patterned wafer used to evaluate the formation of the plastic crystal phase was subjected to the following process to prepare a sample substrate for crack evaluation. The patterned wafer was attached to an MS-A150 spin coater, and 2 cc of substrate treatment solution was dropped onto the patterned wafer and spin-coated at 1,000 rpm for 20 seconds. After spin-coating, the patterned wafer was immediately placed on a metal plate cooled to -120°C to cool the solid film and prevent its sublimation. The top surface of the sample substrate was observed with a cryo-SEM (Helios NanoLab650, Thermo Scientific) at a magnification of 3K within the visible range without moving, and the presence or absence of cracks in the solid film was evaluated. The evaluation criteria were as follows. However, since no solid film formation was confirmed in Comparative Example 2, data could not be obtained. A: No cracks found. B: A crack is discovered.

[0082] [Film thickness measurement for crack evaluation] A slice of the wafer of the sample substrate for crack evaluation is prepared. The cross section of the slice is observed with a cryo-SEM at a magnification of 20K within the visible range without moving, to measure the film thickness. Note that in Comparative Example 2, the formation of a solid film was not confirmed, so data could not be obtained.

[0083] [Residual film evaluation] A sample substrate for evaluating residual film was prepared using the same patterned wafer as used to evaluate the formation of the plastic crystal phase, following the following process. The patterned wafer was attached to an MS-A150 spin coater, and 2 cc of substrate treatment solution was dropped onto the patterned wafer and spin-coated at 1,000 rpm for 20 seconds. The patterned wafer was then immediately heated on a hot plate at 65°C for 120 seconds to sublimate and remove the solid film. A wafer slice was prepared for the sample substrate. The cross section of the slice was observed using an SEM (SU8200, Hitachi High-Technologies) at a magnification of 20K within the visible range without moving, and the presence or absence of residual film was evaluated. The evaluation criteria were as follows. However, since no solid film formation was confirmed in Comparative Example 2, data could not be obtained. A: No residual film was observed. B: Residual membrane is observed.

[0084] [Evaluation of the collapse rate of board patterns] A sample substrate similar to the sample substrate used for residual film evaluation is prepared. The top surface of the sample substrate is observed with an SEM (SU8200) at a magnification of 10K within the visible range without moving, and the collapse rate of the substrate patterns is evaluated. The collapse rate is calculated by dividing the number of collapsed patterns among the substrate patterns in the observed image by the total number of patterns, and multiplying the result by 100. The evaluation criteria are as follows: A: The collapse rate is less than 1%. B: Collapse rate is 1% or more but less than 5%. C: Collapse rate is 5% or more.

[0085] [comprehensive evaluation] Based on the above evaluations, an overall evaluation will be made. The evaluation criteria are as follows: A: The remaining membrane evaluation is A and the collapse rate evaluation is A. B: The remaining membrane evaluation is A and the collapse rate evaluation is B. C: The remaining membrane evaluation is B, or the remaining membrane evaluation is A and the collapse rate evaluation is C.

[0086] Table 2 shows the results of the evaluation of the plastic crystal phase, crack evaluation, film thickness, remaining film evaluation, substrate pattern collapse rate evaluation, and overall evaluation described above.

[0087] [Table 2]

[0088] As can be seen from Table 2, Examples 1 to 15 are superior to Comparative Examples 1 and 2 as substrate processing solutions. [Explanation of symbols]

[0089] 11: Circuit board 12: Coated carbon film layer 13: Silicon-containing anti-reflection film layer 14: Resist pattern 15: Gap 16:Remains (Debris) 17: Cleaning fluid 18:Residue 19: Substrate processing solution 20: Pattern

Claims

1. A substrate processing solution containing a solidifying component, A substrate processing solution that satisfies at least one of the following conditions (i) and (ii): (i) The solidifying component is a plastic crystalline compound having a melting point of 20° C. or higher and 200° C. or lower at normal pressure. (ii) The substrate processing solution further contains a surface modifying component represented by general formula (I). 【Chemistry 1】 (In general formula (I), X's each independently represent a tertiary amine, a secondary amine, a primary amine, -OH, or -SO ２ -NH-SO ２ --CO-NH ２ , -COOH, -CHO, -SO ３ H, —CO—NH—CO—, and —CO—NH—SO ２ - any one of the groups consisting of Y is independently H, C １～１０ Fluoroalkyl having the formula C ５～２０ and at least one of Y is C １～１０ Fluoroalkyl having C ５～２０ is a fluoroaryl having the formula n １１ is 1, 2 or 3, m １１ is 1, 2 or 3, n １１ and m １１ At least one of is 1.)

2. 2. The substrate processing solution according to claim 1, wherein the substrate processing solution is not cooled in a temperature range of from a temperature 5[deg.] C. lower than the freezing point of the solidifying component to a temperature lower than the freezing point of the solidifying component.

3. The substrate processing solution according to claim 1 , wherein the solidifying component has a molecular weight of 58 or more and 200 or less.

4. 2. The substrate processing solution according to claim 1, wherein the content of the solidifying component is 1% by mass or more and 50% by mass or less based on the substrate processing solution.

5. 2. The substrate processing solution according to claim 1, wherein the content of the surface modifying component is 0.01% by mass or more and 1.0% by mass or less based on the substrate processing solution.

6. Further, it contains a solvent, 2. The substrate processing solution according to claim 1, wherein the solvent comprises water and / or an organic solvent including at least one selected from the group consisting of alcohols, alkanes, ethers, lactate esters, acetate esters, aromatic hydrocarbons, ketones, amides, and lactones.

7. 2. The substrate processing solution according to claim 1, wherein the substrate processing solution is used to replace the cleaning solution remaining on the substrate after a substrate pattern on the substrate is cleaned with the cleaning solution.

8. a film is formed from the substrate processing solution, and the solidified component is evaporated, thereby removing the film from the substrate pattern; 2. The substrate processing liquid according to claim 1, wherein the evaporation is sublimation, or when removing a film formed from the substrate processing liquid, at least one step selected from the group consisting of heating the substrate, blowing a gas thereon, and rotating the substrate is performed.

9. 1. A substrate processing solution that is applied to a pattern on a substrate to form a film, wherein a thickness T of the film and a height H of the pattern satisfy the relational expression 1H≦T≦5H.

Images