Substrate processing liquid

Abstract

A substrate treatment liquid which contains a curing component and satisfies at least one of the following conditions (i) and (ii): (i) the curing component is a plastic crystal compound having a melting point of 20 DEG C to 200 DEG C (inclusive); and (ii) the substrate treatment liquid further contains a surface modifying component.

Description

Technical Field

[0001] One embodiment of the present invention relates to a substrate treatment liquid. Background Art

[0002] In the manufacture of devices (electronic components) such as semiconductor devices and liquid crystal display devices, a process is known in which a fine concavo-convex pattern is formed on the surface of a wafer by film formation, photolithography, or etching, and then the surface of the wafer is cleaned. In order to meet the demand for high integration of LSIs, devices tend to be miniaturized, and the above-mentioned concavo-convex pattern has a need to be made narrower in width and higher in aspect ratio. In the cleaning of the surface of the wafer on which the concavo-convex pattern is formed, a technique is known in which a cleaning liquid such as deionized water (DIW) or an organic solvent is supplied to remove contaminants. However, if the concavo-convex pattern is very fine, there is a problem that pattern collapse occurs during the drying process after removing the contaminants due to the surface tension and capillary action of the cleaning liquid.

[0003] In this case, there have been attempts to replace the cleaning liquid in the cleaning step with a filling treatment agent containing a sublimable substance, and then to sublime the sublimable substance to prevent pattern collapse and clean the pattern. Patent Document 1 discloses a technique in which a substrate treatment liquid containing a plastic crystal is supplied to a substrate and cooled to form a semi-cured state to form a plastic crystal layer, and the layer is removed by vaporization to remove the liquid adhering to the substrate surface while preventing pattern collapse. Patent Document 2 discloses a technique in which cyclohexanone oxime is contained as a sublimable substance in a substrate treatment liquid to remove the liquid adhering to the substrate surface while preventing pattern collapse. Patent Document 3 provides a pattern formation method using a gap filling compound.

[0004] [Prior Art Documents]

[0005] [Patent Documents]

[0006] [Patent Document 1] Japanese Patent Application Laid-Open No. 2019-62004

[0007] [Patent Document 2] Japanese Patent Application Laid-Open No. 2021-10002

[0008] [Patent Document 3] International Publication No. 2017 / 174476

[0009] [Non-Patent Documents]

[0010] [Non-Patent Document 1] Toshiba Review, Vol. 59, No. 8 (2004), p. 22-25 Summary of the Invention

[0011] [Problems to be Solved by the Invention]

[0012] The present inventors believe that there are still one or more problems that require improvement. These can be listed as follows, for example. The substrate pattern cannot be cleaned cleanly. Pattern collapse occurs during substrate pattern cleaning. It cannot be filled into fine substrate patterns. A film cannot be formed on fine substrate patterns. A film cannot be formed without cooling. Reduced pressure is required to remove the film. It is not possible to first vaporize the solvent and then gradually vaporize the solidifying component. The amount of the solidifying component remaining in the substrate pattern after removal is large. The solubility of the solidifying component in the solvent is low. The step for removing the film in the process of substrate pattern cleaning is complicated. There is damage to other layers and structures near the substrate pattern during substrate pattern cleaning. The yield is poor. The stability of the substrate treatment liquid is low. There are many residual films after removing the film formed by the substrate treatment liquid. Cracks are generated in the film formed by the substrate treatment liquid. If the thickness of the film formed by the substrate treatment liquid is increased, pattern collapse will occur.

[0013] In view of the above problems, an object of one embodiment of the present invention is to provide a substrate treatment liquid capable of improving the suppression of pattern collapse.

[0014] [Means for Solving the Problems]

[0015] The substrate treatment liquid of one embodiment of the present invention contains a solidifying component and satisfies at least one of the following conditions (i) or (ii):

[0016] (i) The solidifying component is a plastic crystal compound having a melting point of 20°C or higher and 200°C or lower; and

[0017] (ii) The substrate treatment liquid further contains a surface modification component represented by the following general formula (I):

[0018]

[0019] In the general formula (I), each X is independently selected from 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, a fluoroalkyl group having C 1～10 or a fluoroaryl group having C 5～20 At least one of Y is a fluoroalkyl group having C 1～10 or a fluoroaryl group having C 5～20 n 11 is 1, 2, or 3. m 11 is 1, 2, or 3. n 11 and m 11 at least one of them is 1.

[0020] The substrate treatment liquid is not cooled in a temperature range that is higher than a temperature 5°C lower than the freezing point of the solidifying component and lower than the freezing point of the solidifying component.

[0021] The molecular weight of the solidifying component may be 58 or more and 200 or less.

[0022] The content of the solidifying component may be 1% by mass or more and 30% by mass or less based on the substrate treatment liquid.

[0023] The content of the surface modification component may be 0.01% by mass or more and 1.0% by mass or less based on the substrate treatment liquid.

[0024] The substrate treatment liquid further contains a solvent, and the solvent may include an organic solvent containing 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.

[0025] The substrate treatment liquid can be used to replace the cleaning liquid remaining on the substrate when cleaning the substrate pattern with a cleaning liquid.

[0026] In one embodiment of the present invention, a film is formed using the substrate treatment liquid, and then the film is removed from the substrate pattern by vaporizing the solidifying component. The vaporization is preferably sublimation. The vaporization can be carried out by at least one step selected from the group consisting of heating the substrate, blowing a gas, and rotating the substrate when removing the film formed by the substrate treatment liquid.

[0027] In one embodiment of the present invention, the substrate treatment liquid is coated on the pattern of the substrate to form a film, and the thickness T of the film and the height H of the pattern satisfy the relational expression 1H ≦ T ≦ 5H.

[0028] [Effects of the Invention]

[0029] By using the substrate treatment liquid of one embodiment of the present invention, one or more of the following effects can be expected.

[0030] The substrate pattern can be cleaned cleanly. Pattern collapse during substrate pattern cleaning can be suppressed. It can be filled in fine substrate patterns. A film can be formed on fine substrate patterns. A film can be formed without cooling. The film can be removed even without reducing pressure. Pattern collapse can be suppressed by first vaporizing the solvent and then gradually vaporizing the solidifying component. The amount of the solidifying component remaining on the substrate pattern after removal can be reduced. A substrate treatment liquid with good solubility of the solidifying component in the solvent can be obtained. The steps for removing the film in the process of substrate pattern cleaning can be reduced. Damage to other layers and components near the substrate pattern can be reduced. The yield is good. The stability of the substrate treatment liquid is excellent. A plastic crystal phase can be formed from the substrate treatment liquid. The amount of the residual film after removing the film formed from the substrate treatment liquid can be reduced. A film with high toughness can be formed from the substrate treatment liquid. Cracks in the film formed from the substrate treatment liquid can be reduced. Even when a thick film is formed from the substrate treatment liquid, pattern collapse does not occur. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] Figure 1 FIG. is a schematic cross-sectional view illustrating a method of forming a substrate pattern using a substrate treatment liquid according to an embodiment of the present invention. DETAILED DESCRIPTION

[0032] A substrate treatment liquid according to an embodiment of the present invention will be described below.

[0033] [DEFINITIONS]

[0034] In this specification, unless otherwise specifically defined and mentioned, the definitions and examples described in this paragraph are followed.

[0035] The singular form includes the plural form, and "a", "the" mean "at least one". The elements of a concept can be presented in multiple forms, and when the amount thereof (e.g., mass%, mole%) is described, the amount means the sum of multiple ones.

[0036] "And / or" includes all combinations of elements and also includes the use of a single element.

[0037] When a numerical range is expressed using "~ / to", it includes both endpoints and the units are the same. For example, 5~25 mol% means 5 mol% or more and 25 mol% or less.

[0038] "C x～y ", "C x ~C y " and "C x " and the like mean the number of carbons in the molecule or substituent. For example, C 1～6 alkyl means an alkyl chain having 1 or more and 6 or less carbons (methyl, ethyl, propyl, butyl, pentyl, hexyl, etc.).

[0039] When a polymer has multiple repeating units, these repeating units are copolymerized. Such copolymerization can be any one of alternating copolymerization, random copolymerization, block copolymerization, graft copolymerization, or a mixed form thereof. When representing a polymer or resin by a structural formula, n, m, etc. attached after parentheses indicate the number of repetitions.

[0040] The unit of temperature uses Celsius. For example, 20°C means 20 degrees Celsius.

[0041] An additive refers to the compound itself having that function (for example, if it is a base generator, it is the compound itself that generates a base). This compound can also be in a form dissolved or dispersed in a solvent and added to the composition. Such a solvent is preferably contained in the substrate treatment liquid as the solvent (C) described later or other additives.

[0042] [1. Composition of the Substrate Treatment Liquid]

[0043] A substrate treatment liquid according to an embodiment of the present invention contains a curing component (A), a surface modification component (B), a solvent (C), a gasification component (D), and other additives (E). In addition, the surface modification component (B), the gasification component (D), and other additives (E) may also be contained in the substrate treatment liquid as needed. The substrate treatment liquid is preferably a pattern filling substrate treatment liquid and is used in the cleaning step of the substrate pattern.

[0044] Here, the substrate pattern in this specification includes a pattern formed by processing the surface of the substrate. The substrate pattern preferably does not include a pattern formed by other films or layers on the substrate. For example, a form in which a resist pattern composed only of an organic substance is formed on a bare wafer is preferably not included in the substrate pattern. However, a pattern obtained by depositing a metal on the surface of the substrate and processing it is included in the substrate pattern. The surface of the substrate before processing can also be treated with oxygen or nitrogen. A resist pattern containing substances other than organic substances may or may not be included in the substrate pattern of the present invention (more preferably not included). A resist pattern containing substances other than organic substances can be formed by using a curing component (suitably a matrix, more suitably a resin) containing Si or Sn, etc. as a resist composition. It is considered that a resist pattern formed with such a resist composition can be used as the substrate pattern for using the substrate treatment liquid of the present invention due to its high hardness.

[0045] The substrate treatment liquid means a composition filled (allowing overflow) into the gaps of the substrate pattern, and a form of forming a film later is more preferred.

[0046] Hereinafter, each component of the substrate treatment liquid will be described.

[0047] [1-1. Curing Component (A)]

[0048] A substrate treatment liquid according to an embodiment of the present invention contains a solidifying component. As one form, preferably, (i) the solidifying component is a plastic crystal compound having a melting point of 20°C or higher and 200°C or lower at normal temperature.

[0049] A substrate treatment liquid according to an embodiment of the present invention is filled in a substrate pattern to form a film. First, the solvent (C) is vaporized, and the solidifying component (A) forms a film. Then, the solidifying component (A) is vaporized to remove the film. A preferred form of vaporization is sublimation. Preferably, sublimation is a process in which a part of the solidifying component (A) directly changes from the solid phase to the gas phase. More preferably, sublimation is a process in which substantially all of the solidifying component (A) directly changes from the solid phase to the gas phase. Further, as another form of the solidifying component (A), the solidifying component (A) is a substance having a sublimation point that changes from the solid phase to the gas phase without passing through the liquid phase at normal temperature. As another preferred form, the solidifying component (A) is a substance that changes from the solid phase to the gas phase through the liquid phase when heated under normal pressure, has a melting point, and slowly sublimes at a temperature lower than the melting point.

[0050] When removing the film formed by the substrate treatment liquid, heating of the substrate can also be performed. The heating here is more preferably heating at 40°C or higher, further preferably heating at 50°C or higher, and even more preferably heating at 60°C or higher. The upper limit is more preferably 200°C or lower, further preferably 170°C or lower, and even more preferably 150°C or lower. Further, another advantage of the present invention is that when removing the above-mentioned film in the present invention, a cooling step as described in Patent Document 1 is not required. As another form, the film can also be removed by blowing gas or rotating the substrate. Examples of the gas here include: air, Ar, and nitrogen. For example, a gas with reduced humidity and oxygen concentration can be used. In addition, it is also a preferred form of the present invention not to perform decompression (specifically, 80 kPa or lower) for removing the film.

[0051] From the viewpoint of making the substrate pattern clean and reducing the amount remaining on the substrate pattern, the solidifying component (A) is desirably a substance that is easily vaporized. In order to further reduce the remaining amount of the solidifying component (A) having such characteristics, a heating step can also be increased. As an embodiment of the present invention, heating can also be performed when removing the film formed by the substrate treatment liquid. As conditions, it can be listed as: 35 to 150°C (preferably 35 to 120°C, further preferably 40 to 110°C, particularly preferably 40 to 100°C), 10 to 180 seconds (preferably 10 to 120 seconds, further preferably 10 to 90 seconds).

[0052] In one embodiment of the present invention, preferably, the substrate treatment liquid is not cooled at a temperature higher than a temperature 5°C or more lower than the freezing point of the solidifying component (A) and 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) under 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, since the film formed from the substrate treatment liquid is solid at normal temperature (25°C), a cooling device is not required, and thus it is easy to handle.

[0053] Without being limited by theory, when the substrate treatment liquid is cooled at a temperature higher than a temperature 5°C lower than the freezing point of the solidifying component (A) and lower than the freezing point of the solidifying component (A), the cost and time are consumed due to an increase in the processes in the substrate treatment. Furthermore, there is a risk of condensation due to the gas in the system, and it is possible that the condensed water droplets push down the pattern or cause defects on the wafer, which is thus undesirable.

[0054] The concentration of the solidifying component (A) is 1 to 50% by mass (preferably 1 to 30% by mass, more preferably 2 to 20% by mass) based on the substrate treatment liquid. 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. Therefore, it is preferably in the above range.

[0055] The molecular weight of the solidifying component (A) is 58 to 200 (preferably 70 to 180). The molecular weight of the solidifying component (A) is not particularly limited, but if the molecular weight is too large, energy is required for gasification. Therefore, it is preferably in the above range.

[0056] When the solidifying component contained in the substrate treatment liquid of one embodiment of the present invention does not satisfy the above condition (i) but satisfies the above condition (ii), the solidifying component (A) is preferably the gasifying component (D). Specifically, the above gasifying component (D) functions as a solidifying component and is removed by gasification. The gasifying component (D) is contained in the substrate treatment liquid together with the surface modifying component (B).

[0057] The solidifying component (A) is preferably a plastic crystal, more preferably a plastic molecular crystal. A plastic crystal is a substance having a soft property and has a plastic crystal phase as an intermediate phase between the crystalline phase and the 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.

[0058]

[0059]

[0060] [1-2. Surface modification component (B)]

[0061] The substrate treatment liquid according to an embodiment of the present invention may also contain a surface modification component (B). The surface modification component (B) is a compound capable of physically adsorbing on the surface of the substrate. The surface modification component (B) preferably has high volatility. Specifically, the surface modification component (B) preferably vaporizes when the curing component (A) vaporizes, or before or after that, but is not limited thereto. The amount of the surface modification component (B) contained in the substrate treatment liquid is 0.01 to 1.0% by mass based on the substrate treatment liquid, preferably 0.02 to 0.2% by mass, and more preferably 0.03 to 0.2% by mass. In addition, in an embodiment of the present invention, it may also be a form in which the substrate treatment liquid does not contain the surface modification component (B) (0% by mass).

[0062] As one form of the present invention, the substrate treatment liquid contains, in addition to the curing component, (ii) a surface modification component represented by the general formula (I). The formula (I) will be described later.

[0063] The surface modification component (B) is preferably a repellent. Without being limited by theory, in one form of the present invention, it is considered that the surface modification component (B) adsorbs on the surface of the pattern, repels between the patterns, and thus can further prevent pattern collapse.

[0064] Generally, as a surface modifier, a silicon coupling agent is known. However, since the silicon coupling agent reacts with water and alcohol, water and alcohol cannot be used as solvents. Furthermore, a chemical bond is formed between the silicon coupling agent and the substrate surface, and so-called chemical adsorption occurs. Therefore, when removing the silicon coupling agent, treatments such as ashing for cutting the bond are required. Without being limited by theory, since the surface modification component (B) contained in the substrate treatment liquid is physically adsorbed, many types of solvents can be used like the solvent (C) described later. Furthermore, the surface modification component (B) can be removed when the curing component (A) vaporizes. In this case, a treatment for removing only the surface modification component (B) is not required.

[0065] For example, the surface modification component (B) is a compound represented by the general formula (I):

[0066]

[0067] Here, in the general formula (I), each X is independently selected from 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 X is independently preferably a tertiary amine, a primary amine, -OH, -SO2-NH-SO2-, -CO-NH2, -COOH, -CHO, -SO3H, -CO-NH-CO-, or -CO-NH-SO2-, more preferably a tertiary amine, -OH, or -SO2-NH-SO2-, and even more preferably -OH.

[0068] Furthermore, in the general formula (I), each Y is independently H, a fluoroalkyl having C 1～10 , or a fluoroaryl having C 5～20 , and at least one of Ys is a fluoroalkyl having C 1～10 or a fluoroaryl having C 5～20 . Here, the aforementioned fluoroalkyl is an alkyl in which a part or all of Hs of the alkyl are replaced by fluorine (preferably an alkyl in which all Hs of the alkyl are replaced by fluorine). Here, the aforementioned fluoroaryl is an aryl in which a part or all of Hs of the aryl are replaced by fluorine (preferably an aryl in which all Hs of the aryl are replaced by fluorine). Preferred examples of fluorine are F or Cl (a more preferred example is F). Each Y is independently preferably H, a fluoroalkyl having C 1～9 or a fluoroaryl having C6, and more preferably a fluoroalkyl having C 2～4 .

[0069] Furthermore, n 11 is 1, 2, or 3, m 11 is 1, 2, or 3, and at least one of n 11 and m 11 is 1. It is preferably that n 11 is 1, and m 11 is 1, 2, or 3, and more preferably both n 11 and m 11 are 1.

[0070] In addition, the tertiary amine, secondary amine, and primary amine are as follows.

[0071] -NH-, -NH2

[0072] Furthermore, X can also be a polar functional group. In one compound represented by the general formula (I), the sum of the valences of X is equal to the valence of Y. For example, when n 11 = 1, X is a polar functional group with a valence of m 11 , and the number of m 11 is determined by the selected X.

[0073] Specifically, the structure of the surface modification component (B) is as follows. However, the surface modification component (B) is not limited to the following structure.

[0074]

[0075]

[0076] [1-3. Solvent (C)]

[0077] The substrate treatment liquid according to an embodiment of the present invention contains a solvent (C). The solvent (C) preferably can dissolve at least a part of the solidifying component (A) and has volatility. The boiling point of the solvent (C) at 1 atmospheric pressure is 50 to 200°C, preferably 60 to 170°C, more preferably 70 to 150°C. Further, the solvent (C) is preferably a solvent that vaporizes by spin drying. The content of the solvent (C) is 30 to 99% by mass based on the mass of the substrate treatment liquid, preferably 50 to 95% by mass, more preferably 80 to 95% by mass, and particularly preferably 85 to 95% by mass.

[0078] For example, as the solvent (C), water and / or an organic solvent can be used. The solvent (C) can also be a mixture of water and an organic solvent. The water is preferably pure water (deionized water: DIW). In one aspect of the present invention, the solvent (C) is water. It is considered that when the solvent (C) is water, the amount of the organic solvent used can be reduced, which has advantages in the process.

[0079] When the solvent (C) is a mixture of water and an organic solvent, the volume ratio thereof is 1:99 to 99:1, preferably 10:90 to 90:10, more preferably 20:80 to 80:20, and still more preferably 40:60 to 60:40.

[0080] For example, as the organic solvent, alcohols such as methanol (MeOH), ethanol (EtOH), 1-propanol, isopropanol (IPA), 1-butanol, and benzyl alcohol, alkanes such as hexane, heptane, and octane, ethers such as ethyl butyl ether, dibutyl ether, tetrahydrofuran (THF), and anisole, lactate esters such as methyl lactate and ethyl lactate (EL), acetate esters such as ethyl acetate and butyl acetate, aromatic hydrocarbons such as benzene, toluene, and xylene, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-heptanone, cyclopentanone, and cyclohexanone, amides such as N,N-dimethylacetamide and N-methylpyrrolidone, or lactones such as γ-butyrolactone can be used. In addition, as the ethers, in addition to the above, 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) or propylene glycol monoethyl ether acetate can be used. These organic solvents can be used alone or in combination of two or more.

[0081] Here, a preferred form of the organic solvent contained in the substrate treatment liquid will be specifically described.

[0082] The organic solvent contained in the 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. Further, the organic solvent contained in the solvent (C) is preferably one or more selected from the group consisting of MeOH, EtOH, IPA, PGEE, and acetone. Further, the organic solvent contained in the solvent (C) is more preferably one or more selected from the group consisting of MeOH, EtOH, IPA, and PGEE. When the organic solvents are in a combination of two, the mass ratio is from 1:99 to 99:1, preferably from 10:90 to 90:10, more preferably from 20:80 to 80:20, and even more preferably from 40:60 to 60:40.

[0083] [1-4. Vaporization component (D)]

[0084] A substrate treatment liquid according to an embodiment of the present invention may further contain a vaporizable component (D). The vaporizable component (D) is a component that remains in the film formed from the substrate treatment liquid as a solidifying component and can be vaporized. The vaporizable component (D) is preferably a component different from a plastic crystal compound having a melting point of 20°C or higher and 200°C or lower at room temperature, and more preferably a component different from the solidifying component (A). The content of the vaporizable component (D) contained in the substrate treatment liquid is 0 to 20% by mass relative to the substrate treatment liquid. The upper limit of the aforementioned content is preferably 15% by mass, more preferably 10% by mass, further preferably 5% by mass, and even more preferably 2% by mass. The lower limit of the aforementioned content is preferably 0% by mass, more preferably 0.1% by mass, and further preferably 0.5% by mass. Not containing the vaporizable component (D) (0% by mass) is also a preferred form of the present invention. When the solidifying component contained in a substrate treatment liquid according to an 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 vaporizable component (D), the content of the solidifying component (B) shall be prioritized according to the description of the above solidifying component (A).

[0085] For example, the vaporizable component (D) is a compound such as a saturated hydrocarbon ring. Specifically, the vaporizable component (D) is a compound represented by the general formula (II):

[0086]

[0087] Cy 11 and Cy 12 are each independently a saturated or unsaturated hydrocarbon ring or heterocyclic ring. Preferably, Cy 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 so-called heterocyclic ring here may also become a heterocyclic ring by substituting C n1 forming the ring.

[0088] C n1 are each carbon, and n1 is an integer from 10 to 19 (i.e., C 10 , C 11 ,... C 19 ). The remaining bonding hands of C n1 are bonded to H.

[0089] C n1 may also be each independently substituted with -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 -. However, at least one C n1 is replaced by at least one of the above substituents. Of course, non-existent elements are excluded from this proviso. For example, n 11 = n 12 = 0, C 10 to C 14 is replaced by at least one of them. It is suitable that adjacent C n1 are not replaced simultaneously.

[0090] R n1 and R n1 are each independently C 1～5 alkyl (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 , further preferably C1), R n1 and / or R n1 may also be bonded to other R n1 , R n1 and / or C n1 to form a ring. The form in which R n1 and R n1 are bonded to other R n1 , R n1 and / or C n1 to form a ring is preferred.

[0091] 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.

[0092] Furthermore, the vaporized component (D) may also be two or more compounds. In this case, the vaporized component (D) may also contain the compound represented by the general formula (III) and the compound represented by the general formula (II):

[0093]

[0094] Cy 21 Cy 22 Rn2, Rn2, n 21 n 22 and n 23 are each independently the same as the definition, example and description of Cy 11 Cy12 , Rn1, Rn1, n 11 , n 12 and n 13 are the same.

[0095] C n2 The definitions, examples and descriptions of C are each independently the same as those of C n1 . n2 is an integer from 20 to 29 (i.e., C 20 , C 21 , … C 29 ). The examples and descriptions of n2 (20 - 29) are each independently corresponding to those of n1 (10 - 19).

[0096] The scope of the present invention is not limited, but the following compounds can be cited as specific examples of the gasification component (D). That is, the gasification component (D) is 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 or 1 - adamantanamine.

[0097] The scope of the present invention is not limited, but the specific examples of the gasification component (D) represented by the structure are as follows.

[0098]

[0099] Furthermore, the gasification component (D) can also be a low - molecular compound having 2 or more and 25 or less carbon atoms. In this case, the gasification component (D) is, for example: 1,2 - ethylene glycol, 1,2 - propylene glycol, 1,3 - propylene glycol, 1,2 - butylene glycol, 1,3 - butylene glycol, 1,4 - butylene glycol, 3 - methyl - 1,3 - butylene glycol, 3 - phenyl - 1,3 - butylene glycol, 1,2 - pentylene glycol, 1,3 - pentylene glycol, 2,4 - pentylene glycol, 1,5 - pentylene glycol, 1,2 - hexylene glycol, 2,5 - hexylene glycol, 2,4 - diethyl - 1,5 - pentylene glycol, 2,4 - dimethyl - 2,4 - pentylene glycol, 3 - methyl - 1,5 - pentylene glycol, 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 gasification component (D) is 1,2 - butylene glycol, 1,3 - butylene glycol, 1,4 - butylene glycol, 3 - methyl - 1,3 - butylene glycol or 3 - phenyl - 1,3 - butylene glycol.

[0100] Furthermore, the vaporizable component (D) may also be a polymer. In this case, examples of the vaporizable component (D) include: polyethylene glycol, polypropylene glycol, poly(propylene carbonate), poly(ethylene carbonate), poly(ethylene-propylene glycol), polyacetal, etc. Preferably, the vaporizable component (D) is polyethylene glycol or poly(propylene carbonate).

[0101] When the solidifying component contained in the substrate treatment liquid of an 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 vaporizable component (D), specific examples of the solidifying component (A) are the same as the specific examples of the above vaporizable component (D).

[0102] [1-5. Other Additive (E)]

[0103] The substrate treatment liquid of an embodiment of the present invention may further contain other additives (E). The other additives (E) are compounds different from the components (A) to (D) above. The other additives (E) preferably have high volatility. Specifically, the other additives (E) preferably vaporize when the solidifying component (A) vaporizes, or before and after that, but are not limited thereto. The content of the other additives (E) contained in the substrate treatment liquid is 0 to 20% by mass, preferably 0 to 10% by mass, more preferably 0 to 5% by mass with respect to the solidifying component (A). In addition, needless to say, in an embodiment of the present invention, a form in which the substrate treatment liquid does not contain other additives (E) (0% by mass) is included.

[0104] Hereinafter, the other additives (E) will be specifically described.

[0105] An example of the other additives (E) is a surfactant. If the substrate treatment liquid contains a surfactant as the other additives (E), the coatability on the substrate can be improved. The content of the surfactant contained in the substrate treatment liquid is 0 to 2% by mass, preferably 0 to 1% by mass, further preferably 0 to 0.5% by mass with respect to the solidifying component (A).

[0106] Any surfactant can be used. For example, as the surfactant, an anionic surfactant, a cationic surfactant, or a nonionic surfactant can be used. More specifically, as the surfactant, it is preferably to use alkyl sulfonate, alkyl benzene sulfonic acid, and alkyl benzene sulfonate, laurylpyridinium chloride, laurylmethylammonium chloride, polyoxyethylene octyl ether, polyoxyethylene lauryl ether, or polyoxyethylene alkynediol ether. In addition, as the nonionic surfactant, commercially available nonionic alkyl ether surfactants such as those manufactured by Nippon Nyukazai are available.

[0107] Furthermore, another example of the other additive (E) is an antibacterial agent, a bactericide, a preservative, or a fungicide. If an antibacterial agent, a bactericide, a preservative, or a fungicide is contained as the other additive (E), the propagation of bacteria or fungi in the substrate treatment liquid can be prevented, and the change of the substrate treatment liquid over time can be suppressed. The content of the antibacterial agent, bactericide, preservative, or fungicide contained in the substrate treatment liquid is 0 to 1% by mass, preferably 0 to 0.1% by mass, and more preferably 0 to 0.01% by mass with respect to the curable component (A).

[0108] For example, as the antibacterial agent, bactericide, preservative, or fungicide, an alcohol such as phenoxyethanol or isothiazolone can be used. In addition, as the preservative, fungicide, or bactericide, Bestside (trade name) manufactured by Nippon Soda Co., Ltd. is commercially available.

[0109] Furthermore, a further other example of the other additive (E) is an acid or a base. If an acid or a base is contained as the other additive (E), the properties of the substrate treatment liquid such as the adjustment of the pH of the substrate treatment liquid or the adjustment of the solubility of the above components (A) to (D) contained in the substrate treatment liquid can be improved. The acid or base can also be prepared according to the material of the substrate coated with the substrate treatment liquid and added to the substrate treatment liquid. The content of the acid or base contained in the substrate treatment liquid is 0 to 1% by mass, preferably 0 to 0.5% by mass, and more preferably 0 to 0.2% by mass with respect to the curable component (A).

[0110] The acid or base can be arbitrarily selected within the range that does not impair the effects of the present invention. For example, as the acid or base, carboxylic acid, amines, or ammonium salts can be used. Among the carboxylic acid, amines, or ammonium salts here, fatty acids, aromatic carboxylic acids, primary amines, secondary amines, tertiary amines, or ammonium compound classes are included, and they may also be substituted by substituents as the case may be. More specifically, as the acid or base, 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, etc. can be used.

[0111] [2. Use of Substrate Treatment Liquid]

[0112] Refer to Figure 1 of (A) to Figure 1 of (E), the use of the substrate treatment liquid according to an embodiment of the present invention will be described.

[0113] Figure 1 of (A) to Figure 1 of (E) is a schematic cross-sectional view showing a method of forming a substrate pattern using the substrate treatment liquid according to an embodiment of the present invention.Figure 1 In (A) to Figure 1 In (E), the steps of the method for forming a substrate pattern are described in sequence. The method for forming a substrate pattern can be arbitrarily selected from well-known methods such as dry etching. For example, an example of the method for forming a substrate pattern is also disclosed in Non-Patent Document 1. In addition, in the formation of the substrate pattern, various pre-treatments can be combined.

[0114] Figure 1 In (A), a state is shown in which a coated carbon film layer 12, a silicon-containing antireflection film layer 13, and a resist pattern 14 are sequentially formed on a substrate 11.

[0115] The substrate 11 is a semiconductor wafer, a glass substrate for a liquid crystal display device, a glass substrate for an organic EL display device, a glass substrate for a plasma display, a substrate for an optical disc, a substrate for a magnetic disk, a substrate for a magneto-optical disc, a glass substrate for a photomask, or a substrate for a solar cell, etc. The substrate 11 can also be an unprocessed substrate (for example, a bare wafer), or a processed substrate (for example, a patterned substrate). That is, in the substrate 11, a conductive film, wiring, or semiconductor elements, etc. can also be formed. The substrate can also be a structure formed by laminating multiple layers. The substrate 11 is preferably a semiconductor. The semiconductor can also be composed of an oxide, a nitride, a metal, or any combination thereof. Therefore, the material of the substrate 11 is not particularly limited, for example, it is: Si, Ge, SiGe, SiO2, TiO2, Al2O3, SiON, HfO2, Ta2O5, HfSiO4, Y2O3, GaN, TiN, TaN, Si3N4, NbN, Cu, Ta, W, Hf, or Al, etc.

[0116] The coated carbon film layer 12 includes a coated carbon film (also referred to as a coated C film, a spin-on carbon film). The coated carbon film layer 12 is formed by coating through a well-known method such as spin coating and then performing pre-baking. Furthermore, the coated carbon film layer 12 can also be formed by film formation using a CVD (chemical vapor deposition) method or an ALD (atomic layer deposition) method.

[0117] The silicon-containing antireflection film layer 13 includes a silicon-containing antireflection film (also referred to as a Si-ARC film). The silicon-containing antireflection film layer 13 is formed by coating through a known method such as spin coating and then performing pre-baking. By forming the silicon-containing antireflection film layer 13, the profile shape and exposure margin can be improved. In addition, when the silicon-containing antireflection film layer 13 is used as an etching mask, the silicon-containing antireflection film layer 13 preferably has etching resistance.

[0118] The resist pattern 14 can be formed by combining known methods. For example, a method for forming a resist pattern 14 is disclosed in Patent Document 3.

[0119] In the etching of the substrate 11, after etching the silicon-containing antireflection film layer 13 using the resist pattern 14 as a mask, the coated carbon film layer 12 and the substrate 11 are etched using the silicon-containing antireflection film layer 13 as a mask. Alternatively, after etching the silicon-containing antireflection film layer 13 and the coated carbon film layer 12 using the resist pattern 14 as a mask, the substrate 11 is etched using the silicon-containing antireflection film layer 13 and the coated carbon film layer 12 as a mask. Or, using the resist pattern 14 as a mask, the silicon-containing antireflection film layer 13, the coated carbon film layer 12, and the substrate 11 can be etched continuously. In addition, the etching can be wet etching or dry etching.

[0120] Figure 1 In (B) thereof, a state is shown in which the substrate 11 is dry-etched and a gap 15 is formed on the surface of the substrate 11. The type of gas for dry etching is not particularly limited, but generally a fluorocarbon gas is used. As Figure 1 shown in (B) thereof, residues (debris) 16 remain in the gap 15 after dry etching.

[0121] Figure 1 In (C) thereof, a state is shown in which the etched substrate 11 is cleaned with the cleaning liquid 17. The cleaning method using the cleaning liquid 17 can be a known method, for example: a coating method, a dropping method, and a liquid immersion method, or a combination thereof. By cleaning with the cleaning liquid 17, the residues 18 are removed. The cleaning liquid 17 is preferably an organic solvent, and more preferably IPA.

[0122] Figure 1 In (D) thereof, a state is shown in which the substrate treatment liquid 19 is filled in the gap 15. Specifically, Figure 1In (D), a film formed by the substrate treatment liquid 19 is formed so as to cover the gap 15. The substrate treatment liquid 19 is applied (including dropping or liquid immersion) in a state where the cleaning liquid 17 remains in the gap 15. The application of the substrate treatment liquid 19 is not particularly limited. For example, a method of dropping and spreading the substrate treatment 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 treatment liquid 19 on the surface of the stationary substrate 11 and then rotating the substrate 11 at 1 to 3,000 rpm to spread the substrate treatment liquid 19, a method of immersing the substrate 11 in the substrate treatment liquid 19, or a method of supplying the substrate treatment liquid 19 by spraying or blowing can be used. Among them, a method of dropping and spreading on the surface of the substrate 11 while rotating the substrate 11 at 1 to 3,000 rpm or a method of dropping the substrate treatment liquid 19 on the surface of the stationary substrate 11 and then rotating the substrate 11 at 1 to 3,000 rpm to spread the substrate treatment liquid 19 is preferred. At this time, at least a part of the cleaning liquid 17 in the gap 15 is replaced, and the substrate treatment liquid 19 fills the gap 15. In order to fully exhibit the effects of the present invention, it is preferred that the cleaning liquid 17 is sufficiently replaced by the substrate treatment liquid 19.

[0123] The cleaning can also be in multiple steps. For example, after applying a cleaning liquid (such as an acid or a base) that dissolves / removes inorganic substances, a cleaning liquid (such as deionized water or an organic solvent) that is highly compatible with the substrate treatment liquid 19 can be applied. Even in this case, it is still preferred that the cleaning liquid present in the gap 15 is sufficiently replaced by the substrate treatment liquid 19.

[0124] After the above steps, the substrate 11 can be rotated at a speed faster than 50 rpm but lower than 5,000 rpm. Through this rotation, the excessive organic solvents and water of the substrate treatment liquid 19 are removed from the substrate 11, but at least a part of the solidified component (A) remains. Since all of the components of the substrate treatment liquid 19 are not removed from the gap 15, a film can be formed to prevent pattern collapse.

[0125] The film thickness T of the film formed by the substrate treatment liquid 19 is, for example, 0.02 to 5 μm, preferably 0.05 to 4 μm, and more preferably 0.1 to 3 μm. Further, the relationship between the film thickness T of the film and the height H of the pattern 20 described later, for example, satisfies 1H ≦ T ≦ 5H, preferably 1.2H ≦ T ≦ 4H, and more preferably 1.5H ≦ T ≦ 3H. If the film thickness of the film formed by the conventional substrate treatment liquid increases, there is a problem that cracks occur in the film. That is, the conventional film has a large dependence on the film thickness and a narrow process window. Without being limited by theory, it is considered that in one aspect of the present invention, the film formed by the substrate treatment liquid 19 is a film formed of a plastic solidified component (A), has high toughness, and is difficult to crack even when it is a thick film. Therefore, it is considered that the process window of the film formed by the substrate treatment liquid 19 is wide, and even in the case of a thick film, pattern collapse can be prevented.

[0126] Figure 1 In (E), a state is shown in which the pattern 20 is formed by removing the substrate treatment liquid 19 filled in the gap 15. The removal of the substrate treatment liquid 19 can also be performed by heating, air drying (blowing), rotation, standing, or a combination thereof. As long as the shape of the pattern 20 is not damaged, any method can be used for the removal method of the substrate treatment liquid 19. In the removal of the substrate treatment liquid 19 by heating, the heating time is not particularly limited, for example, it is 0 to 180 seconds, preferably 10 to 120 seconds, and more preferably 10 to 90 seconds. The removal of the substrate treatment liquid 19 by air drying can be performed by holding the pattern 20 in an air stream. At this time, the air stream can be a positive pressure or a negative pressure. Specifically, an air stream can be generated by blowing a gas. In this case, the gas to be blown is not particularly limited. Gases such as air can also be used, but inert gases such as argon or nitrogen are preferably used. The flow rate of the air stream is not particularly limited, and the conditions for removing the substrate treatment liquid 19 can be appropriately selected. In the removal of the substrate treatment liquid 19, it is preferable that the humidity of the environment or the gas forming the air stream 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 the removal of the substrate treatment liquid 19 by rotation, the rotation speed and rotation time of the substrate are not particularly limited, for example, they are 20 to 200 rpm, 30 to 300 seconds.

[0127] Here, as Figure 1 shown in (E), the line width of the pattern 20 is set to x, and the height is set to H. The aspect ratio of the pattern 20 is represented by H / x. As the range in which the above-described method for forming a substrate pattern can be effectively applied, the height H of the pattern is, for example, 0.01 to 6 μm or less, preferably 0.05 to 5 μm, and more preferably 0.1 to 3 μm. Further, the aspect ratio H / x is, for example, 5 to 25, preferably 15 to 22.

[0128] In the method for forming a substrate pattern using a substrate treatment liquid according to an embodiment of the present invention, even for a fine pattern, the collapse rate of the substrate pattern can be suppressed. For example, a pillar pattern in which the middle part of a cylindrical shape becomes thinner than the bottom and / or the top is likely to collapse, but even for such a pillar pattern, by using the above-described method for forming a substrate pattern, the collapse rate of the substrate pattern can be suppressed and cleaning can be performed.

[0129] It is considered that a line space pattern as a wall structure is more difficult to collapse than a pillar pattern, but by using the above-described method for forming a substrate pattern, the collapse rate can be further reduced.

[0130] The above pattern 20 can be processed further to fabricate a device. Examples of the device include: a semiconductor device, a liquid crystal display device, an organic EL display device, a plasma display device, or a solar cell device, etc. The device is preferably a semiconductor. These processes can use known methods. After the device is formed, if necessary, the substrate can be cut into chips, connected to a lead frame, and encapsulated with resin. An example of the encapsulated device is a semiconductor.

[0131] [Examples]

[0132] Hereinafter, based on examples, a substrate treatment liquid according to an embodiment of the present invention will be described in more detail. In addition, the substrate treatment liquid according to an embodiment of the present invention is not limited to the following examples.

[0133] [Preparation of Example 1]

[0134] As the curing component (A), 2,2-dimethyl-1-propanol (S1) was added to IPA as the solvent (C) so as to be 10% by mass based on the prepared substrate treatment liquid. The container was covered and stirred overnight, and visual confirmation was made that the solute was dissolved. The solution obtained above was filtered through a filter with a pore size of 0.1 μm to obtain a substrate treatment liquid (Example 1).

[0135] [Preparation of Examples 2 to 15 and Comparative Examples 1 to 2]

[0136] As shown in Table 1, the types and concentrations of the curing component (A), the surface modification component (B), and the solvent (C) were changed, and other than that, the preparation was carried out in the same manner as in Example 1 to obtain substrate treatment liquids (Examples 2 to 15, Comparative Examples 1 to 2). In addition, the concentration of the surface modification component (B) is based on the prepared substrate treatment liquid.

[0137] [Table 1]

[0138]

[0139] Here, S1 in Table 1 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-dimethylpropanoic acid, S5 is DL-pantolactone, S6 is cyclohexanone oxime, and S7 is cyclohexane. Further, F1 in Table 1 is perfluorotriethylamine, 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.

[0140] [Evaluation of the Formation of Plastic Crystal Phase]

[0141] A wafer on which a column pattern has been formed (hereinafter referred to as a pattern wafer) is mounted on an MS-A150 spin coater (Mikasa), 2 cc of a substrate treatment liquid is dropped onto the pattern wafer, and spin coating is performed at 1,000 rpm for 20 seconds. In addition, the pattern wafer has a column pattern formed on a silicon wafer, with the top diameter of the cylinder being approximately 30 nm, the bottom diameter being approximately 65 nm, and the height being approximately 600 nm (provided by Interuniversity Microelectronics Centre (IMEC)), and is cut into a square of approximately 3 cm on a side for use. Visual confirmation is made as to whether a plastic crystal phase formed by the solidified component (A) in the substrate treatment liquid is formed. The evaluation criteria are as follows. However, in Comparative Example 2, the formation of a solid film was not confirmed, so data could not be obtained.

[0142] A: A plastic crystal layer is formed.

[0143] B: A plastic crystal layer is not formed.

[0144] [Evaluation of Cracks]

[0145] The following treatment is performed using the same pattern wafer as that used for the evaluation of the formation of the plastic crystal phase to produce a sample substrate for the evaluation of cracks. The pattern wafer is mounted on an MS-A150 spin coater, 2 cc of a substrate treatment liquid is dropped onto the pattern wafer, and spin coating is performed at 1,000 rpm for 20 seconds. Immediately after spin coating, the pattern wafer is placed on a metal plate cooled to -120 °C to cool the solid film and suppress the sublimation of the solid film. The upper surface of the sample substrate is observed using Cryo-SEM (Helios NanoLab 650, Thermo Scientific) at a magnification of 3K in the range where visual recognition is possible without movement to evaluate the presence or absence of cracks in the solid film. The evaluation criteria are as follows. However, in Comparative Example 2, the formation of a solid film was not confirmed, so data could not be obtained.

[0146] A: No cracks are found.

[0147] B: Cracks are found.

[0148] [Measurement of Film Thickness in Crack Evaluation]

[0149] Slice the wafer for the sample substrate used in crack evaluation. Using Cryo-SEM, observe the cross-section of the slice within the visually recognizable range without moving at a magnification of 20K to measure the film thickness. In addition, in Comparative Example 2, the formation of a solid film was not confirmed, so data could not be obtained.

[0150] [Residual Film Evaluation]

[0151] Perform the following process using the same patterned wafer as used in the evaluation of the formation of the plastic crystal phase to fabricate a sample substrate for residual film evaluation. Mount the patterned wafer on an MS-A150 spin coater, drop 2 cc of the substrate treatment liquid on the patterned wafer, and spin coat for 20 seconds at 1,000 rpm. Immediately thereafter, heat the patterned wafer on a hot plate at 65 °C for 120 seconds to sublime and remove the solid film. Slice the wafer for the sample substrate. Using SEM (SU8200, Hitachi HighTechnologies), observe the cross-section of the slice within the visually recognizable range without moving at a magnification of 20K to evaluate the presence of a residual film. The evaluation criteria are as follows. However, in Comparative Example 2, the formation of a solid film was not confirmed, so data could not be obtained.

[0152] A: No residual film was confirmed.

[0153] B: A residual film was confirmed.

[0154] [Evaluation of Substrate Pattern Collapse Rate]

[0155] Fabricate a sample substrate identical to the sample substrate for residual film evaluation. Using SEM (SU8200), observe the upper surface of the sample substrate within the visually recognizable range without moving at a magnification of 10K to evaluate the substrate pattern collapse rate. The collapse rate is calculated by dividing the number of collapsed patterns by the total number of patterns in the substrate pattern in the observed image and multiplying it by 100 times. The evaluation criteria are as follows.

[0156] A: The collapse rate is less than 1%.

[0157] B: The collapse rate is 1% or more and less than 5%.

[0158] C: The collapse rate is 5% or more.

[0159] [Comprehensive Evaluation]

[0160] Based on the above evaluations, perform a comprehensive evaluation. The evaluation criteria are as follows.

[0161] A: The residual film evaluation is A and the collapse rate evaluation is A.

[0162] B: The residual film is evaluated as A, and the collapse rate is evaluated as B.

[0163] C: The residual film is evaluated as B, or the residual film is evaluated as A and the collapse rate is evaluated as C.

[0164] The evaluation results of the plastic crystal phase, crack, film thickness, residual film, collapse rate of the substrate pattern, and comprehensive evaluation described above are shown in Table 2.

[0165] [Table 2]

[0166]

[0167] As can be seen from Table 2, Examples 1 to 15 are more excellent as the substrate treatment liquid compared with Comparative Examples 1 to 2.

[0168] [Symbol Explanation]

[0169] 11: Substrate

[0170] 12: Coated carbon film layer

[0171] 13: Silicon-containing antireflection film layer

[0172] 14: Resist pattern

[0173] 15: Gap

[0174] 16: Residue (fragment)

[0175] 17: Cleaning liquid

[0176] 18: Residue

[0177] 19: Substrate treatment liquid

[0178] 20: Pattern.

Claims

1. A substrate treatment liquid containing a curing component, satisfying at least one of the following conditions (i) or (ii): (i) The curing component is a plastic crystal compound having a melting point of 20 °C or higher and 200 °C or lower; and (ii) The substrate treatment liquid further contains a surface modification component represented by the following general formula (I): wherein each X is independently selected from 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-; Y is independently H, a fluoroalkyl group having C 1～10 , or a fluoroaryl group having C 5～20 . At least one of Y is a fluoroalkyl group having C 1～10 or a fluoroaryl group having C 5～20 . where n 11 is 1, 2, or 3, where m 11 is 1, 2 or 3, and where n 11 and m 11 is at least one of 1.

2. The substrate treatment liquid according to claim 1, wherein, The substrate treatment liquid is not cooled at a temperature higher than a temperature 5 °C lower than the freezing point of the curing component and lower than the freezing point of the curing component.

3. The substrate treatment liquid according to claim 1, wherein, The molecular weight of the curing component is 58 or more and 200 or less.

4. The substrate treatment liquid according to claim 1, wherein, The content of the curing component is 1% by mass or more and 50% by mass or less based on the substrate treatment liquid.

5. The substrate treatment liquid according to claim 1, wherein, The content of the surface modification component is 0.01% by mass or more and 1.0% by mass or less based on the substrate treatment liquid.

6. The substrate treatment liquid according to claim 1, further containing a solvent, wherein the solvent includes an organic solvent containing 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.

7. The substrate treatment liquid according to claim 1, wherein, The substrate treatment liquid is used to replace the cleaning liquid remaining on the substrate when cleaning a substrate pattern on the substrate with a cleaning liquid.

8. The substrate treatment liquid according to claim 1, Among them, A film is formed using the substrate treatment liquid, and then the film is removed from the substrate pattern by vaporizing the curing component, The vaporization is sublimation, or when removing the film formed from the substrate treatment liquid, it is carried out by at least one step selected from the group consisting of heating the substrate, blowing a gas, and rotating the substrate.

9. The substrate treatment liquid according to claim 1, Among them, The substrate treatment liquid is coated on a pattern of a substrate to form a film, and wherein, the thickness T of the film and the height H of the pattern satisfy the relationship of 1H ≦ T ≦ 5H.

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