Substrate cleaning solution, method for manufacturing a cleaned substrate using the same, and method for manufacturing a device

Abstract

To obtain a substrate cleaning solution capable of cleaning the substrate and removing particles. [Solution] A substrate cleaning solution comprising a polymer (A), a heat-responsive soluble compound (B), and a solvent (C) is provided.

Description

[Technical Field]

[0001] This invention relates to a substrate cleaning solution, a method for manufacturing a cleaned substrate using the same, and a method for manufacturing a device.

[0002] Conventionally, the manufacturing process of substrates can generate foreign matter, for example, during the lithography process. Therefore, the manufacturing process of substrates sometimes includes a cleaning process to remove particles from the substrate. As a substrate cleaning process, a method has been considered in which a film is formed on the substrate to retain particles within the film, and then the film is removed with a removal solution. If the formed film is completely dissolved with the removal solution, the particles retained within the film may reattach. Therefore, a method has been considered in which the formed film is partially dissolved, and the undissolved portion is removed in a solid state. Patent documents 1 and 2 describe studies on forming a film using a cleaning solution containing a sparingly soluble or insoluble solute, a soluble solute, and water, and then removing the film. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] International release 2020 / 120667 [Patent Document 2] International release 2021 / 245014 [Overview of the project] [Problems that the invention aims to solve]

[0004] The inventors believed that there was still one or more issues that needed improvement in the technology of forming a film on a substrate to remove particles. These included, for example: chemical cleaning that removes the film with a removal solution does not completely remove the formed film and leaves some on the substrate; particle removal is not efficient; and it is not possible to prevent the detachment of retained particles. This invention is based on the technical background described above and provides a substrate cleaning solution.

Means for Solving the Problem

[0005] The substrate cleaning liquid according to the present invention comprises a polymer (A), a thermoresponsive soluble compound (B), and a solvent (C). Here, (C) component comprises water (C-1); The content of (B) component is 1 to 200% by mass based on the total mass of (A) component; (B) component comprises an ammonium salt; and (B) component is a crack promoting component (B’), and the decomposition temperature in the atmosphere is 30 to 200°C.

[0006] The method for manufacturing a cleaned substrate according to the present invention comprises the following steps. (1) Drop the above-mentioned substrate cleaning liquid onto the substrate; (2) Remove at least a part of the (C) component in the substrate cleaning liquid to form a film; (3) Hold the particles on the substrate on the film; (4) Remove the film on which the particles on the substrate are held by physical cleaning.

[0007] The method for manufacturing a device according to the present invention comprises the method for manufacturing the above-mentioned cleaned substrate.

Advantages of the Invention

[0008] By using the substrate cleaning liquid according to the present invention, it is possible to expect one or more of the following effects. Efficient particle removal is possible; the formed film can be sufficiently peeled off and removed from the substrate; since the peeling trigger part is in the film, the film can be sufficiently removed; efficient removal can be achieved for both hydrophobic and hydrophilic substrates; it is possible to prevent the detachment of the held particles; the film can be efficiently removed by physical cleaning.

Brief Description of the Drawings

[0009] [Figure 1] Figure 1 is a schematic cross-sectional view illustrating the state of the substrate surface during the cleaning of the substrate according to this invention. [Modes for carrying out the invention]

[0010] The embodiments of the present invention will be described in detail as follows.

[0011] definition In this specification, unless otherwise specified, the definitions and examples set forth in this paragraph shall prevail. The singular form includes the plural form, and "one" or "that" means "at least one." An element of a certain concept can be expressed by multiple types, and when a quantity (e.g., mass %) is given, that quantity represents the sum of those multiple types. "and / or" includes all combinations of elements, as well as their use individually. When a numerical range is indicated using "~" or "-", it includes both endpoints and has the same unit. For example, 5~25 mol% means between 5 mol% and 25 mol%. "C x-y The notations "Cx~Cy" and "Cx" indicate the number of carbon atoms in the molecule or substituent. For example, C 1-6 Alkyl refers to an alkyl chain having between 1 and 6 carbon atoms (such as methyl, ethyl, propyl, butyl, pentyl, and hexyl). When a polymer has multiple types of repeating units, these repeating units copolymerize. These copolymerizations may be alternating copolymerization, random copolymerization, block copolymerization, graft copolymerization, or a mixture of these. When polymers and resins are shown in structural formulas, the n, m, etc., in parentheses indicate the number of repeating units. The unit of temperature used is Celsius. For example, 20 degrees means 20 degrees Celsius. An additive refers to the compound itself that has the function (for example, in the case of a base generator, it is the compound itself that generates a base). The compound may also be dissolved or dispersed in a solvent and added to the composition. In one embodiment of the present invention, it is preferable that such a solvent is included in the composition according to the present invention as solvent (C) or other component.

[0012] <Circuit board cleaning solution> The substrate cleaning solution according to the present invention comprises a polymer (A) (hereinafter sometimes referred to as component (A); the same applies to (B) and subsequent components), a heat-responsive soluble compound (B), and a solvent (C). In the present invention, the "soluble compound" is not limited to being dissolved in solvent (C), but is also acceptable in a suspended state. In a preferred embodiment of the present invention, the components and additives contained in the substrate cleaning solution are dissolved in solvent (C). A substrate cleaning solution in this form is considered to have good embedding performance or film uniformity.

[0013] Preferably, the substrate cleaning solution according to the present invention is dropped onto the substrate and dried, at least a portion of the solvent (C) is removed, forming a film, and then the film is removed from the substrate by physical cleaning. "To form a film" means to form a single film and to coexist within that single film. One form of film formation is the "solidification" of the polymer. The film obtained from the substrate cleaning solution only needs to be firm enough to hold the particles, and the solvent (C) is not completely removed (e.g., by vaporization). The substrate cleaning solution gradually shrinks as the solvent (C) evaporates, forming a film. It is acceptable for very small amounts of components (A) and (B) to be removed (e.g., by evaporation, volatilization). For example, it is acceptable for 0 to 10% by mass (preferably 0 to 5% by mass, more preferably 0 to 3% by mass, even more preferably 0 to 1% by mass, and even more preferably 0 to 0.5% by mass) to be removed compared to the original amount. There is no intention to limit the scope of rights, and we are not bound by theory, but it is thought that the aforementioned film holds particles on the substrate, and the particles are removed by peeling it off through the physical cleaning described below. Component (B) is thought to create a part that triggers the peeling of the film.

[0014] <Polymer (A)> The substrate cleaning solution according to the present invention comprises polymer (A). Examples of polymer (A) include novolac derivatives, phenol derivatives, polystyrene derivatives, polyacrylic acid derivatives, polymethacrylic acid derivatives, polyacrylamide derivatives, polyethylene oxide derivatives, polyvinylamide derivatives, polyamine derivatives, polymaleic acid derivatives, polycarbonate derivatives, polyvinylpyrrolidone derivatives, polyvinyl alcohol derivatives, and copolymers of combinations thereof. Preferably, polymer (A) is selected from the group consisting of polyacrylic acid derivatives, polymethacrylic acid derivatives, and polyvinyl alcohol derivatives. The polymer (A) preferably has hydrophilic groups in its repeating units. Examples of hydrophilic groups include hydroxyl groups, amino groups, carboxyl groups, carbonyl groups, alkylamino groups, amide groups, ester groups, keto groups, sulfo groups, 2-oxy-1-pyrrolidinyl groups, 2-oxy-1-piperidinyl groups, or aldehyde groups, and preferably the hydrophilic groups include hydroxyl groups or carboxyl groups.

[0015] Preferably, component (A) comprises at least one repeating unit represented by formula (A-1) or (A-2). In one preferred embodiment, component (A) comprises formulas (A-1) and (A-2), more preferably substantially comprised of formulas (A-1) and (A-2), and even more preferably comprised of formulas (A-1) and (A-2). In another preferred embodiment, component (A) comprises formula (A-2), more preferably substantially comprised of formula (A-2), and even more preferably comprised of formula (A-2).

[0016] Equation (A-1) is as follows: [Chemical formula] Here, R 11 is C 1-8 alkyl, preferably methyl or ethyl, more preferably methyl. R 12 , R 13 and R 14 are each independently hydrogen, C 1-5 alkyl (where the methylene in the alkyl may be replaced by oxy), or -L1-COOH, preferably hydrogen or methyl, more preferably hydrogen. L1 is a single bond or C 1-4 alkylene, preferably a single bond.

[0017] Examples of formula (A-1) include the following. [Chemical formula]

[0018] Formula (A-2) is as follows. [Chemical formula] Here, R 21 , R 22 , and R 23 are each independently hydrogen, C 1-5 alkyl (where the methylene in the alkyl may be replaced by oxy), or -L1-COOH, preferably hydrogen or methyl, more preferably hydrogen. L1 is a single bond or C 1-4 alkylene, preferably a single bond. X is a hydrophilic group, preferably a hydroxyl group, amino group, carboxyl group, carbonyl group, alkylamino group, amide group, ester group, keto group, sulfo group, 2-oxy-1-pyrrolidinyl group, 2-oxy-1-piperidinyl group, or aldehyde group, more preferably a hydroxyl group, carboxyl group, or ester group, and more preferably a carboxyl group or a hydroxyl group.

[0019] Examples of equation (A-2) include the following: [ka]

[0020] Component (A) may further include at least one repeating unit represented by formula (A-3) or (A-4). In one preferred embodiment, component (A) comprises formulas (A-1), (A-2), and (A-4), more preferably substantially comprising formulas (A-1), (A-2), and (A-4), and even more preferably comprising formulas (A-1), (A-2), and (A-4).

[0021] Equation (A-3) is as follows: [ka] Here, R 31 , R 32 , and R 33 These are, independently, hydrogen or C 1-5 The alkyl group is preferably hydrogen or methyl, and more preferably hydrogen, and the methylene group in the alkyl group may be replaced by an oxy group. Y is a hydrophobic group, preferably -C(O)-N(CH3)2, -C(O)-O-CH3, -C(O)-O-C2H5, -C(O)-O-C2H5-N(CH3)2, -C6H5, and more preferably -C(O)-N(CH3)2-C(O)-O-CH3.

[0022] Examples of equation (A-3) include the following: [ka]

[0023] Equation (A-4) is as follows: [ka] Here, R 41 , R 42 , R 43 , R 44 , R 45 , and R 46 These are, independently, hydrogen or C 1-5 The alkyl group is preferably hydrogen or methyl, and more preferably hydrogen, and the methylene group in the alkyl group may be replaced by an oxy group. R 47 is hydrogen, or C 1-8 Alkyl, more preferably C 1-5 It is alkyl.

[0024] Examples of equation (A-4) include the following: [ka]

[0025] (A) Number of repeating units n of repeating units (A-1), (A-2), (A-3), and (A-4) in component (A) A-1 , n A-2 , n A-3 , and n A-4 teeth, n A-1 / (n A-1 +n A-2 +n A-3 +n A-4 ) is preferably 0-95%, more preferably 0-80%, n A-2 / (n A-1 +n A-2 +n A-3 +nA-4 ) is preferably 5-100%, more preferably 20-100%, n A-3 / (n A-1 +n A-2 +n A-3 +n A-4 ) is preferably 0-20%, more preferably 0-15%, or n A-4 / (n A-1 +n A-2 +n A-3 +n A-4 ) is preferably 0 to 50%, and more preferably 0 to 40. (A) The total number of repeating units in all components n total So, (n A-1 +n A-2 +n A-3 +n A-4 ) / n total The percentage is preferably 80-100%, and more preferably 90-100%.

[0026] The mass-average molecular weight Mw of component (A) is preferably 500 to 300,000, more preferably 5,000 to 300,000, and more preferably 8,000 to 250,000. Here, the mass-average molecular weight is the mass-average molecular weight on a polymethyl methacrylate basis, which can be measured by gel permeation chromatography using polymethyl methacrylate as the reference. The same applies to the following components.

[0027] The content of component (A) is preferably 0.5 to 50% by mass, more preferably 1 to 30% by mass, and even more preferably 2 to 20% by mass, based on the total mass of the substrate cleaning solution.

[0028] <Thermally responsive soluble compound (B)> The substrate cleaning solution according to the present invention comprises a heat-responsive soluble compound (B). Component (B) is a crack-promoting component (B'). There is no intention to limit the scope of rights, and we are not bound by theory, but it is thought that when the substrate cleaning solution dries and forms a film on the substrate, and the film is removed by physical cleaning, component (B) creates a point where the film can peel off.

[0029] In this invention, thermal responsiveness means decomposition by heat. The decomposition temperature of component (B) in air is 30 to 200°C, preferably 50 to 180°C. In this specification, the decomposition temperature means the temperature at which the substance ceases to be a solid or liquid, and is not intended to be the temperature at which thermal decomposition begins. Solubility can be evaluated by known methods. For example, under conditions of 20-35°C (more preferably 25±2°C), 10.0 g of component (B) and 100 mL of water are introduced into a flask, the lid is closed, and the flask is shaken for 3 hours with a shaker to determine whether component (B) has dissolved. Shaking may also be replaced with stirring. Solubility can also be judged visually. If it does not dissolve, it is considered insoluble or sparingly soluble; if it dissolves, it is considered soluble. Preferably, component (B) is soluble in water.

[0030] (B) Examples of component include azo compounds, nitroso compounds, hydrazine derivatives, and ammonium salts, and preferably contains an ammonium salt, and more preferably an ammonium salt, based on its thermal decomposition temperature and solubility in water. Examples of ammonium salts include ammonium carbonate, ammonium acetate, ammonium carbamate, ammonium oxalate, ammonium hydrogen phosphate, ammonium sulfamate, ammonium bicarbonate, ammonium formate, ammonium citrate, and ammonium phosphate, with ammonium carbonate and ammonium acetate being preferred.

[0031] The molecular weight of component (B) is preferably 50 to 300, and more preferably 50 to 270.

[0032] The content of component (B) is 1 to 200% by mass, preferably 1 to 180% by mass, and more preferably 2 to 160% by mass, based on the total mass of component (A).

[0033] <Solvent (C)> The substrate cleaning solution according to the present invention comprises a solvent (C). The solvent (C) comprises water (C-1). Water (C-1) is preferably deionized water (DIW). The water (C-1) contained in the substrate cleaning solution may be partially removed during film formation, but at least a portion of it remains in the film after formation. The water (C-1) content is preferably 10 to 100% by mass, and more preferably 15 to 100% by mass, based on the solvent (C).

[0034] The solvent (C) may further contain an organic solvent (C-2). The content of component (C-2) is preferably 0 to 90% by mass, and more preferably 0 to 85% by mass, based on the total mass of component (C). (C-2) Examples of components include alcohols such as isopropanol (IPA), 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), propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monoethyl ether acetate, lactic acid esters such as methyl lactate and ethyl lactate (EL), aromatic hydrocarbons such as toluene and xylene, ketones such as methyl ethyl ketone, 2-heptanone and cyclohexanone, amides such as N,N-dimethylacetamide and N-methylpyrrolidone, and lactones such as γ-butyrolactone. These organic solvents can be used individually or in combination of two or more. In a preferred form, the (C-2) component is selected from IPA, PGME, PGEE, EL, PGMEA, or any combination thereof.

[0035] The content of component (C) is preferably 1 to 99% by mass, and more preferably 70 to 99% by mass, based on the total mass of the substrate cleaning solution.

[0036] <Other additives (D)> The substrate cleaning solution of the present invention may further contain other additives (D) in addition to components (A) to (C). Here, the other additives (D) include surfactants, acids, bases, antibacterial agents, disinfectants, preservatives, or antifungal agents, and may include any combination thereof. In one preferred embodiment, component (D) comprises a surfactant. The content of component (D) (or the sum of multiple components) is preferably 0 to 10 mass, preferably 0 to 10% by mass, more preferably 0 to 5% by mass, even more preferably 0 to 3% by mass, and even more preferably 0 to 1% by mass, based on the total mass of component (A). It is also an embodiment of the present invention that the substrate cleaning solution does not contain component (D) (0% by mass).

[0037] Without the intention to limit the present invention and without being bound by theory, one embodiment of a method for manufacturing a cleaned substrate using the substrate cleaning solution according to the present invention will be explained using schematic diagrams for the purpose of understanding the present invention. The substrate cleaning solution used in the embodiment shown in Figure 1 comprises components (A), (B), and (C). (a) shows a state in which particles 2 are attached to the substrate 1. When the substrate cleaning solution according to the present invention is dropped onto this substrate and a portion of the solvent (C) is dried, the state in which components (A) and (B) form a film is shown in (b). Component (A) adheres to the substrate with a moderate adhesive force. It is preferable that component (A) has hydrophilic groups, as this allows it to adhere to a hydrophobic substrate with a moderate adhesive force. In (b), the film becomes a particle-retaining layer 3. A thermally responsive soluble compound (B) 4 exists within the particle-retaining layer 3. Component (B) decomposes upon heating, generating gas. This state is shown in (c). Since the volume of the generated gas exceeds 200 times that of component (B), cracks are formed in the film (b) due to the gas, and a portion of the cracked film peels off from the substrate due to the gas. This state is shown in (d). The particle-holding layer 3 has cracks while retaining particles. Because the adhesion of component (A) to the substrate is not too strong, the particle-holding layer 3 with cracks is removed from the substrate while retaining particles by physical cleaning with a small physical force, which is the state shown in (e). The state of the substrate obtained after cleaning is shown in (f).

[0038] <Cleaning of circuit boards> The substrate cleaning solution of the present invention can be used to clean substrates. Known methods and apparatus can be used to clean substrates. The present invention provides, in one embodiment, a method for manufacturing a cleaned substrate. In the following sections, the method for cleaning the circuit board will be explained using more specific examples. In the following sections, the numbers in parentheses indicate the order of the steps. For example, if steps (0-1), (0-2), and (1) are listed, the order of the steps is as described above. The method for manufacturing a cleaned substrate according to the present invention comprises the following steps. (1) Drop the substrate cleaning solution according to the present invention onto the substrate; (2) Remove at least a portion of the solvent (C) from the substrate cleaning solution and form a film; (3) The film holds particles on the substrate; (4) Remove the film on which the particles on the substrate are retained by physical cleaning.

[0039] (1) is performed by dropping the substrate cleaning solution onto the approximate center of a horizontally positioned substrate using a nozzle or the like in an apparatus suitable for substrate cleaning. The dropping can be in a columnar form or as a fall. During the dropping process, the substrate can be rotated at, for example, 10 to several tens of rpm to suppress the occurrence of droplet marks. The amount to be dispensed is preferably 0.5 to 10 cc. These conditions can be adjusted to ensure that the substrate cleaning solution is applied and spread evenly. The removal of solvent (C) in (2) above is carried out by drying, preferably by spin-drying. Spin-drying is preferably performed at 500 to 3,000 rpm and preferably for 0.5 to 90 seconds. This allows the solvent (C) to be dried while the substrate cleaning solution is spread over the entire surface of the substrate. Preferably, the substrate is a disc-shaped substrate with a diameter of 200 to 600 mm (more preferably 200 to 400 mm). The process involves heating, preferably at 50-200°C, more preferably at 50-190°C, for 60-600 seconds, more preferably at 60-300 seconds, after the removal of the solvent. This heating causes the decomposition of component (B). The retention of particles in (3) is achieved by the removal of solvent (C) in (2), which causes polymer (A) to form a film and retain the particles. In other words, steps (2) and (3) can be said to occur continuously in a single operation. Here, the removal of solvent (C) in (2) means that it is permissible for a small amount of solvent (C) to remain in the film. In one embodiment of the present invention, at the end of steps (2) and (3), 95% or more (preferably 98% or more, more preferably 99% or more) of solvent (C) is volatilized and does not remain in the film.

[0040] (4) The film (particle-holding layer) on which the particles on the substrate are held is removed by physical cleaning. In this specification, physical cleaning means cleaning that removes adhering substances from the substrate surface by applying a physical force greater than the adhesive force to the adhering substances. Physical cleaning preferably comprises at least one of brush scrubbing, gas blowing, ice scrubbing, dry ice scrubbing, spray showering, and ultrasonic irradiation, and more preferably is performed by brush scrubbing or gas blowing. In a preferred embodiment of the present invention, the particle-holding layer is removed from the substrate while retaining the particles, rather than being broken down into particles of the size of the particles during physical cleaning. It is thought that the particle-holding layer is removed by being broken into small pieces, for example, by the aforementioned "parts that trigger peeling."

[0041] <Circuit board> Examples of substrates to be cleaned in the present invention include semiconductor wafers, glass substrates for liquid crystal displays, glass substrates for organic EL displays, glass substrates for plasma displays, substrates for optical discs, substrates for magnetic discs, substrates for magneto-optical discs, glass substrates for photomasks, substrates for solar cells, and the like. The substrate may be an unprocessed substrate (e.g., a bare wafer) or a processed substrate (e.g., a patterned substrate). The substrate may be composed of multiple layers stacked on top of each other. Preferably, the surface of the substrate is a semiconductor. The semiconductor may be composed of oxides, nitrides, metals, or any combination thereof. Preferably, the surface of the substrate is selected from the group consisting of Si, Ge, SiGe, Si3N4, TaN, SiO2, TiO2, Al2O3, SiON, HfO2, T2O5, HfSiO4, Y2O3, GaN, TiN, SiCN, NbN, Cu, Ta, W, Hf, Ru, Co, amorphous carbon, and Al.

[0042] <device> A device can be manufactured by further processing a substrate cleaned by the cleaning method according to the present invention. Examples of devices include semiconductors, liquid crystal display elements, organic EL display elements, plasma display elements, and solar cell elements. Known methods can be used for these processing steps. After device formation, the substrate can be cut into chips as needed, connected to a lead frame, and packaged with resin. One example of such a packaged product is a semiconductor.

[0043] [Examples] The present invention will be described below with reference to various examples. However, the embodiments of the present invention are not limited to these examples.

[0044] <Example 1 of washing solution preparation for Example 1> DIW is used as the solvent (C). Polymer 1, shown below, is used as polymer (A), and ammonium carbonate is used as the heat-responsive soluble compound (B). (A) and (B) are added to solvent (C) such that the content of (B) is 5.0% by mass based on (A), and the solid component concentration in the washing solution (sum of (A) and (B)) is 5.0% by mass. The mass ratio of (A) to (B) is as shown in Table 1. This is stirred with a stirring bar for 1 hour to obtain a solution with a solid component concentration of 5% by mass. This solution is filtered using an Optimizer UPE (Nippon Integris Co., Ltd., UPE, pore size 10 nm). This obtains the washing solution of Example 1.

[0045] <Examples of cleaning solution preparation for Examples 2-21 and Comparative Examples 1-4> The washing solutions for Examples 2-21 and Comparative Examples 1-4 were prepared in the same manner as in Preparation Example 1, except that each component and its ratio was changed as shown in Table 1. [Table 1] In the table above, the lower row for polymer (A) and thermally responsive soluble compound (B) represents the mass ratio of (A) to (B), and the lower row for solvent represents the mass ratio of (C-1) to (C-2). In the table, each polymer has the following structure. Mw below represents the weight-average molecular weight on a polymethyl methacrylate basis. Polymer 1: m:n = 99:1 (molar ratio), Mw = 200,000. [ka] Polymer 2: m:n = 85:15 (molar ratio), Mw = 30,000. [ka] Polymer 3: l:m:n = 30:69:1 (molar ratio), Mw = 20,000. [ka] Polymer 4: Mw = 15,000. [ka]

[0046] <Preparation of the evaluation substrate for removal evaluation> A substrate with a water contact angle of 78° is obtained by dropping 10 mL of hexamethyldisilazane (HMDS) onto a 12-inch bare Si substrate, coating and drying by rotating at 1,000 rpm for 60 seconds, and then heating at 100°C for 60 seconds. Particles are then attached to the obtained substrate. Ultra-high purity colloidal silica (PL-10H, Fuso Chemical Industries, average primary particle size 90 nm) is used as the experimental particles. 50 mL of the silica nanoparticle composition is dropped onto the substrate and coated by rotating at 500 rpm for 5 seconds. Then, the solvent of the silica nanoparticle composition is spin-dried by rotating at 1,000 rpm for 30 seconds. This obtains an evaluation substrate.

[0047] <Removal Evaluation> Use the evaluation board prepared as described above. Using the Coater Developer RF3 (SOKUDO), 10cc of cleaning solution is dropped onto the evaluation substrate and coated and dried by rotating at 1,500 rpm for 60 seconds to form a film. After heating the substrate at the temperature listed in Table 1 for 180 seconds, the film is peeled off and removed by blowing with N2 or brush scrubbing with a PVA brush. The amount of particles remaining on these substrates will be compared using a dark-field defect inspection system (LS-9110, Hitachi High-Tech Corporation). The coating status and film removal status are checked, the number of remaining particles is counted, and the evaluation is performed according to the following criteria. The evaluation results are recorded in Table 1. AA:≦10 pieces A:>10 pieces, ≦100 pieces B:>100 pieces, ≦1,000 pieces C:>1000 pieces D: The film is not applied uniformly, or the film is not removed. [Explanation of Symbols]

[0048] 1. Circuit board 2. Particles 3. Particle retention layer 4. Thermally responsive soluble compounds (B) 5. Traces of decomposition of thermally responsive soluble compound (B) 6. Crack

Claims

1. A substrate cleaning solution comprising a polymer (A), a heat-responsive soluble compound (B), and a solvent (C), Here, (C) component comprises water (C-1); The content of component (B) is 1 to 200% by mass, based on the total mass of component (A); (B) Component comprises an ammonium salt; and A substrate cleaning solution in which component (B) is a crack-promoting component (B') and has a decomposition temperature of 30 to 200°C in air.

2. The substrate cleaning solution according to claim 1, wherein component (A) is a polymer comprising at least one repeating unit represented by formula (A-1) or (A-2). 【Chemistry 1】 (Here, R １１ C １－８ It is alkyl; R １２ 、 R １３ 、 R １４ 、 R ２１ 、 R ２２ 、 and R ２３ are each independently hydrogen, C １－５ alkyl (wherein methylene in the alkyl may be replaced by oxy), or -L １ -COOH; L １ is a single bond or C １－４ It is alkylene, X is a hydrophilic group.

3. The substrate cleaning solution according to claim 2, wherein component (A) further comprises at least one repeating unit represented by formula (A-3) or (A-4). 【Chemistry 2】 (Here, R ３１ , R ３２ , R ３３ , R ４１ , R ４２ , R ４３ , R ４４ , R ４５ , and R ４６ These are, independently, hydrogen or C １－５ It is an alkyl group (where the methylene group in the alkyl group may be replaced by an oxy group); Y is a hydrophobic group; R ４７ is hydrogen, or C １－８ (It is alkyl.)

4. The substrate cleaning solution according to at least one of claims 1 to 3, wherein component (C) further comprises an organic solvent (C-2), and the content of the organic solvent (C-2) is 0 to 50% by mass based on the total mass of component (C).

5. The substrate cleaning solution according to claim 2 or 3, wherein the hydrophilic group comprises at least one of a hydroxyl group, an amino group, a carboxyl group, a carbonyl group, an alkylamino group, an amide group, an ester group, a keto group, a sulfo group, a 2-oxy-1-pyrrolidinyl group, a 2-oxy-1-piperidinyl group, or an aldehyde group.

6. (A) Number of repeating units n of repeating units (A-1), (A-2), (A-3), and (A-4) in component (A) Ａ－１ , n Ａ－２ , n Ａ－３ , and n Ａ－４ but, n Ａ－１ / (n Ａ－１ +n Ａ－２ +n Ａ－３ +n Ａ－４ )=0~95%、 n Ａ－２ / (n Ａ－１ +n Ａ－２ +n Ａ－３ +n Ａ－４ )=5~100%、 n Ａ－３ / (n Ａ－１ +n Ａ－２ +n Ａ－３ +n Ａ－４ ) = 0-20%, or n Ａ－４ / (n Ａ－１ +n Ａ－２ +n Ａ－３ +n Ａ－４ The substrate cleaning solution according to claim 2 or 3, wherein the concentration is 0 to 50%: Preferably, the total number of repeating units in component (A) n ｔｏｔａｌ So, (n Ａ－１ +n Ａ－２ +n Ａ－３ +n Ａ－４ ) / n ｔｏｔａｌ =80~100% It satisfies the condition.

7. The substrate cleaning solution according to at least one of claims 1 to 6, wherein the content of component (A) is 0.5 to 50% by mass, based on the total mass of the substrate cleaning solution.

8. The substrate cleaning solution according to at least one of claims 1 to 7, wherein the mass-average molecular weight (Mw) of component (A) is 500 to 300,000.

9. The substrate cleaning solution according to at least one of claims 1 to 8, wherein the content of component (C) is 1 to 99% by mass, based on the total mass of the substrate cleaning solution.

10. A substrate cleaning solution according to at least one of claims 1 to 9, further comprising other additives (D); Here, component (D) comprises a surfactant, acid, base, antibacterial agent, disinfectant, preservative, or antifungal agent, and the content of component (D) is 0 to 10% by mass based on the total mass of component (A).

11. A method for manufacturing a cleaned substrate comprising the following steps; (1) Drop the substrate cleaning solution according to at least one of claims 1 to 10 onto the substrate; (2) Remove at least a portion of component (C) from the substrate cleaning solution and form a film; (3) The film holds particles on the substrate; (4) The film on which the particles on the substrate are retained is removed by physical cleaning.

12. The method for manufacturing a cleaned substrate according to claim 11, wherein the substrate described in (1) is an unprocessed substrate or a substrate to be processed; Preferably, the surface of the substrate is a semiconductor, Preferably, the surface of the substrate is Si, Ge, SiGe, Si ３ N ４ , TaN, SiO ２ , TiO ２ Al ２ O ３ SiON, HfO ２ Ta ２ O ５ , HfSiO ４ , Y ２ O ３ It is selected from the group consisting of GaN, TiN, SiCN, NbN, Cu, Ta, W, Hf, Al, Ru, Co, and amorphous carbon.

13. A method for manufacturing a cleaned substrate according to claim 11 or 12, wherein step (2) includes heating to 50 to 200°C.

14. A method for manufacturing a cleaned substrate according to at least one of claims 11 to 13, wherein step (4) comprises at least one of brush scrubbing, gas blowing, ice scrubbing, dry ice scrubbing, spray showering, and ultrasonic irradiation.

15. A method for manufacturing a device comprising the method for manufacturing a cleaned substrate according to at least one of claims 11 to 14.

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