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

Abstract

To obtain a substrate cleaning composition capable of cleaning a substrate and removing particles.SOLUTION: A substrate cleaning composition comprises an insoluble or hardly soluble solute (A). The insoluble or hardly soluble solute (A) is a monomer of (A-1) and / or a polymer of (A-1). The insoluble or hardly soluble solute (A) has a pKa of 9.5 to 4, or the insoluble or hardly soluble solute (A) has a pKb of 9.5 to 4, and / or (A-1) contains 2 to 4 polar groups. The polar group is selected from at least one of the group consisting of -OH, -COOH, -NO2, -NH2, and -NH-.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a substrate cleaning composition, a method for producing a cleaned substrate using the same, and a method for producing a device.

[0002] Conventionally, substrate manufacturing processes have sometimes generated foreign matter, for example, during lithography processes. Therefore, substrate manufacturing processes sometimes include a cleaning process to remove particles from the substrate. Cleaning processes include a method of physically removing particles by supplying a cleaning liquid such as deionized water (DIW) to the substrate, and a method of chemically removing particles using a chemical solution. However, as patterns become finer and more complex, the patterns become more susceptible to physical or chemical damage.

[0003] As a substrate cleaning process, a method has been studied in which a film is formed on a substrate, particles are retained in the film, and the film is then removed using a removal solution. If the formed film is completely dissolved with a removal solution, the particles retained in the film may reattach. Therefore, a method has been studied in which the formed film is partially dissolved and the undissolved portions are removed in a solid state. Patent Documents 1 and 2 study the formation and removal of a film using a cleaning solution containing a poorly soluble or insoluble solute, a soluble solute, and water. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] International Publication No. 2020 / 120667 [Patent Document 2] International Publication No. 2021 / 245014 Summary of the Invention [Problem to be solved by the invention]

[0005] The inventors have found that there are one or more problems that require improvement in the technology for forming a film on a substrate and removing particles, such as the following: particle removal is inefficient; the removal solution for the formed film is an alkaline aqueous solution; the formed film cannot be completely removed with the removal solution and remains on the substrate; an organic solvent is used for cleaning after removal with the removal solution; removal is not efficient for both hydrophobic and hydrophilic substrates; The present invention has been made based on the above-mentioned technical background, and provides a substrate cleaning composition. [Means for solving the problem]

[0006] The substrate cleaning composition according to the present invention comprises an insoluble or poorly soluble solute (A), The insoluble or slightly soluble solute (A) is a monomer of (A-1) and / or a polymer of (A-1), the pKa of the insoluble or slightly soluble solute (A) is 9.5 to 4, or the pKb of the insoluble or slightly soluble solute (A) is 9.5 to 4, and / or (A-1) contains 2 to 4 polar groups; The polar group is selected from at least one of the group consisting of -OH, -COOH, -NO2, -NH2 and -NH-.

[0007] The method for producing a cleaned substrate according to the present invention comprises the following steps. (1) applying the substrate cleaning composition described above onto a substrate; (2) forming a film from the substrate cleaning composition; (3) retaining particles on a substrate with the film; and (4) A remover is supplied onto the substrate to remove the film on which the particles are held.

[0008] A method for manufacturing a device according to the present invention comprises the method for manufacturing the above-described cleaned substrate. [Effects of the Invention]

[0009] By using the substrate cleaning composition according to the present invention, one or more of the following effects can be expected. Efficient particle removal is possible; the formed film can be sufficiently peeled off and removed from the substrate using water as a removal solution; the film can be efficiently removed using an alkaline aqueous solution as a cleaning solution after removing the removal solution; Particles can be efficiently removed from both hydrophobic and hydrophilic substrates; and the force that draws the removal solution to the interface between the film containing component (A) and the substrate can be strengthened. [Brief explanation of the drawings]

[0010] [Figure 1] FIG. 1 is a cross-sectional view for explaining the state of a substrate surface during cleaning of the substrate according to the present invention. DETAILED DESCRIPTION OF THE INVENTION

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

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

[0013] <Substrate cleaning composition> The substrate cleaning composition according to the present invention comprises an insoluble or slightly soluble solute (A) (hereinafter sometimes referred to as component (A) or solute (A), and the same applies to (B) and subsequent solutes). Here, solute (A) is a monomer of (A-1) and / or a polymer of (A-1), and solute (A) has a pKa of 9.5 to 4 or a pKb of 9.5 to 4, and / or (A-1) contains two to four polar groups, each of which is selected from the group consisting of -OH, -COOH, -NO2, -NH2, and -NH-. Preferably, the insoluble or poorly soluble solute (A) is insoluble or poorly soluble (more preferably poorly soluble) in the removal liquid. Preferably, the soluble solute (B) is soluble in the removal liquid. The substrate cleaning composition according to the present invention may contain a solvent (C). In the present invention, the "solute" is not limited to a state in which it is dissolved in the solvent (C), but also includes a state in which it is suspended, or a solid state without containing the solvent (C). In a preferred embodiment, the solutes, components, and additives contained in the substrate cleaning composition are dissolved in the solvent (C). The substrate cleaning composition in this form is considered to have good embedding performance or film uniformity.

[0014] In a preferred embodiment, the substrate cleaning composition according to the present invention is applied to a substrate and dried to remove at least a portion of the solvent (C) and form a film, and then the film is removed from the substrate with a removal liquid. In another preferred embodiment, the substrate cleaning composition according to the present invention is applied onto a substrate and heated to form a film, and then the film is removed from the substrate with a removal liquid. "Forming a film" refers to a state in which a continuous film is formed on a substrate. When a solidifying component other than solute (A) (e.g., solute (B)) is contained, it is preferable that a single film is formed and that the components coexist in a single film. One form of film formation is "solidification" of the solute. Note that the film obtained from the substrate cleaning composition only needs to be hard enough to retain particles. When a solvent (C) is contained, the solvent (C) is not completely removed (e.g., by evaporation). In a preferred form, the substrate cleaning composition gradually shrinks to form a film as the solvent (C) evaporates. It is acceptable for a very small amount of the insoluble or slightly soluble solute (A) and other components contained as needed to be removed (e.g., evaporated or volatilized). 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 relative to the original amount. Without intending to limit the scope of the invention and without being bound by theory, it is believed that the film holds particles on the substrate and is removed by the removal solution described below. When the film contains a soluble solute (B), it is believed that this creates areas that trigger the film to peel off, thereby achieving more efficient removal.

[0015] <Insoluble or slightly soluble solute (A)> The substrate cleaning composition according to the present invention comprises an insoluble or sparingly soluble solute (A). The component (A) is a monomer of (A-1) and / or a multimer of (A-1), and may be a mixture of the monomer and the multimer. Preferably, the component (A) is a multimer of (A-1). Component (A) satisfies at least one of the following (i) to (iii), preferably (iii), and more preferably (i) and (iii). Preferably, component (A) does not satisfy (i) and (ii) simultaneously. (i) pKa is 9.5-4; (ii) pKb is 9.5–4; (iii) (A-1) preferably contains 2 to 4 polar groups, selected from at least one of the group consisting of -OH, -COOH, -NO2, -NH2, and -NH-, and each polar group may be the same or different, including, for example, -OH and -COOH. When the substrate cleaning composition of the present invention is used, component (A) forms a film that holds particles, which can then be easily removed with water.

[0016] Preferably, (A-1) is represented by formula (a-1). [ka] where: Cy 01 is an unsaturated hydrocarbon ring, preferably a 5-membered or 6-membered ring, more preferably a 6-membered ring (n 03 is 1), and Cy 01 One to three of the Cs constituting the group may be independently substituted with N, S, or O (more preferably, not substituted). 01 is preferably cyclopentane, cyclohexane, benzene, pyridine, diazine, or triazine (more preferably, benzene or triazine; even more preferably, benzene). 01 is preferably an aromatic ring (more preferably an aromatic hydrocarbon ring or an aromatic heterocyclic ring; even more preferably an aromatic hydrocarbon ring). Each X is independently -OH, -COOH, -NO2, or -NR'R'', preferably -OH, -COOH, or -NH2, more preferably -OH or -NH2. R' and R'' are each independently hydrogen, C 1-5It is alkyl, preferably hydrogen, methyl, ethyl, n-propyl, n-butyl, or cyclopropyl. R is independently C 1-10 alkyl, -CHO, -C(=O)CH3, -C(=O)C2H5, -CH=CH2, or -OC(=O)-CH=CH2, preferably C 1-3 It is alkyl or -OC(=O)-CH=CH2, more preferably -OC(=O)-CH=CH2. n 01 is 0 to 4, preferably 2 to 4, more preferably 2 to 3, and even more preferably 3. n 02 is 0 to 3, preferably 0 or 1, and more preferably 0. When the component (A) is a polymer of (A-1), n 02 It is also preferred that is 1. n 03 is 0 to 1, preferably 1. 0≦(n 01 +n 02 )≦(5+n 03 )

[0017] When component (A) is a monomer (A-1), examples of component (A) include phloroglucinol, benzenetriol, melamine, phloroglucinol carboxaldehyde, 2-acetylphloroglucinol, flopropione, 2,4,6-triformylphloroglucinol, N,N-dimethylmelamine, N,N-diethylmelamine, N-butylmelamine, and cyromazine. Preferably, the monomer (A-1) does not include a form in which the same unit is repeatedly bonded two or more times.

[0018] When the component (A) is a multimer of (A-1), examples thereof include a multimer obtained by addition condensation of the (A-1) monomer with formaldehyde or the like, and a multimer obtained by addition polymerization of the C=C double bond of the (A-1) monomer. Preferably, the multimer of (A-1) is one in which the same unit is repeatedly linked two or more times. The polymer of (A-1) preferably comprises a repeating unit represented by formula (a-1-1) or a repeating unit represented by formula (a-1-2), and more preferably comprises a repeating unit represented by formula (a-1-1).

[0019] Formula (a-1-1) is as follows: [ka] where Cy 01 ,X,R,n 01 , n 02 and n 03 is as described above. m1 is a number of 1 or more, preferably 1 to 3 (more preferably 1 to 2; even more preferably 1 or 2; still more preferably 1). In formula (a-1-1), a hydrogen atom in X or Cy 01 The hydrogen atom directly attached to the ring is removed and linked to -CH2-. For example, X is -NH2, and this hydrogen atom is removed to form -NH-, which is then bonded to a methylene.

[0020] In a preferred embodiment, formula (a-1-1) is represented by formula (a-1-1α) or formula (a-1-1β). More preferably, formula (a-1-1) is represented by formula (a-1-1α). [ka] The symbols in the formula have the same meanings as above.

[0021] Examples of the repeating unit represented by formula (a-1-1) include the following: [ka]

[0022] Equation (a-1-2) is as follows: [ka] where Cy 01 ,X,R,n 01 , n 02 and n 03 is as described above. m3 is 0 to 1, preferably 0 or 1 (more preferably 0).

[0023] Examples of the repeating unit represented by formula (a-1-2) include the following: [ka]

[0024] The multimer of (A-1) may contain repeating units represented by a structure other than formula (a-1-1) or formula (a-1-2), the proportion of which is preferably 5% or less, more preferably 1% or less, based on the total number of repeating units contained in (A-1). The total number of repeating units contained in the polymer of (A-1), the number of repeating units of the structure of formula (a-1-1) contained in the polymer of (A-1), and the number of repeating units of the structure of formula (a-1-2) contained in the polymer of (A-1) are respectively represented by N (A-1) , N (a-1―1) and N (a-1―2) Let's say. Preferably, {N (a-1―1) +N (a-1―2)} / N (A-1) = 40 to 100% (more preferably 70 to 100%; even more preferably 90 to 100%; and even more preferably 95 to 100%). In a preferred embodiment, the polymer of (A-1) does not contain any structure other than that of formula (a-1-1) or formula (a-1-2). The terminal of the polymer of (A-1) may be modified with H, methyl, or OH. At the terminal of the polymer of (a-1-1α) and (a-1-1β), the methylene in the repeating unit may be substituted with H. Specific preferred examples of the polymer (A-1) include phloroglucinol resin, benzenetriol resin, melamine resin, or any combination thereof (more preferably phloroglucinol resin or melamine resin).

[0025] The molecular weight of component (A) (when it is a polymer, the mass average molecular weight Mw) is preferably 100 to 50,000. When component (A) is a multimer of (A-1), Mw is preferably 250 to 10,000, more preferably 250 to 5,000, and even more preferably 250 to 1,500. Here, the mass average molecular weight is the mass average molecular weight in terms of polystyrene, and can be measured by gel permeation chromatography using polystyrene as the standard. The same applies hereinafter. When component (A) is a monomer (A-1), its molecular weight is preferably 100 to 200 (more preferably 100 to 150; even more preferably 100 to 130).

[0026] The content of component (A) is preferably 1.0 to 100 mass %, more preferably 1.0 to 50 mass %, and even more preferably 1.0 to 20 mass %, based on the substrate cleaning composition.

[0027] Solubility can be evaluated by known methods. For example, component (A) or component (B) can be added to a flask at 20 to 35°C (more preferably 25±2°C) in water to a concentration of 3000 ppm, the flask is capped, and the mixture is shaken in a shaker for 1 hour to determine whether component (A) or component (B) has dissolved. Shaking may be by stirring. Dissolution can also be determined visually. If the mixture does not dissolve, the solubility is 3000 ppm or less, and if the mixture dissolves, the solubility is greater than 3000 ppm. In this specification, a solubility of 3000 ppm or less is considered insoluble or slightly soluble, and a solubility of more than 3000 ppm is considered soluble. Furthermore, a solubility of 100 ppm or less is considered insoluble. In this specification, solubility increases in the order of insoluble, slightly soluble, and soluble. Preferably, the solubility of component (A) in water is 3000 ppm or less, and the solubility of component (B) in water is more than 3000 ppm. The water used in evaluating solubility is preferably DIW. Component (A) is insoluble or slightly soluble, but is preferably slightly soluble. The water used in the solubility evaluation may be replaced with another removal liquid (described later) used in a subsequent process. For example, to determine whether a substance is insoluble, slightly soluble, or soluble in a removal liquid, it is preferable to replace the water used in the above-described solubility evaluation with the removal liquid.

[0028] <Soluble solute (B)> The substrate cleaning composition according to the present invention may further comprise a soluble solute (B). Component (B) is preferably soluble in the removal solution. Component (B) is preferably a substance comprising carboxy, sulfo, or phospho; more preferably a substance comprising carboxy or phospho; and even more preferably a substance comprising carboxy.

[0029] The acid dissociation constant pKA(H2O) of the component (B) is preferably -5 to 11; more preferably -1 to 8; even more preferably 1 to 7; and even more preferably 2 to 6.

[0030] In a preferred embodiment of the present invention, the component (B) present in the film formed from the substrate cleaning composition is dissolved by the remover, triggering the film to peel off. The solute (B) is preferably a crack-promoting component (B'), which preferably comprises a hydrocarbon containing a carboxyl group. Without being bound by theory, when the substrate cleaning composition according to the present invention contains component (B), it is believed that the substrate cleaning composition forms a film on the substrate, and when the remover removes the film, component (B) creates a portion that triggers the film to peel off. For this reason, it is preferable that component (B) has a higher solubility in the remover than component (A).

[0031] The component (B) preferably comprises a repeating unit represented by formula (b-1). [ka] where: L1 is a single bond, C 1-4It is selected from the group consisting of alkylene, phenylene, ether, carbonyl, amide, and imide; preferably selected from the group consisting of a single bond, methylene, ethylene, phenylene, and amide; more preferably a single bond and phenylene; and even more preferably a single bond. When L1 is an amide or an imide, H present at a position other than the link between R1 and the main chain may be substituted with methyl or may be unsubstituted; more preferably, it is unsubstituted. R1 is carboxy, sulfo, or phospho; preferably, carboxy or sulfo; more preferably, carboxy. R2 is hydrogen, methyl, or carboxy; preferably hydrogen or carboxy. It is sil; more preferably hydrogen. R3 is hydrogen or methyl; preferably hydrogen.

[0032] Component (B) is preferably a polymer comprising a structural unit represented by formula (b-1). Preferred examples of polymers comprising a structural unit represented by formula (b-1) include polyacrylic acid, polymaleic acid, polystyrene sulfonic acid, or a polymer of a combination thereof. More preferred examples are polyacrylic acid and maleic-acrylic acid copolymers. In the case of copolymerization, random copolymerization or block copolymerization is preferred, and random copolymerization is more preferred. As an example, the following maleic acrylic acid copolymer is described: It has two types of repeating units represented by (b-1). [ka]

[0033] The molecular weight of component (B) (when it is a polymer, the mass average molecular weight Mw) is preferably 500 to 500,000; preferably 1,000 to 100,000; more preferably 2,000 to 50,000, even more preferably 5,000 to 50,000; and still more preferably 5,000 to 40,000.

[0034] Component (B) can be obtained either synthetically or commercially from suppliers such as Sigma-Aldrich, Tokyo Chemical Industry Co., Ltd., and Nippon Shokubai.

[0035] The content of component (B) is preferably 0 to 50 mass % based on the substrate cleaning composition; more preferably 1 to 50 mass %; even more preferably 1 to 30 mass %; and still more preferably 1 to 10 mass %.

[0036] <Solvent (C)> The substrate cleaning composition according to the present invention may further comprise a solvent (C). In one embodiment of the present invention, the solvent (C) can contain water (C-1). The water (C-1) is preferably deionized water (DIW). When water (C-1) is contained, some of it may be removed during membrane formation, but at least some of it remains in the membrane after membrane formation. Without being bound by theory, it is believed that the presence of water (C-1) in the membrane promotes penetration of the removal solution into the membrane, enabling more efficient membrane removal. The content of water (C-1) is preferably 0.1 to 10% by mass, more preferably 0.01 to 20% by mass, and even more preferably 0.05 to 20% by mass, based on the solvent (C). % by volume. A preferred embodiment of the present invention is one in which the composition does not contain water (C-1) (0 mass %).

[0037] The solvent (C) preferably comprises an organic solvent (C-2). The organic solvent (C-2) is preferably volatile. In the present invention, "volatile" means that the volatility is higher than that of water. For example, the boiling point of the solvent (C-2) at 1 atmosphere is preferably 50 to 250°C, more preferably 50 to 200°C, even more preferably 60 to 170°C, and even more preferably 70 to 150°C.

[0038] Examples of the organic solvent (C-2) 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 monomethyl ether acetate (PGMEA), and propylene glycol monomethyl ether acetate (PGMEA). Examples of suitable organic solvents include propylene glycol monoalkyl ether acetates such as 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, lactones such as γ-butyrolactone, etc. These organic solvents can be used alone or in combination of two or more. In a preferred embodiment, the organic solvent (C-2) is selected from IPA, PGME, PGEE, EL, PGMEA, and any combination thereof. When two organic solvents are used in combination, the volume ratio is preferably 20:80 to 80:20, and more preferably 30:70 to 70:30. The organic solvent (C-2) preferably has a water solubility of 10 g / 100 g HO or more, more preferably 20 g / 100 g HO or more, even more preferably 25 to 1,000 g / 100 g HO, and even more preferably 50 to 200 g / 100 g HO. The water solubility is preferably measured at room temperature and pressure; room temperature is 20 to 30°C, preferably 22 to 28°C; and normal pressure is preferably standard atmospheric pressure or a range of ±15% around standard atmospheric pressure.

[0039] The content of the solvent (C) is preferably 0 to 99.0 mass%, more preferably 50 to 99.9 mass%, more preferably 75 to 99.5 mass%, even more preferably 80 to 99 mass%, and still more preferably 90 to 99 mass%, based on the substrate cleaning composition. In one preferred embodiment of the present invention, the solvent (C) is not contained.

[0040] <Other additives (D)> The substrate cleaning composition of the present invention may further contain an additive (D) other than components (A) to (C). Here, the additive (D) may include a surfactant, an acid, a base, an antibacterial agent, a disinfectant, a preservative, or an antifungal agent, or any combination thereof. In one preferred embodiment, component (D) comprises a surfactant. In one embodiment of the present invention, the content of component (D) (or the sum of the contents when multiple components are present) is 0 to 100 mass % (preferably 0 to 10 mass %, more preferably 0 to 5 mass %, even more preferably 0 to 3 mass %, and still more preferably 0 to 1 mass %) based on component (A). In one preferred embodiment of the present invention, the substrate cleaning composition does not contain component (D) (0 mass %).

[0041] <Removal liquid> As described above, the substrate cleaning composition of the present invention is applied to a substrate to form a film. The film is then removed from the substrate with a remover. The film can retain particles present on the substrate, and in one preferred embodiment of the present invention, the film is removed with a remover while retaining the particles. The removal liquid may be alkaline, neutral, or acidic, but is preferably neutral. In one embodiment of the present invention, the removal liquid has a pH of 6 to 8; preferably 6.5 to 7.5; more preferably 6.8 to 7.2; and even more preferably 6.9 to 7.1. One specific embodiment of the removal liquid is water. Carbon dioxide gas may be dissolved in the removal liquid. In one preferred embodiment, the removal liquid is carbonated water with CO2 dissolved therein, and the resistivity is preferably 0.1 to 5.0 MΩ cm. It is preferable to measure pH after degassing to avoid the influence of carbon dioxide gas dissolved in the air. Without being bound by theory, the film formed from the substrate cleaning composition of the present invention can be removed with the above-mentioned remover, so that it is possible to reduce the amount of damage when cleaning a substrate that would be damaged by a highly alkaline solution, for example.

[0042] Without intending to limit the present invention and without being bound by theory, a schematic diagram will be used to explain one embodiment of a method for producing a cleaned substrate using a substrate cleaning composition according to the present invention in order to facilitate understanding of the present invention. The substrate cleaning composition used in the embodiment shown in FIG. 1 comprises an insoluble or slightly soluble solute (A), a soluble solute (B), and a solvent (C). (a) shows a state in which particles 2 are attached to a substrate 1. (b) shows a state in which the substrate cleaning composition of the present invention is dropped onto this substrate, and a portion of the solvent (C) is dried, resulting in a film of components (A) and (B). In (b), the film becomes a particle-retaining layer 3. Component (B) is present within the particle-retaining layer 3. (c) shows a state in which component (B) is dissolved into the removal liquid 5 after being applied to the film. As the component (B) dissolves, traces 6 are formed in the particle-retaining layer 3. (d) shows a state in which cracks 7 extend from the traces 6. (e) shows a state in which the film is separated by the extension of the cracks 7 and removed from the substrate, still retaining the particles. (f) shows the state of the cleaned substrate.

[0043] <How to clean the substrate> The substrate cleaning composition of the present invention can be used to clean a substrate. The present invention provides, in one aspect, a method for producing a cleaned substrate. The method for cleaning a substrate will be described below in more specific form. The numbers in parentheses indicate the order of the steps. For example, steps (1), (2), and (3) are written. If so, the order of steps will be as described above. The method for producing a cleaned substrate according to the present invention comprises the following steps. (1) applying a substrate cleaning composition according to the present invention onto a substrate; (2) forming a film from the substrate cleaning composition; (3) retaining particles on a substrate with the film; and (4) A remover is supplied onto the substrate to remove the film on which the particles are held.

[0044] In a preferred embodiment of step (1), the substrate cleaning composition can be dropped onto the approximate center of a horizontally positioned substrate using a nozzle or the like in an apparatus suitable for substrate cleaning. The substrate can be rotated, for example, at 10 to several tens of rpm to prevent drip marks from appearing. The amount dropped is preferably 0.5 to 10 cc. These conditions can be adjusted so that the substrate cleaning composition is applied and spread evenly. In another embodiment, the solid composition can be spread on the substrate using a scraper, roller, or the like. Before applying step (1), the surface of the substrate may be subjected to a hydrophobic treatment.

[0045] Step (2) is preferably carried out by spin-drying or heating the substrate. When the composition according to the present invention contains a solvent (C), the solvent (C) is removed by drying, preferably by spin drying. Spin drying is preferably performed at 500 to 3,000 rpm (more preferably 500 to 1,500 rpm, even more preferably 500 to 1,000 rpm) for preferably 0.5 to 90 seconds (more preferably 5 to 80 seconds, even more preferably 15 to 70 seconds, and even more preferably 30 to 60 seconds). This allows the solvent (C) to dry while the substrate cleaning composition is spread over the entire surface of the substrate. When the composition according to the present invention does not contain a solvent (C), the substrate cleaning composition can be dissolved and formed into a film by heating, preferably at 250 to 450°C (more preferably 250 to 350°C), for preferably 0.5 to 10 seconds (more preferably 0.5 to 5 seconds; even more preferably 1 to 5 seconds). Preferably, the substrate is a disk-shaped substrate having a diameter of 200 to 600 mm (more preferably 200 to 400 mm).

[0046] The retention of particles in step (3) is achieved by the formation of a film of component (A). In other words, steps (2) and (3) can be said to occur continuously in a single operation. When the substrate cleaning composition according to the present invention contains solvent (C), a state in which a small amount of solvent (C) remains in the film is acceptable. 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. In steps (2) and / or (3), the temperature inside the apparatus may be increased. This increase in temperature is expected to promote the evaporation of the (C) solvent and the film formation of solid components such as component (A). When the temperature is increased, it is preferably 40 to 150°C.

[0047] In step (4), a remover is supplied onto the substrate to remove the film (particle retention layer) on which the particles are retained. The supply can be performed by dripping, spraying, or immersion. The dripping may be performed so as to form a puddle on the substrate, or may be performed continuously. In one embodiment of the present invention, the remover is dripped onto the center of the substrate while the substrate is rotating at 500 to 800 rpm. In a preferred embodiment of the present invention, the particle retention layer is removed from the substrate while retaining the particles without being completely dissolved by the remover. In one preferred embodiment, the particle retention layer is removed in a state of being cut into small pieces by the "parts that trigger peeling," for example. Without being bound by theory, it is believed that the substrate cleaning composition of the present invention, when component (A) forms a film, has a strong ability to attract a removing solution to the interface between the film and the substrate, thereby enabling more efficient removal of a film carrying particles. The film-formed component (A) is characterized by the aforementioned pKA, pKb, or polar group, which is believed to enhance this ability to attract a removing solution. Without being bound by theory, it is believed that when the substrate surface is hydrophilic, the hydrophobic-hydrophobic interaction at the interface between the film and the substrate is not very strong, but when the substrate surface is hydrophobic, this hydrophobic-hydrophobic interaction becomes strong, making it difficult for the removing solution to penetrate the interface. As described above, it is believed that the use of the substrate cleaning composition of the present invention allows efficient attraction of a removing solution to the interface and removal of a film carrying particles, even if the substrate surface is hydrophobic.

[0048] The substrate cleaning method according to the present invention also preferably includes at least one other step than those described above. Such a step includes any step known in the art for cleaning substrates. For example, the following steps may be included: (0-1) Etching a substrate to form a pattern, and then removing the etching mask; (0-2) Clean the substrate; (0-3) Prewetting the substrate; (0-4) Clean the substrate; (5) The substrate is further cleaned by dropping water, an alkaline aqueous solution, or an organic solvent onto the substrate from which the particle-holding film has been removed, and then removing the water, alkaline aqueous solution, or organic solvent. In the step (0-1), the substrate to be cleaned may be a substrate to be processed, and the processing may be performed by a lithography technique. In step (0-2), the substrate may be washed with a known cleaning solution (such as a rinse solution) to reduce the number of particles on the substrate. One of the objects of the present invention is to remove any small amount of particles that remain even after washing. The pre-wetting step (0-3) can be performed to improve the coating properties of the substrate cleaning composition of the present invention and spread it evenly on the substrate. The liquid (pre-wetting liquid) preferably used for pre-wetting includes IPA, PGME, PGMEA, PGEE, n-butanol (nBA), pure water, and any combination thereof. The step (0-4) can be performed to replace the pre-wet liquid in the step (0-3). By adding the step (0-2), the step (0-4) can be made unnecessary, which is also one aspect of the present invention.

[0049] In step (5), it is also a preferred embodiment to further rinse the substrate with water, an alkaline aqueous solution, or an organic solvent to remove localized film residues and particle residues. The cleaning solution is preferably IPA or an alkaline aqueous solution, more preferably an alkaline aqueous solution, and even more preferably a TMAH aqueous solution. Without being bound by theory, the substrate can be further rinsed without using an organic solvent in step (5). Therefore, the use of the substrate cleaning composition of the present invention can reduce the amount of organic solvent used throughout the process, which is advantageous from the standpoint of safety.

[0050] <Substrate> 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 disks, substrates for magnetic disks, substrates for magneto-optical disks, glass substrates for photomasks, and substrates for solar cells. 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 together. Preferably, the surface of the substrate is a semiconductor. The semiconductor may be composed of an oxide, a nitride, a metal, or any combination thereof. Also, preferably, the surface of the substrate is selected from the group consisting of Si, Ge, SiGe, Si3N4, TaN, SiO2, TiO2, Al2O3, SiON, HfO2, Ta2O5, HfSiO4, Y2O3, GaN, TiN, SiCN, NbN, Cu, Ta, W, Hf, Ru, Co, amorphous carbon and Al, and more preferably selected from the group consisting of Si, TiO2, SiON, TiN, SiCN, Cu, W, Ru, and Co.

[0051] <device> The substrate produced by the cleaning method of the present invention can be further processed to produce devices. Examples of such devices include semiconductor elements, liquid crystal display elements, organic EL display elements, plasma display elements, and solar cell elements. These devices can be processed using known methods.

[0052] The present invention will be described below with reference to various examples. It is not limited to only

[0053] <Preparation of cleaning liquid composition of Example 1> Phloroglucinol resin (Mw 250) was used as component (A), and polyacrylic acid (Mw 5,000) was used as component (B). Components (A) and (B) were added to solvent (C) PGME so that the solid content (total of components (A) and (B)) of the composition was 10% by mass. The mass ratio of (A) to (B) was as shown in Table 1. That is, for the composition of Example 1, the above addition was performed in a ratio of 5 parts by mass of component (B) to 100 parts by mass of component (A). The mixture was stirred with a stirrer for 1 hour to obtain a composition with a solid content of 10% by mass. This composition was then filtered through Optimizer UPE (Nippon Entegris, UPE, pore size 10 nm). This yielded the cleaning liquid composition of Example 1. [ka]

[0054] <Preparation of cleaning compositions of Examples 2 to 20 and Comparative Examples 1 to 7> Each cleaning composition was prepared in the same manner as in Example 1, except that the components (A) and (B), solvent, and blending amounts were changed as shown in Tables 1 and 2. When two solvents were used, the mixing ratio (by mass) was shown in the table. [Table 1] [Table 2] In Table 1, Phloroglucinol [ka] Phloroglucinol resin [ka] Benzenetriol resin [ka] ·melamine [ka] Melamine resin [ka] ·PHS resin [ka] Phenolic resin [ka] Novolac resin [ka] Polybutyl acrylate [ka] Polycarbonate [ka] Polymethyl methacrylate [ka] Dihydroxytetraphenylmethane [ka]

[0055] <Evaluation of solubility> Place 4 mg of each component in a 50 mL sample bottle and add DIW to bring the total volume to 40 g. Cover the bottle and shake for 1 hour to obtain an aqueous solution with a component concentration of 100 ppm. A 3,000 ppm aqueous solution is obtained in the same manner as above, except that the amount of each component added is changed. The solubility of these materials was confirmed visually. The evaluation criteria were as follows. The evaluation results are shown in Tables 1 and 2. X: Residual dissolution was confirmed at 100 ppm. It was judged to be insoluble. Y: No residue was found at 100 ppm, but residue was found at 3,000 ppm. It is judged to be difficult to dissolve. Z: No residue was found at 3,000 ppm. It is judged to be soluble.

[0056] <Preparation of particle removal evaluation substrate> An 8-inch bare silicon substrate (SUMCO) is used as the hydrophilic substrate. The hydrophobic substrate used was an 8-inch bare silicon substrate (SUMCO) on which a 5,000 nm SiCN film was formed by plasma CVD processing. Particles were attached to a hydrophilic substrate and a hydrophobic substrate. Ultra-high purity colloidal silica (PL-10H, Fuso Chemical Co., Ltd., average primary particle size approximately 90 nm) was used as the particles for the experiment. 50 mL of silica microparticle composition was dropped and applied by rotating at 500 rpm for 5 seconds. The solvent of the silica microparticle composition was then spin-dried by rotating at 1,000 rpm for 30 seconds. This resulted in a particle-removal evaluation substrate.

[0057] <Particle removal evaluation> When using cleaning compositions other than those of Examples 16 and 20, use Coater Developer RF 3 Using a SOKUDO, 10 cc of the cleaning composition is dropped onto the particle removal evaluation substrate, and the substrate is rotated at 1,500 rpm for 60 seconds to coat and dry the composition, forming a film. When using the cleaning compositions of Examples 16 and 20, the cleaning composition is spread evenly on the particle removal evaluation substrate, and then the wafer is heated at 350° C. for 3 seconds to melt the composition and form a film. While the substrate on which the film was formed was rotated at 100 rpm, water (deionized water) was dropped as a removal solution for 10 seconds, covering the entire substrate with water. This state was maintained for 60 seconds, and then the substrate was rotated at 1,500 rpm to peel off and remove the film, and the substrate was dried. Using a dark-field defect inspection system (LS-9110, Hitachi High-Technologies Corporation), the amount of remaining particles on these substrates was counted and evaluated according to the following criteria. The evaluation results are shown in Tables 1 and 2. AA:≦10 pieces A:>10 pieces, ≦100 pieces B:>100 pieces, ≦1,000 pieces C:>1000 pieces D: Film is not evenly applied or removed

[0058] <Suitable for both boards> The suitability for both substrates was evaluated according to the following criteria, and the evaluation results are shown in Tables 1 and 2. A: Particle removal evaluation is AA or A for both hydrophilic and hydrophobic substrates. B: The particle removal evaluation is AA or A for either the hydrophilic or hydrophobic substrate, but B or C for the other. C: Particle removal evaluation was rated B or C for both hydrophilic and hydrophobic substrates. [Explanation of symbols]

[0059] 1. Substrate 2. Particles 3. Particle retention layer 4. Soluble Solute (B) 5.Removal liquid 6. Traces of soluble solute (B) dissolved 7. Crack

Claims

1. A substrate cleaning composition comprising an insoluble or poorly soluble solute (A), The insoluble or slightly soluble solute (A) is a monomer of (A-1) and / or a polymer of (A-1), the pKa of the insoluble or slightly soluble solute (A) is 9.5 to 4, or the pKb of the insoluble or slightly soluble solute (A) is 9.5 to 4, and / or (A-1) contains 2 to 4 polar groups; The polar group is —OH, —COOH, —NO ２ , -NH ２ and —NH—, Optionally, the substrate cleaning composition comprises a solvent (C); Optionally, the substrate cleaning composition is applied onto a substrate and dried to remove at least a portion of the solvent (C) and form a film, and then the film is removed from the substrate with a removal liquid; Optionally, the substrate cleaning composition is applied onto a substrate and heated to form a film, and then the film is removed from the substrate with a removal liquid; and / or Optionally, the insoluble or sparingly soluble solute (A) is insoluble or sparingly soluble in the removal liquid.

2. The substrate cleaning composition according to claim 1, wherein (A-1) is represented by formula (a-1): 【Chemistry 1】 where: Cy ０１ is an unsaturated hydrocarbon ring, optionally containing Cy ０１ 1 to 3 of the C's may be independently substituted with N, S, or O, X's each independently represent -OH, -COOH, or -NO ２ or -NR'R'', R′ and R″ are each independently hydrogen, C １－５ is alkyl, Each R is independently C １－１０ Alkyl, —CHO, —C(═O)CH ３ , -C(=O)C ２ H ５ , -CH=CH ２ or —O—C(═O)—CH═CH ２ and n ０１ is 0 to 4, and n ０２ is 0 to 3, and n ０３ is 0 to 1, where 0≦(n ０１ +n ０２ )≦(5+n ０３ ) is satisfied.

3. 3. The substrate cleaning composition of claim 1 or 2, further comprising a soluble solute (B): Optionally, the soluble solute (B) is soluble in the removal solution; optionally, the content of the insoluble or slightly soluble solute (A) is 1.0 to 100 mass % based on the substrate cleaning composition; Optionally, the content of the solvent (C) is 0 to 99.0% by weight, based on the substrate cleaning composition; and / or Optionally, the content of the soluble solute (B) is 0 to 50 wt % based on the substrate cleaning composition.

4. The substrate cleaning composition according to any one of claims 1 to 3, wherein the solvent (C) comprises water (C-1): Optionally, the content of water (C-1) is 0.1 to 10% by weight based on the solvent (C).

5. The substrate cleaning composition according to any one of claims 1 to 4, wherein the multimer of (A-1) comprises a repeating unit represented by formula (a-1-1) or a repeating unit represented by formula (a-1-2): 【Chemistry 2】 Here, Cy ０１ , X, R, n ０１ , n ０２ and n ０３ is as defined in claim 2, m1 is a number of 1 or more, m3 is a number of 0 to 1, In formula (a-1-1), a hydrogen atom in X or a hydrogen atom directly bonded to the ring is removed to form —CH ２ - is connected to Optionally, when the insoluble or slightly soluble solute (A) comprises a polymer of (A-1), it may contain a repeating unit represented by a structure other than formula (a-1-1) or formula (a-1-2), and / or Optionally, when the insoluble or slightly soluble solute (A) is a polymer of (A-1), it has a Mw of 250 to 50,000.

6. The substrate cleaning composition according to at least one of claims 1 to 5, wherein the soluble solute (B) comprises a repeating unit represented by formula (b-1): 【Transformation 3】 where: L １ is a single bond, C １－４ selected from the group consisting of alkylene, phenylene, ether, carbonyl, amide and imide; R １ is carboxy, sulfo, or phospho; R ２ is hydrogen, methyl, or carboxyl; R ３ is hydrogen or methyl, Optionally, the acid dissociation constant pKA (H) of the soluble solute (B) ２ O) is -5 to 11, and / or Optionally, the molecular weight of the soluble solute (B) is from 500 to 500,000.

7. The substrate cleaning composition according to claim 1 , wherein the solvent (C) further comprises an organic solvent (C-2).

8. The substrate cleaning composition according to at least any one of claims 1 to 7, wherein the insoluble or slightly soluble solute (A) has a solubility in water of 3,000 ppm or less, and the soluble solute (B) has a solubility in water of more than 3,000 ppm; Optionally, the solubility is determined by adding 3,000 ppm of (A) or (B) to water in a flask at 20 to 35°C, covering the flask, and shaking the flask in a shaker for 1 hour to determine whether (A) or (B) dissolves.

9. The substrate cleaning composition according to claim 1 , further comprising other additives (D); wherein the other additive (D) comprises a surfactant, an acid, a base, an antibacterial agent, a disinfectant, a preservative, or an antifungal agent; Optionally, the content of other additives (D) is 0 to 100% by weight based on the insoluble or slightly soluble solute (A).

10. A method for producing a cleaned substrate comprising the steps of: (1) applying the substrate cleaning composition according to at least one of claims 1 to 9 onto a substrate; (2) forming a film from the substrate cleaning composition; (3) retaining particles on the substrate with the film; (4) A remover is supplied onto the substrate to remove the film on which the particles are held.

11. The method for producing a cleaned substrate according to claim 10, wherein the step (2) is carried out by spin-drying or heating the substrate. Optionally, the spin drying is performed at 500 to 3,000 rpm for 0.5 to 90 seconds; Optionally, removing at least a portion of the solvent (C) in the substrate cleaning composition by spin drying to form a film from the composition; Optionally, the substrate is a disk-shaped substrate having a diameter of 200 to 600 mm; and / or Optionally, heating is carried out at 250-450° C. for 0.5-10 seconds.

12. 12. The method for producing a cleaned substrate according to claim 10 or 11, wherein the substrate according to (1) is a non-processed substrate or a processed substrate; Optionally, the surface of the substrate is a semiconductor; Optionally, prior to application of the substrate cleaning composition, the surface of the substrate is hydrophobically treated; and / or Optionally, 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 , GaN, TiN, SiCN, NbN, Cu, Ta, W, Hf, Al, Ru, Co, and amorphous carbon.

13. The method for producing a cleaned substrate according to at least one of claims 10 to 12, further comprising at least one of the following steps: (0-1) Etching a substrate to form a pattern, and then removing the etching mask; (0-2) Clean the substrate; (0-3) Pre-wet the substrate; (0-4) Clean the substrate; (5) The substrate is further cleaned by dropping water, an alkaline aqueous solution, or an organic solvent onto the substrate from which the particle-holding film has been removed, and then removing the water, alkaline aqueous solution, or organic solvent.

14. A method for manufacturing a device, comprising the method for manufacturing a cleaned substrate according to at least one of claims 10 to 13.

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