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

Abstract

The purpose of the present invention is to obtain a substrate cleaning composition capable of cleaning a substrate and removing particles. [Solution] Provided is a substrate cleaning composition containing an insoluble or poorly soluble solute (A), in which the insoluble or poorly soluble solute (A) is a monomer of (A-1) and / or a multimer of (A-1); the pKa of the insoluble or poorly soluble solute (A) is 9.5-4, the pKb of the insoluble or poorly soluble solute (A) is 9.5-4, and / or (A-1) contains 2-4 polar groups; and the polar group is at least one selected from the group consisting of-OH,-COOH,-NO2,-NH2 and-NH-.

Description

Technical Field

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

[0002] In the conventional manufacturing process of a substrate, for example, foreign matters may be generated due to a photolithography process or the like. Therefore, the manufacturing process of the substrate sometimes includes a cleaning step of removing particles from the substrate. In the cleaning step, there are the following methods: a method of physically removing particles by supplying a cleaning liquid such as deionized water (DIW) to the substrate, a method of chemically removing particles by a chemical agent, and the like. However, as the pattern becomes finer and more complex, the pattern is likely to be physically or chemically damaged.

[0003] As a cleaning step of a substrate, there has been a study on a method of forming a film on the substrate to hold particles in the film and then removing the film with a removing liquid. When the formed film is completely dissolved with the removing liquid, the particles held in the film may reattach. Therefore, there has been a study on a method of partially dissolving the formed film and removing the undissolved solid part. In Patent Documents 1 and 2, studies have been conducted on forming a film with a cleaning liquid containing a sparingly soluble or insoluble solute, a soluble solute, and water and removing the film.

[0004] [Prior Art Documents]

[0005] [Patent Documents]

[0006] [Patent Document 1] WO 2020 / 120667

[0007] [Patent Document 2] WO 2021 / 245014 Summary of the Invention

[0008] [Problems to be Solved by the Invention]

[0009] The present inventors consider that there are one or more problems to be improved in the technology of forming a film on a substrate to remove particles. They can be listed as follows, for example: poor removal efficiency of particles; the removing liquid of the formed film is an alkaline aqueous solution; the formed film cannot be completely removed by the removing liquid and remains on the substrate; after removing with the removing liquid, organic solvents are used for cleaning; efficient removal cannot be performed for both hydrophobic substrates and hydrophilic substrates;

[0010] The present invention has been completed based on the above technical background, and provides a substrate cleaning composition.

[0011] [Means for Solving the Problems]

[0012] The substrate cleaning composition of the present invention contains an insoluble or sparingly soluble solute (A):

[0013] wherein the insoluble or sparingly soluble solute (A) is a monomer of (A-1) and / or a multimer of (A-1);

[0014] the pKa of the insoluble or sparingly soluble solute (A) is 9.5 to 4, the pKb of the insoluble or sparingly soluble solute (A) is 9.5 to 4, and / or (A-1) contains 2 to 4 polar groups; and

[0015] the polar group is at least one selected from the group consisting of -OH, -COOH, -NO2, -NH2, and -NH-.

[0016] The method for manufacturing a cleaned substrate of the present invention includes the following steps:

[0017] (1) Applying the above-mentioned substrate cleaning composition onto the substrate;

[0018] (2) Forming a film from the substrate cleaning composition;

[0019] (3) Retaining the particles on the substrate in the film; and

[0020] (4) Supplying a removal liquid to the substrate to remove the film retaining the particles.

[0021] The method for manufacturing a device of the present invention includes the method for manufacturing the above-mentioned cleaned substrate.

[0022] [Advantages of the Invention]

[0023] By using the substrate cleaning composition of the present invention, one or more of the following effects can be expected.

[0024] Particles can be efficiently removed; by using water as the removal liquid for the formed film, it can be sufficiently peeled off and removed from the substrate; an alkaline aqueous solution can be used as the cleaning liquid after removing the removal liquid to efficiently remove the film; particles can be efficiently removed for both hydrophobic substrates and hydrophilic substrates; the force for attracting the removal liquid to the interface between the film containing the (A) component and the substrate can be strengthened. Description of the Drawings

[0025] Figure 1 It is a cross-sectional view schematically showing the situation of the substrate surface during the cleaning of the substrate of the present invention. Detailed Description

[0026] [Embodiments for Carrying Out the Invention]

[0027] The embodiments of the present invention will be described in detail below.

[0028] [Definition]

[0029] In this specification, as long as not specifically defined or mentioned otherwise, the definitions and examples described in this paragraph shall apply.

[0030] The singular form includes the plural form, and "a", "an", and "the" mean "at least one". The elements of a concept can be presented in various ways. When recording amounts (such as mass %, mole %), the amount represents the sum of various amounts.

[0031] "And / or" includes all combinations of elements, and also includes the use of a single element.

[0032] When using "~ / to" or "-" to represent a numerical range, the endpoints on both sides are included and the units are the same. For example, 5 ~ 25 mol% means 5 mol% or more and 25 mol% or less.

[0033] "C x-y ", "C x -C y ", and "C x " and other notations represent the number of carbon atoms in a molecule or substituent. For example, C 1-6 alkyl represents an alkyl chain having 1 to 6 carbon atoms (such as methyl, ethyl, propyl, butyl, pentyl, hexyl, etc.).

[0034] 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 to the parentheses represent the number of repetitions.

[0035] The unit of temperature is Celsius. For example, 20 degrees represents 20 degrees Celsius.

[0036] An additive refers to the compound itself having its function (for example, if it is a base generator, it is the compound itself that generates a base). Such a compound can also be in a form added to the composition by being dissolved or dispersed in a solvent. In one aspect of the present invention, such a solvent is preferably contained in the composition of the present invention as a solvent (C) or other component.

[0037] <Substrate cleaning composition>

[0038] The substrate cleaning composition of the present invention has an insoluble or hardly soluble solute (A) (hereinafter sometimes referred to as component (A) or solute (A); the same applies to (B)). Here, the solute (A) is a monomer of (A-1) and / or a polymer of (A-1); the pKa of the solute (A) is 9.5 to 4, the pKb of the solute (A) is 9.5 to 4, and / or (A-1) contains 2 to 4 polar groups; the polar group is at least one selected from the group consisting of -OH, -COOH, -NO2, -NH2, and -NH-.

[0039] The insoluble or hardly soluble solute (A) is preferably insoluble or hardly soluble (more preferably hardly soluble) in the removal liquid. The soluble solute (B) is preferably soluble in the removal liquid.

[0040] The substrate cleaning composition of the present invention may also contain a solvent (C).

[0041] In the present invention, the so-called "solute" is not limited to the state of being dissolved in the solvent (C), and a suspended state or a solid state without the solvent (C) is also allowed.

[0042] In a preferred form, the solutes, components, and additives contained in the substrate cleaning composition are dissolved in the solvent (C). It is considered that the substrate cleaning composition in this form has good filling performance or film uniformity.

[0043] In a preferred form, the substrate cleaning composition of the present invention is applied to a substrate, at least a part of the solvent (C) is removed by drying to form a film, and then the film is removed from the substrate by a removal liquid.

[0044] In another preferred form, the substrate cleaning composition of the present invention is applied to a substrate and a film is formed by heating, and then the film is removed from the substrate by a removal liquid.

[0045] "Forming a film" means a state of forming a continuous film on a substrate. When a curing component other than the solute (A) (for example, the solute (B)) is included, it is preferably a state of coexisting in a single film as a single film. One form of forming a film is the "curing" of the solute. In addition, the film obtained from the substrate cleaning composition only needs to have a hardness sufficient to hold particles. In the case of containing the solvent (C), the solvent (C) is not completely removed (for example, by vaporization). In a preferred form, the substrate cleaning composition gradually shrinks as the solvent (C) volatilizes and becomes a film. The insoluble or hardly soluble solute (A) and other components included as required are allowed to be removed (for example, evaporated, volatilized) in a very small amount. For example, compared with the original amount, 0 to 10% by mass (preferably 0 to 5% by mass, more preferably 0 to 3% by mass, further preferably 0 to 1% by mass, and even more preferably 0 to 0.5% by mass) is allowed to be removed.

[0046] Although there is no intention of limiting the scope of the rights and it is not limited to theory, it is believed that: the film will retain the particles on the substrate and be peeled off by the removal liquid described later, whereby the particles can be removed. When the soluble solute (B) is included, it is believed that a part serving as a starting point for film peeling will be generated, and it is believed that more efficient peeling can be achieved.

[0047] <Insoluble or poorly soluble solute (A)>

[0048] The substrate cleaning composition of the present invention contains an insoluble or poorly soluble solute (A).

[0049] The component (A) is a monomer of (A-1) and / or a polymer of (A-1), and may also be a mixture of a monomer and a polymer. The component (A) is preferably a polymer of (A-1).

[0050] The component (A) satisfies at least one of the following (i) to (iii), preferably satisfies (iii), and more preferably satisfies (i) and (iii). It is preferred that the component (A) does not satisfy (i) and (ii) simultaneously.

[0051] (i) The pKa is 9.5 to 4;

[0052] (ii) The pKb is 9.5 to 4;

[0053] (iii) (A-1) preferably contains 2 to 4 polar groups. The polar group is at least one selected from the group consisting of -OH, -COOH, -NO2, -NH2, and -NH-, and each polar group may be the same or different. For example, it contains -OH and -COOH.

[0054] When the substrate cleaning composition of the present invention is used, after the component (A) forms a film and retains the particles, it can be easily removed with water.

[0055] (A-1) is preferably represented by the formula (a-1):

[0056]

[0057] Here,

[0058] Cy 01 is an unsaturated hydrocarbon ring, preferably a 5-membered ring or a 6-membered ring, more preferably a 6-membered ring (n 03 is 1), and 1 to 3 C atoms constituting Cy 01 may each independently be replaced by N, S, or O (more preferably unsubstituted). Cy 01 is preferably cyclopentane, cyclohexane, benzene, pyridine, diazine, or triazine (more preferably benzene or triazine; further preferably benzene). Cy 01Preferably an aromatic ring (more preferably an aromatic hydrocarbon ring or an aromatic heterocyclic ring; still more preferably an aromatic hydrocarbon ring).

[0059] Each X is independently -OH, -COOH, -NO2 or -NR’R”, preferably -OH, -COOH or -NH2, more preferably -OH or -NH2.

[0060] Each of R’ and R” is independently hydrogen or a C 1-5 alkyl group, preferably hydrogen, methyl, ethyl, n-propyl, n-butyl or cyclopropyl.

[0061] Each R is independently a C 1-10 alkyl group, -CHO, -C(=O)CH3, -C(=O)C2H5, -CH=CH2 or -O-C(=O)-CH=CH2, preferably a C 1-3 alkyl group or -O-C(=O)-CH=CH2, more preferably -O-C(=O)-CH=CH2.

[0062] n 01 is from 0 to 4, preferably from 2 to 4, more preferably from 2 to 3, still more preferably 3.

[0063] n 02 is from 0 to 3, preferably 0 or 1, more preferably 0. When the component (A) is a polymer of (A-1), n 02 is further preferably 1.

[0064] n 03 is from 0 to 1, preferably 1.

[0065] And 0 ≤ (n 01 + n 02 ) ≤ (5 + n 03 ).

[0066] When the component (A) is a monomer of (A-1), examples of the component (A) include, for example: phloroglucinol, benzene triol, melamine, phloroglucinol carboxyaldehyde, 2-acetylphloroglucinol, flopropione, 2,4,6-triformylphloroglucinol, N,N-dimethylmelamine, N,N-diethylmelamine, N-butylmelamine, cyromazine.

[0067] Preferably, the monomer of (A-1) does not include a form in which the same unit is repeatedly bonded more than twice.

[0068] When the component (A) is a polymer of (A-1), examples include, for example: a polymer formed by addition condensation of a monomer of (A-1) with formaldehyde or the like, and a polymer formed by addition polymerization of a C=C double bond possessed by a monomer of (A-1).

[0069] Preferably, the polymer of (A-1) has a form in which the same unit is repeatedly bonded two or more times.

[0070] The polymer of (A-1) preferably contains a repeating unit represented by formula (a-1-1) or a repeating unit represented by formula (a-1-2). More preferably, the polymer of (A-1) contains a repeating unit represented by formula (a-1-1).

[0071] Formula (a-1-1) is as follows:

[0072]

[0073] Here,

[0074] Cy 01 , X, R, n 01 , n 02 and n 03 are as described above.

[0075] m1 is a number of 1 or greater, preferably 1 to 3 (more preferably 1 to 2; still more preferably 1 or 2; even more preferably 1).

[0076] And in formula (a-1-1), a hydrogen atom in X or a hydrogen atom directly bonded to the Cy 01 ring detaches and bonds to -CH2-. As an example, there is the following form: X is -NH2, and this hydrogen atom detaches to become -NH- and then bonds to the methylene group.

[0077] In a preferred form, 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).

[0078]

[0079] The notations in the formula have the same meanings as described above.

[0080] Examples of the repeating unit represented by formula (a-1-1) include the following:

[0081]

[0082] Formula (a-1-2) is as follows:

[0083]

[0084] Here,

[0085] Cy 01 , X, R, n 01 , n 02 and n 03As described above.

[0086] m3 is from 0 to 1, preferably 0 or 1 (more preferably 0).

[0087] Examples of the repeating unit represented by formula (a-1-2) are as follows.

[0088]

[0089] The polymer of (A-1) may also contain repeating units represented by structures other than formula (a-1-1) or formula (a-1-2). In terms of its ratio, based on the total number of repeating units contained in (A-1), it is preferably 5% or less, more preferably 1% or less.

[0090] Let 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) be N (A-1) , N (a-1-1) and N (a-1-2) .

[0091] Preferably, {N (a-1-1) +N (a-1-2)} / N (A-1) = 40 to 100% (more preferably 70 to 100%; further preferably 90 to 100%; even more preferably 95 to 100%). In a preferred form, the polymer of (A-1) does not contain structures other than formula (a-1-1) or formula (a-1-2). The terminal of the polymer of (A-1) may also be modified via H, methyl or OH. At the terminal of the polymer of (a-1-1α) and (a-1-1β), the methylene group described in the repeating unit may also be replaced via H.

[0092] As a specific example of the polymer of (A-1), preferably, phloroglucinol resin, phlorotriol resin, melamine resin or any combination thereof (more preferably phloroglucinol resin or melamine resin) can be cited.

[0093] The molecular weight of component (A) (when it is a polymer, it is the weight-average molecular weight Mw) is preferably 100 to 50,000. When component (A) is the polymer of (A-1), Mw is preferably 250 to 10,000, more preferably 250 to 5,000, and further preferably 250 to 1,500. The weight-average molecular weight here refers to the polystyrene-equivalent weight-average molecular weight, which can be measured using gel permeation chromatography based on polystyrene. The same applies hereinafter.

[0094] When the component (A) is a monomer of (A-1), its molecular weight is preferably 100 to 200 (more preferably 100 to 150; further preferably 100 to 130).

[0095] Based on the substrate cleaning composition, the content of the component (A) is preferably 1.0 to 100% by mass, preferably 1.0 to 50% by mass, more preferably 1.0 to 20% by mass.

[0096] The solubility can be evaluated by a known method. For example, under the condition of 20 to 35 °C (more preferably 25 ± 2 °C), 3000 ppm of the component (A) or the component (B) is added to water in a flask, the flask is covered with a lid and vibrated with a vibrator for 1 hour, and it is determined by whether the component (A) or the component (B) is dissolved. The vibration can also be stirring. It can also be visually judged whether it is dissolved. If it is not dissolved, the solubility is 3000 ppm or less, and if it is dissolved, the solubility exceeds 3000 ppm. In this specification, a solubility of 3000 ppm or less is insoluble or hardly soluble, and a solubility exceeding 3000 ppm is soluble. Furthermore, a solubility of 100 ppm or less is regarded as insoluble. In this specification, the solubility increases in the order of insoluble, hardly soluble, and soluble.

[0097] Preferably, the solubility of the component (A) in water is 3000 ppm or less, and the solubility of the component (B) in water exceeds 3000 ppm. The water used in the evaluation of solubility is preferably DIW.

[0098] The component (A) is insoluble or hardly soluble, but preferably hardly soluble.

[0099] The water used in the evaluation of solubility can also be changed to other removal liquids (described later) used in the subsequent process. For example, in order to determine whether the removal liquid is insoluble, hardly soluble or soluble, it is preferable to change the water used in the above evaluation of solubility to the removal liquid.

[0100] <Soluble Solute (B)>

[0101] The substrate cleaning composition of the present invention may further contain a soluble solute (B). The component (B) is preferably soluble in the removal liquid.

[0102] The component (B) preferably contains a carboxyl group, a sulfo group or a phospho group, more preferably a substance containing a carboxyl group or a phospho group, and further preferably a substance containing a carboxyl group.

[0103] The acid dissociation constant pKA (H2O) of the component (B) is preferably -5 to 11, more preferably -1 to 8, further preferably 1 to 7, and even more preferably 2 to 6.

[0104] In a preferred embodiment of the present invention, the component (B) present in the film formed from the substrate cleaning composition is dissolved out by the removal liquid, thereby providing a starting point for film peeling. The solute (B) is preferably a cleavage-promoting component (B'), and the cleavage-promoting component (B') preferably contains a carboxyl group-containing hydrocarbon.

[0105] When the substrate cleaning composition of the present invention contains the component (B), although not limited to theory, it is considered that when the substrate cleaning composition forms a film on the substrate and the removal liquid peels off the film, the component (B) generates a part that serves as a starting point for film peeling. Therefore, it is preferred that the solubility of the component (B) in the removal liquid is higher than that of the component (A).

[0106] (B) The component preferably contains a repeating unit represented by the formula (b-1):

[0107]

[0108] Here,

[0109] L1 is selected from the group consisting of a single bond, C 1-4 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; even more preferably a single bond.

[0110] When L1 is an amide or imide, the H present outside the linking portion of R1 and the main chain may also be substituted via a methyl group or may be unsubstituted; more preferably it is unsubstituted.

[0111] R1 is a carboxyl group, a sulfo group, or a phosphoryl group; preferably a carboxyl group or a sulfo group; more preferably a carboxyl group.

[0112] R2 is hydrogen, methyl, or a carboxyl group; preferably hydrogen or a carboxyl group; more preferably hydrogen.

[0113] R3 is hydrogen or methyl; preferably hydrogen.

[0114] (B) The component is preferably a polymer containing a structural unit represented by the formula (b-1). Preferred examples of the polymer containing the structural unit represented by the 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 acid-acrylic acid copolymer.

[0115] In the case of copolymerization, random copolymerization or block copolymerization is preferred, and random copolymerization is more preferred.

[0116] The following maleic acid-acrylic acid copolymer is given as an example for illustration. It has two repeating units represented by (b-1).

[0117]

[0118] (B) component's molecular weight (in the case of a polymer, it is the mass average molecular weight Mw) is preferably 500 to 500,000; more preferably 1,000 to 100,000; still more preferably 2,000 to 50,000, further preferably 5,000 to 50,000; even more preferably 5,000 to 40,000.

[0119] (B) component can be obtained by synthesis or purchase. Suppliers can include: Sigma - Aldrich, Tokyo Chemical Industry Co., and Nippon Shokubai Co., Ltd.

[0120] (B) component's content is preferably 0 to 50 mass% based on the substrate cleaning composition; more preferably 1 to 50 mass%; still more preferably 1 to 30 mass%; even more preferably 1 to 10 mass%.

[0121] <Solvent (C)>

[0122] The substrate cleaning composition of the present invention may further contain solvent (C).

[0123] In one aspect of the present invention, solvent (C) may contain water (C - 1). Water (C - 1) is preferably deionized water (DIW). When water (C - 1) is included, a part of it may be removed during film formation, but at least a part of it remains in the film after film formation.

[0124] Although not limited to theory, it is considered that: because water (C - 1) exists in the film, it promotes the penetration of the removal liquid into the film, and the film can be removed more effectively.

[0125] Based on solvent (C), the content of water (C - 1) is preferably 0.1 to 10 mass%; more preferably 0.01 to 20 mass%; still more preferably 0.05 to 20 mass%.

[0126] Not containing water (C - 1) (0 mass%) is also a preferred aspect of the present invention.

[0127] Solvent (C) preferably contains organic solvent (C - 2).

[0128] Organic solvent (C - 2) preferably has volatility. In the present invention, having volatility means having a higher volatility than water. For example, the boiling point of solvent (C - 2) at one atmosphere is preferably 50 to 250 °C, more preferably 50 to 200 °C, still more preferably 60 to 170 °C, even more preferably 70 to 150 °C.

[0129] As the organic solvent (C-2), examples include: alcohols such as isopropyl alcohol (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; lactate 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.

[0130] In a preferred form, the organic solvent (C-2) is selected from IPA, PGME, PGEE, EL, PGMEA, and any combination thereof. When the organic solvent is a combination of two, the volume ratio is preferably 20:80 to 80:20, more preferably 30:70 to 70:30.

[0131] The organic solvent (C-2) preferably has a solubility in water of 10 g / 100 g H2O or more; more preferably 20 g / 100 g H2O or more; further preferably 25 to 1,000 g / 100 g H2O; still more preferably 50 to 200 g / 100 g H2O. The measurement of the solubility in water is preferably carried out at normal temperature and pressure. Normal temperature refers to 20 to 30°C, preferably 22 to 28°C, and normal pressure refers to standard atmospheric pressure or a range of ±15% centered on standard atmospheric pressure.

[0132] Based on the substrate cleaning composition, the content of the solvent (C) is preferably 0 to 99.0% by mass; more preferably 50 to 99.9% by mass; more preferably 75 to 99.5% by mass; further preferably 80 to 99% by mass; still more preferably 90 to 99% by mass.

[0133] The absence of the solvent (C) is also a preferred form of the present invention.

[0134] <Other additives (D)>

[0135] In the substrate cleaning composition of the present invention, in addition to the components (A) to (C), other additives (D) may further be included. The other additives (D) include surfactants, acids, bases, antibacterial agents, fungicides, preservatives, or antifungal agents, and may also include any combination thereof.

[0136] In a preferred embodiment, component (D) contains a surfactant. As one embodiment of the present invention, based on component (A), the content of component (D) (in many cases, the sum thereof) is 0 to 100% by mass (preferably 0 to 10% by mass; more preferably 0 to 5% by mass; still more preferably 0 to 3% by mass; even more preferably 0 to 1% by mass). It is also one of the preferred embodiments of the present invention that the substrate cleaning composition does not contain component (D) (0% by mass).

[0137] <Removing liquid>

[0138] As described above, the substrate cleaning composition of the present invention is applied to a substrate to form a film. Then, the film is removed from the substrate by a removing liquid. One preferred embodiment of the present invention is that the film can hold the particles present on the substrate and remove them with the removing liquid while in the held state.

[0139] The removing liquid can be alkaline, neutral or acidic, and is preferably neutral. As one embodiment of the present invention, the pH of the removing liquid is 6 to 8; preferably 6.5 to 7.5; more preferably 6.8 to 7.2; still more preferably 6.9 to 7.1. One preferred embodiment of the removing liquid is water. The removing liquid can also dissolve carbon dioxide gas. In a preferred embodiment, the removing liquid is carbonated water dissolved with CO2, and its resistivity is preferably 0.1 to 5.0 MΩ·cm.

[0140] To avoid the influence caused by the dissolution of carbon dioxide gas in the air, the measurement of pH is preferably carried out after exhausting. Although not limited to theory, the film formed by the substrate cleaning composition of the present invention can be removed by the above-mentioned removing liquid. Therefore, for example, when cleaning a substrate that may be damaged by a strongly alkaline solution, the amount of damage can be reduced.

[0141] Although not limiting the intention of the present invention and not limited to theory, for the purpose of understanding the present invention, one embodiment of the method for manufacturing a cleaned substrate using the substrate cleaning composition of the present invention will be described using a schematic diagram.

[0142] Figure 1The substrate cleaning composition used in the form contains an insoluble or sparingly soluble solute (A), a soluble solute (B), and a solvent (C). (a) shows the state where particles 2 are attached to substrate 1. The substrate cleaning composition of the present invention is dropped on this substrate, and a state where a part of the solvent (C) dries and components (A) and (B) form a film is shown as (b). In (b), the film is the particle holding layer 3. Component (B) exists within the particle holding layer 3. Subsequently, a state where a removal liquid 5 is supplied to the film and component (B) is dissolved into the removal liquid 5 is shown as (c). By dissolution, traces 6 of the dissolution of component (B) are generated in the particle holding layer 3. A state where cracks 7 develop starting from the traces 6 is shown as (d). A state where the film broken due to the development of the cracks 7 is removed from the substrate while holding the particles is shown as (e). The state of the substrate obtained after cleaning is shown as (f).

[0143] <Substrate cleaning method>

[0144] The substrate cleaning composition of the present invention can be used for cleaning substrates. Substrate cleaning can use known methods or apparatuses. The present invention provides a method for manufacturing a cleaned substrate as one form.

[0145] The following uses a more specific form to illustrate the substrate cleaning method. The numbers in the following parentheses indicate the step order. For example, when steps (1), (2), and (3) are described, the order of the steps is as described.

[0146] The method for manufacturing a cleaned substrate of the present invention includes the following steps:

[0147] (1) Apply the substrate cleaning composition of the present invention to the substrate;

[0148] (2) Form a film from the substrate cleaning composition;

[0149] (3) Hold the particles on the substrate in the film; and

[0150] (4) Supply a removal liquid to the substrate and remove the film holding the particles.

[0151] In step (1), in a preferred form, the substrate cleaning composition can be dropped at approximately the center of the substrate in a horizontal posture through a nozzle or the like in an apparatus applicable to substrate cleaning. The substrate can be rotated at 10 to several tens of rpm, for example, to suppress the generation of dripping marks. The dropped amount is preferably 0.5 to 10 cc. These conditions can be adjusted to uniformly coat and spread the substrate cleaning composition.

[0152] In another form, the composition in a solid state can also be spread over the substrate. In this case, a squeegee, a roller, etc. can be used.

[0153] Before the application in step (1), the surface of the substrate may also be subjected to a hydrophobic treatment.

[0154] Step (2) is preferably carried out by spin-drying or heating the substrate.

[0155] When the composition of the present invention contains a (C) solvent, the removal of the (C) solvent is carried out by drying, preferably by spin-drying. The spin-drying is preferably carried out at 500 to 3,000 rpm (more preferably 500 to 1,500 rpm, further preferably 500 to 1,000 rpm), and preferably carried out for 0.5 to 90 seconds (more preferably 5 to 80 seconds, further preferably 15 to 70 seconds, still further preferably 30 to 60 seconds). Thereby, the substrate cleaning composition can be spread over the entire surface of the substrate, and at the same time, the (C) solvent can be dried.

[0156] When the composition of the present invention does not contain a (C) solvent, the substrate cleaning composition can be dissolved by heating to form a film. The heating is preferably carried out 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; further preferably 1 to 5 seconds).

[0157] The substrate is preferably a disk-shaped substrate with a diameter of 200 to 600 mm (more preferably 200 to 400 mm).

[0158] The retention of the particles in step (3) can be carried out by forming a film of the (A) component. That is, it can also be said that steps (2) and (3) occur continuously through one operation. When the substrate cleaning composition of the present invention contains a (C) solvent, a state where a little (C) solvent remains in the film is allowed. As one aspect of the present invention, at the end of steps (2) and (3), more than 95% (preferably more than 98%, more preferably more than 99%) of the (C) solvent volatilizes and does not remain in the film.

[0159] In step (2) and / or step (3), the temperature inside the apparatus may also be raised. By raising the temperature, it is expected to promote the volatilization of the (C) solvent and the formation of a film of solid components such as the (A) component. When the temperature is raised, it is preferably 40 to 150 °C.

[0160] In step (4), the removal liquid is supplied to the substrate, and the film (particle retention layer) holding the particles is removed. The supply can be carried out by dropping, spraying, or liquid immersion. The dropping can also be carried out by forming a liquid pool (puddle / spin coating immersion) on the substrate, and continuous dropping is also possible. As one aspect of the present invention, while the substrate is rotating at 500 to 800 rpm, the removal liquid is dropped onto the center of the substrate.

[0161] It is also a preferred embodiment of the present invention that the particle holding layer is not completely dissolved by the removing liquid and is removed from the substrate while holding the particles. In a preferred embodiment, the particle holding layer becomes, for example, a state of being shredded by "the part that is the starting point of peeling" and is then removed.

[0162] Although not limited to theory, it is considered that: the substrate cleaning composition of the present invention forms a film with the component (A), and the force attracting the removing liquid to the surface of the film and the substrate becomes stronger, and the film holding the particles can be removed more effectively. It is considered that: the formed film of the component (A) has the above-mentioned pKA, pKb or polar group as its characteristics, so the force attracting the removing liquid becomes stronger. Although not limited to theory, it is considered that: when the surface of the substrate is hydrophilic, the hydrophobic-hydrophobic interaction at the interface between the film and the substrate is not very strong, but when the surface of the substrate is hydrophobic, this hydrophobic-hydrophobic interaction becomes stronger and the removing liquid is less likely to enter the interface. It is considered that: as described above, when using the substrate cleaning composition of the present invention, even if the surface of the substrate is hydrophobic, the removing liquid can be effectively attracted to the interface, and the film holding the particles can be removed.

[0163] As a cleaning method of the substrate of the present invention, an embodiment further including at least one step other than the above is also preferred. Such steps include steps well-known in the cleaning of the substrate. For example, the following steps can be cited.

[0164] (0-1) Processing the substrate by etching to form a pattern and removing the etching mask;

[0165] (0-2) Cleaning the substrate;

[0166] (0-3) Pre-wetting the substrate;

[0167] (0-4) Cleaning the substrate;

[0168] (5) Dropping water, an alkaline aqueous solution or an organic solvent on the substrate from which the film holding the particles has been removed, and then removing the water, the alkaline aqueous solution or the organic solvent, thereby further cleaning the substrate.

[0169] In step (0-1), the substrate to be cleaned can be an unprocessed substrate, and this processing can be carried out by lithography technology.

[0170] In step (0-2), in order to reduce the number of particles on the substrate, the substrate can be cleaned with a well-known cleaning liquid (such as a rinsing liquid, etc.). One of the purposes of the present invention is to remove a small amount of particles remaining even after this step.

[0171] The pre-wetting step of steps (0 - 3) is carried out to improve the coatability of the substrate cleaning composition of the present invention so as to spread evenly on the substrate. As the liquid for pre-wetting (pre-wetting liquid), preferably, IPA, PGME, PGMEA, PGEE, n-butanol (nBA), pure water, and any combination thereof can be cited.

[0172] Step (0 - 4) is carried out to displace the pre-wetting liquid of step (0 - 3). It is also a form of the present invention that step (0 - 4) is not required by adding step (0 - 2).

[0173] In step (5), it is also a preferred form to further clean the substrate with water, an alkaline aqueous solution or an organic solvent in order to remove local film residues and particle residues. As the cleaning liquid, IPA or an alkaline aqueous solution is preferably used, more preferably an alkaline aqueous solution, and further preferably a TMAH aqueous solution. Although not limited to theory, since the substrate can be further cleaned even without using an organic solvent in step (5), using the substrate cleaning composition of the present invention can reduce the amount of organic solvent used in the whole method, which is advantageous from the viewpoint of safety.

[0174] <Substrate>

[0175] As the substrate to be cleaned in the present invention, semiconductor wafers, glass substrates for liquid crystal display devices, glass substrates for organic EL display devices, glass substrates for plasma display devices, substrates for optical discs, substrates for magnetic disks, substrates for magneto-optical discs, glass substrates for photomasks, substrates for solar cells, etc. can be cited. The substrate can be an unprocessed substrate (e.g., a bare wafer) or a processed substrate (e.g., a patterned substrate). The substrate can be formed by laminating multiple layers. Preferably, the surface of the substrate is a semiconductor. The semiconductor can be composed of any one of oxides, nitrides, metals, and any combination thereof. Further, the surface of the substrate is preferably 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.

[0176] <Device>

[0177] By further processing the substrate manufactured by the cleaning method of the present invention, a device can be manufactured. As the device, semiconductor devices, liquid crystal display devices, organic EL display devices, plasma display devices, and solar cell devices can be cited. These processes can use known methods.

[0178] The present invention will be described below with reference to each embodiment. In addition, the forms of the present invention are not limited to these embodiments.

[0179] <Preparation of the cleaning liquid composition of Example 1>

[0180] Phloroglucinol resin (Mw: 250) was used as the component (A), and polyacrylic acid (Mw: 5,000) was used as the component (B). The components (A) and (B) were added to PGME as the solvent (C) such that the solid content (the sum of the components (A) and (B)) accounted for 10% by mass in the composition. The mass ratio of (A) to (B) is as described in Table 1. That is, in the composition of Example 1, the above addition was carried out such that the component (B) was 5 parts by mass relative to 100 parts by mass of the component (A). It was stirred with a stirrer for 1 hour to obtain a composition with a solid content concentration of 10% by mass. This composition was filtered using Optimizer UPE (Nihon Entegris, UPE, pore size 10 nm). Thus, the cleaning liquid composition of Example 1 was obtained.

[0181] Phloroglucinol resin (Mw = 250)

[0182] Polyacrylic acid (Mw = 5,000)

[0183] <Preparation of the cleaning liquid compositions of Examples 2 to 20 and Comparative Examples 1 to 7>

[0184] The components (A) and (B), the solvent, and the blending amounts were changed respectively according to the descriptions in Table 1 and Table 2. Except for this, the preparation was carried out in the same manner as the preparation of the cleaning composition of Example 1 to obtain the respective cleaning compositions. When there were two solvents, their mixing ratio (mass basis) was described in the table.

[0185] [Table 1]

[0186]

[0187] [Table 2]

[0188]

[0189] In Table 1 and Table 2: · Phloroglucinol

[0190]

[0191] · Phloroglucinol resin

[0192]

[0193] · Benzotriol resin

[0194]

[0195] · Melamine

[0196]

[0197] · Melamine resin

[0198]

[0199] · PHS resin

[0200]

[0201] · Phenol resin

[0202]

[0203] · Novolac resin

[0204]

[0205] · Butyl acrylate

[0206]

[0207] · Polycarbonate

[0208]

[0209] · Polymethyl methacrylate

[0210]

[0211] · Dihydroxytetraphenylmethane

[0212]

[0213] <Evaluation of solubility>

[0214] Put 4 mg of each of the components used into a 50 mL sample bottle, and add DIW to make the total amount 40 g. Cover it with a lid and shake and stir for 1 hour. Thus, an aqueous solution with a component concentration of 100 ppm is obtained.

[0215] Change the addition amount of each component, and perform the same operations as above to obtain an aqueous solution of 3,000 ppm.

[0216] Visually confirm their solubility. The evaluation criteria are as follows. The evaluation results are shown in Table 1 and Table 2.

[0217] X: Dissolution residue was confirmed at 100 ppm, and it was judged as insoluble.

[0218] Y: Dissolution residue was not confirmed at 100 ppm, but was confirmed at 3,000 ppm, judged as hardly soluble.

[0219] Z: Dissolution residue was not confirmed at 3,000 ppm, judged as soluble.

[0220] <Preparation of Substrate for Particle Removal Evaluation>

[0221] An 8-inch bare silicon substrate (SUMCO) was used as the hydrophilic substrate.

[0222] A substrate formed with a 5,000 nm SiCN film by plasma CVD treatment of an 8-inch bare silicon substrate (SUMCO) was used as the hydrophobic substrate.

[0223] Particles were attached to the hydrophilic substrate and the hydrophobic substrate. Ultra-high purity colloidal silica (PL-10H, Fuso Chemical Industry, average primary particle size: 90 nm) was used as the particles for the experiment. 50 mL of the silica microparticle composition was dropped and rotated at 500 rpm for 5 seconds for coating. Thereafter, it was rotated at 1,000 rpm for 30 seconds to spin-dry the solvent of the silica microparticle composition. Thus, a substrate for particle removal evaluation was obtained.

[0224] <Particle Removal Evaluation>

[0225] When using a cleaning composition other than those of Examples 16 and 20, Coater / Developer RF 3 (SOKUDO) was used to drop 10 cc of the cleaning composition onto the substrate for particle removal evaluation and rotate it at 1,500 rpm for 60 seconds for coating and drying to form a film.

[0226] When using the cleaning compositions of Examples 16 and 20, the cleaning composition was spread on the substrate for particle removal evaluation, and then the wafer was heated at 350 °C for 3 seconds to melt it to form a film.

[0227] While rotating the substrate formed with the film at 100 rpm, water (deionized water) as the removal liquid was dropped for 10 seconds to cover the entire substrate with water. After maintaining this state for 60 seconds, it was rotated at 1,500 rpm to peel off and remove the film, and the substrate was dried.

[0228] A dark field defect inspection device (LS-9110, Hitachi High-Technologies) was used to calculate the particle residue amount of these substrates, and evaluation was performed according to the following criteria. The evaluation results are shown in Tables 1 and 2.

[0229] AA: ≤10

[0230] A: > 10 and ≤ 100

[0231] B: > 100 and ≤ 1,000

[0232] C: > 1,000

[0233] D: The film is not uniformly coated or the film is not removed.

[0234] <Suitability for Two Substrates>

[0235] Evaluate the suitability for two substrates according to the following criteria. The evaluation results are shown in Table 1 and Table 2.

[0236] A: The particle removal evaluation is AA or A in both the hydrophilic substrate and the hydrophobic substrate.

[0237] B: The particle removal evaluation is AA or A in one of the hydrophilic substrate or the hydrophobic substrate, and B or C in the other.

[0238] C: The particle removal evaluation is B or C in both the hydrophilic substrate and the hydrophobic substrate.

[0239] [Symbol Explanation]

[0240] 1: Substrate

[0241] 2: Particle

[0242] 3: Particle retention layer

[0243] 4: Soluble solute (B)

[0244] 5: Removing liquid

[0245] 6: Trace of soluble solute (B) dissolution

[0246] 7: Crack.

Claims

1. A substrate cleaning composition, which comprises an insoluble or hardly soluble solute (A): Among them, 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, 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; and The polar group is at least one selected from the group consisting of -OH, -COOH, -NO2, -NH2, and -NH-; Optionally, the substrate cleaning composition contains a solvent (C); Optionally, the substrate cleaning composition is applied to a substrate, at least a part of the solvent (C) is removed by drying to form a film, and then the film is removed from the substrate by a removing liquid; Optionally, the substrate cleaning composition is applied to a substrate and a film is formed by heating, and then the film is removed from the substrate by a removing liquid; and / or Optionally, the insoluble or hardly soluble solute (A) is insoluble or hardly soluble in the removing liquid.

2. The substrate cleaning composition according to claim 1, wherein (A-1) is represented by formula (a-1): Herein, Cy 01 is an unsaturated hydrocarbon ring, and optionally, 1 to 3 C atoms constituting Cy 01 can each independently be replaced by N, S or O Each X is independently -OH, -COOH, -NO2, or -NR’R”, R’ and R” are each independently hydrogen or C 1-5 alkyl group, Each R is independently C 1-10 alkyl, -CHO, -C(=O)CH3, -C(=O)C2H5, -CH=CH2 or -O-C(=O)-CH=CH2; and n 01 is from 0 to 4, n 02 is from 0 to 3, n 03 is from 0 to 1, provided that 0 ≤ (n 01 + n 02 ) ≤ (5 + n 03 ).

3. The substrate cleaning composition according to claim 1 or 2, which further comprises a soluble solute (B); Optionally, the soluble solute (B) is soluble in the removing liquid; Optionally, based on the substrate cleaning composition, the content of the insoluble or hardly soluble solute (A) is 1.0 to 100% by mass; Optionally, based on the substrate cleaning composition, the content of the solvent (C) is 0 to 99.0% by mass; and / or Optionally, based on the substrate cleaning composition, the content of the soluble solute (B) is 0 to 50% by mass.

4. The substrate cleaning composition according to one or more of claims 1 to 3, wherein The solvent (C) contains water (C-1); Optionally, based on the solvent (C), the content of water (C-1) is 0.1 to 10% by mass.

5. The substrate cleaning composition according to one or more of claims 1 to 4, wherein, The polymer of (A-1) contains a repeating unit represented by formula (a-1-1) or a repeating unit represented by formula (a-1-2): Herein, Cy 01 、X, R, n 01 、n 02 and n 03 As recited in claim 2, m1 is a number of 1 or greater, m3 is 0 to 1, In formula (a-1-1), a hydrogen atom in X or a hydrogen atom directly bonded to the ring detaches and links to -CH2-; Optionally, when the insoluble or hardly soluble solute (A) contains the polymer of (A-1), it may also 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 hardly soluble solute (A) is a polymer of (A-1), its Mw is 250 to 50,000.

6. The substrate cleaning composition according to one or more of claims 1 to 5, wherein, The soluble solute (B) contains a repeating unit represented by formula (b-1): Wherein, L1 is selected from the group consisting of a single bond, C 1-4 an alkylene group, a phenylene group, an ether group, a carbonyl group, an amide group, and an imide group R1 is a carboxyl group, a sulfo group, or a phosphoryl group, R2 is hydrogen, methyl, or a carboxyl group, and R3 is hydrogen or methyl; Optionally, the acid dissociation constant pKa(H2O) of the soluble solute (B) is -5 to 11; and / or Optionally, the molecular weight of the soluble solute (B) is 500 to 500,000.

7. The substrate cleaning composition according to one or more of claims 1 to 6, wherein, The solvent (C) further contains an organic solvent (C-2).

8. The substrate cleaning composition according to one or more of claims 1 to 7, wherein, The solubility of the insoluble or poorly soluble solute (A) in water is 3,000 ppm or less, and the solubility of the soluble solute (B) in water is greater than 3,000 ppm; Optionally, the solubility is determined by adding 3,000 ppm of the above (A) or (B) to water in a flask under the condition of 20 - 35 °C, covering the flask with a lid and vibrating it with a vibrator for 1 hour, and checking whether (A) or (B) dissolves.

9. The substrate cleaning composition according to one or more of claims 1 to 8, which further comprises other additives (D); Here, the other additives (D) include surfactants, acids, bases, antibacterial agents, fungicides, preservatives or antifungal agents; Optionally, based on the insoluble or poorly soluble solute (A), the content of the other additives (D) is 0 - 100% by mass.

10. A method for manufacturing a cleaned substrate, which comprises the following steps: (1) Applying the substrate cleaning composition according to one or more of claims 1 to 9 to the substrate; (2) Forming a film from the substrate cleaning composition; (3) Retaining the particles on the substrate in the film; (4) Supplying a removing liquid to the substrate to remove the film retaining the particles.

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

12. The method of manufacturing a cleaned substrate according to claim 10 or 11, wherein, The substrate in (1) is an unprocessed substrate or a processed substrate; Optionally, the surface of the substrate is a semiconductor; Optionally, before applying the substrate cleaning composition, the surface of the substrate is subjected to a hydrophobic treatment; and / or Optionally, 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, Al, Ru, Co and amorphous carbon.

13. The method for manufacturing a cleaned substrate according to one or more of claims 10 to 12, which comprises at least one of the following steps: (0-1) Processing the substrate by etching to form a pattern and removing the etching mask; (0-2) Cleaning the substrate; (0-3) Pre-wetting the substrate; (0-4) Cleaning the substrate; (5) Dropping water, an alkaline aqueous solution or an organic solvent on the substrate from which the film retaining the particles has been removed, and then removing the water, the alkaline aqueous solution or the organic solvent, thereby further cleaning the substrate.

14. A method for manufacturing a device, which comprises the method for manufacturing a cleaned substrate according to one or more of claims 10 to 13.

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