TW202033725A - Composition for forming substrate treatment film and method for cleaning semiconductor substrate - Google Patents

Abstract

The present invention is a composition for forming a substrate treatment film to be used in a method for cleaning a semiconductor substrate, the method being equipped with a step for applying a composition for forming a substrate treatment film to a substrate, and a step for bringing the substrate treatment film formed through the application step into contact with a substrate treatment film removal solution, wherein the composition for forming a substrate treatment film is characterized by containing a polymer and a solvent, the polymer having a C2-20 monovalent hydrocarbon group.

Description

Composition for forming substrate treatment film and cleaning method of semiconductor substrate

The present invention relates to a composition for forming a substrate treatment film and a method for cleaning a semiconductor substrate.

In the manufacturing process of the semiconductor substrate, washing is performed in order to remove particles attached to the surface of the patterned substrate. In recent years, the miniaturization of formed patterns has progressed, whereby, for example, it has become more difficult to remove particles with finer pattern sizes from a patterned substrate, and this has become a main cause of a decrease in the yield of semiconductor substrates.

Japanese Patent Laid-Open No. 7-74137 discloses a method of supplying a coating liquid to the surface of a substrate to form a film, and then peeling the film with an adhesive tape or the like to remove particles on the surface of the substrate.

Japanese Patent Laid-Open No. 2014-99583 discloses a substrate cleaning device and a substrate cleaning method as follows: a processing liquid for forming a film is supplied to the surface of the substrate, and after curing or hardening, the removal liquid The cured or hardened treatment liquid is completely dissolved, thereby removing particles on the surface of the substrate. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 7-74137 [Patent Document 2] Japanese Patent Laid-Open No. 2014-99583

[The problem to be solved by the invention] The object of the present invention is to provide a composition for forming a substrate treatment film and a method for cleaning a semiconductor substrate, which can easily form a treatment film on the surface of a semiconductor substrate and remove fine particles attached to the surface of the substrate. The particles and the formed treatment film are removed from the surface of the substrate. [Means to solve the problem]

The invention made in order to solve the above-mentioned problems is a composition for forming a substrate treatment film, which is used in a cleaning method of a semiconductor substrate. The cleaning method of the semiconductor substrate includes: coating a substrate treatment film forming composition on a substrate And the step of contacting the substrate treatment film removal liquid with the substrate treatment film formed by the coating step, and the substrate treatment film formation composition is characterized by containing: a polymer and a solvent, and The polymer has a monovalent hydrocarbon group with 2-20 carbon atoms.

Another invention made in order to solve the above-mentioned problem is a method for cleaning a semiconductor substrate, including: applying a substrate treatment film forming composition on the substrate; and applying a substrate treatment film removal liquid and using the coating step The step of contacting the formed substrate treatment film and the method for cleaning the semiconductor substrate is characterized in that the composition for forming the substrate treatment film contains a polymer and a solvent, and the polymer has a carbon number of 2-20 Monovalent hydrocarbon group. [Effects of the invention]

According to the composition for forming a substrate treatment film and the method for cleaning a semiconductor substrate of the present invention, in the process of forming a treatment film on the surface of a semiconductor substrate and removing minute particles attached to the surface of the substrate, it is possible to easily remove all materials from the surface of the substrate. The particles and the formed treatment film. Therefore, the present invention can be suitably used in the manufacturing steps of semiconductor elements that are expected to develop more and more miniaturized in the future.

<Composition for forming substrate processing film> The composition for forming a substrate treatment film is used in a method for cleaning a semiconductor substrate, and the method for cleaning the semiconductor substrate includes: applying the composition for forming a substrate treatment film on the substrate; and applying a substrate treatment film removal liquid A step of contacting the substrate processing film formed by the coating step. The composition for forming a substrate processing film contains a polymer (hereinafter, also referred to as "[A] polymer") and a solvent (hereinafter, also referred to as "[B] solvent"), and the [A] polymer has A monovalent hydrocarbon group having 2 to 20 carbon atoms.

According to the composition for forming a substrate treatment film, by forming a treatment film on the surface of a semiconductor substrate and removing the treatment film, it is possible to easily remove particles attached to the surface of the semiconductor substrate, especially the patterned semiconductor substrate (hereinafter , Also called "particle removability"), and can easily remove the formed treatment film from the substrate surface (hereinafter, also called "film removability").

The composition for forming a substrate treatment film contains [A] polymer and [B] solvent, and the [A] polymer has a monovalent hydrocarbon group having 2 to 20 carbon atoms, thereby having excellent film removability and particle removability. The reason why the composition for forming a substrate treatment film exhibits the effect by including the above structure is not necessarily clear. For example, it is considered that the [A] polymer has a monovalent hydrocarbon group having 2 to 20 carbon atoms and therefore has moderate hydrophobicity. It is believed that by promoting the entrapment of particles into the treatment film formed of the [A] polymer, the particle removal performance is improved, and the film removal performance of the treatment film is improved.

In addition to the [A] polymer and [B] solvent, the composition for forming a substrate processing film may also contain a compound having at least one of a carboxyl group and an alcoholic hydroxyl group (hereinafter, also referred to as "[C] compound") As a suitable component, other arbitrary components may be contained within the range which does not impair the effect of this invention. Hereinafter, each component will be described.

＜[A] Polymer＞ [A] The polymer is a polymer having a monovalent hydrocarbon group having 2 to 20 carbon atoms (hereinafter also referred to as "group (I)"). The "polymer" refers to a compound having two or more structural units. [A] The lower limit of the molecular weight of the polymer is preferably 300, and more preferably 500. [A] The polymer can be used alone or in combination of two or more.

Examples of the group (I) include a monovalent aliphatic hydrocarbon group having 2 to 20 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, and the like.

Examples of monovalent aliphatic hydrocarbon groups having 2 to 20 carbon atoms include alkyl groups such as ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl, and ethylene Alkenyl, propenyl, butenyl and other alkenyl groups; monovalent chain hydrocarbon groups with 2 to 20 carbons such as alkynyl groups such as ethynyl, propynyl and butynyl; cycloalkyl groups such as cyclopentyl and cyclohexyl, ring Cycloalkenyl groups such as pentenyl and cyclohexenyl, bridged ring saturated hydrocarbon groups such as norbornenyl, adamantyl, and tricyclodecyl group, bridged ring unsaturated hydrocarbon groups such as norbornenyl group and tricyclodecenyl group, etc. A monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, etc.

Examples of monovalent aromatic hydrocarbon groups having 6 to 20 carbon atoms include aryl groups such as phenyl, tolyl, xylyl, naphthyl, anthryl, benzyl, phenylethyl, naphthylmethyl, and anthracene. Aralkyl groups such as methyl groups, etc.

The group (I) is preferably a monovalent aliphatic hydrocarbon group having 2 to 20 carbons, more preferably a monovalent aliphatic hydrocarbon group having 2 to 10 carbons, and still more preferably an alkyl group having 2 to 6 carbons or a carbon number Cycloalkyl groups of 3 to 6 are particularly preferably ethyl, tertiary butyl or cyclohexyl, more preferably ethyl or tertiary butyl, and most preferably tertiary butyl. [A] The polymer has more moderate hydrophobicity by having the group, and as a result, the film removability and particle removability can be further improved.

[A] The polymer includes, for example, novolak resin, resole resin, aromatic ring-containing vinyl resin, acrylic resin, calixarene resin, and the like.

(Novolak resin) Novolac resin is a chain polymer obtained by reacting a compound having an aromatic ring to which a phenolic hydroxyl group is bonded (hereinafter also referred to as a "phenol compound") with an aldehyde compound using an acid catalyst. In the novolak resin having the group (I), the group (I) is usually bonded to the aromatic ring to which the phenolic hydroxyl group is bonded and/or the methylene group derived from the aldehyde compound. When the group (I) is bonded to the benzene ring to which the phenolic hydroxyl group is bonded, the position of the group (I) relative to the 1-position of the phenolic hydroxyl group of the benzene ring may be 2-position, 3-position, or 4-position. Any of the bits.

The novolak resin having a group (I) has, for example, a structural unit represented by the following formula (1) (hereinafter, also referred to as "structural unit (I)").

[化1]

In the formula (1), Ar ¹ is a (p1+q1+r+2) valence obtained by removing (p1+q1+r+2) hydrogen atoms on the aromatic ring from an aromatic hydrocarbon with 6 to 20 carbon atoms的基。 The base. X ¹ is the base (I). p1 is an integer of 1-9. When p1 is 2 or more, a plurality of X ¹ are the same or different from each other. Y ¹ is a monovalent organic group having 1 to 20 carbon atoms or a halogen atom other than the group (I). q1 is an integer of 0-8. When q1 is 2 or more, a plurality of Y ¹ are the same or different from each other. r is an integer of 1-9. Here, p1+q1+r is 10 or less. R ¹ is a hydrogen atom or group (I).

Examples of aromatic hydrocarbons having 6 to 20 carbon atoms that provide Ar ¹ include benzene, naphthalene, anthracene, phenanthrene, fused tetrabenzene, pyrene, terphenylene, fluorene, and the like. Among these, benzene or naphthalene is preferred, and benzene is more preferred.

The so-called "organic group" refers to a group containing at least one carbon atom. As the monovalent organic group having 1 to 20 carbons, for example, a monovalent hydrocarbon group having 1 to 20 carbons, a group containing a divalent heteroatom-containing group between carbon and carbon of the hydrocarbon group, the hydrocarbon group, and the A group in which a part or all of the hydrogen atoms of the group including a heteroatom-containing group is substituted with a monovalent heteroatom-containing group, etc. Examples of the monovalent organic group having 1 to 20 carbon atoms other than the group (I) represented by Y ¹ include groups other than the group (I) among the groups exemplified as the monovalent organic group having 1 to 20 carbon atoms. The base and so on.

Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms include a methyl group and the same groups as those exemplified as the group (I).

Examples of the heteroatom constituting the divalent or monovalent heteroatom-containing group include an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, a silicon atom, and a halogen atom.

As the divalent heteroatom-containing group, for example, -O-, -CO-, -S-, -CS-, -NR'-, a group formed by combining two or more of these, and the like can be cited. R'is a hydrogen atom or a monovalent hydrocarbon group. Among these, -O- and -S- are preferable.

Examples of the monovalent heteroatom-containing group include halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, a hydroxyl group, a carboxyl group, a cyano group, an amino group, and a sulfanyl group.

As p1, 1 to 3 are preferable, 1 or 2 is more preferable, and 1 is still more preferable. As q1, 0-2 is preferable, 0 or 1 is more preferable, and 0 is still more preferable. As r, 1 to 3 are preferable, 1 or 2 is more preferable, and 1 is still more preferable. As R ¹ , a hydrogen atom is preferred.

Examples of the phenol compound having group (I) used as the raw material compound of the novolak resin include 2-ethylphenol, 3-ethylphenol or 4-ethylphenol, 2-tert-butylphenol, 3- Tertiary butyl phenol or 4-tertiary butyl phenol, 2-cyclohexyl phenol, 3-cyclohexyl phenol or 4-cyclohexyl phenol, 2-phenyl phenol, 3-phenyl phenol or 4-phenyl phenol, 2-benzylphenol, 3-benzylphenol or 4-benzylphenol, 2-tertiary butyl naphthol, 3-tertiary butyl naphthol, 4-tertiary butyl naphthol, 5-tertiary butyl naphthol Naphthol, 6-tert-butyl naphthol, 7-tert-butyl naphthol, 8-tert-butyl naphthol, etc.

As the aldehyde compound used as the raw material compound of the novolak resin, for example, formaldehyde, acetaldehyde, etc. can be used, and as the aldehyde compound having the group (I), for example, propionaldehyde, butyraldehyde, cyclohexyl formaldehyde, and benzaldehyde can be used. , Pyrene formaldehyde (formylpyrene), etc. Furthermore, paraformaldehyde can be used instead of formaldehyde, and paraldehyde can also be used instead of acetaldehyde.

Examples of acidic catalysts include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid; organic acids such as methanesulfonic acid, p-toluenesulfonic acid, and oxalic acid; Lewis acids such as boron trifluoride, anhydrous aluminum chloride, and zinc acetate ( lewis acid) and so on. Among these, organic acid is preferred, and p-toluenesulfonic acid is more preferred.

(Resole phenolic resin) Resole phenol resin is a polymer obtained by reacting a phenol compound and an aldehyde compound using a basic catalyst. In the resole resin having the group (I), the group (I) is usually bonded to the aromatic ring to which the phenolic hydroxyl group is bonded and/or the methylene group derived from the aldehyde compound.

Examples of the phenol compound and aldehyde compound used as the raw material compound of the resol resin include the same compounds as the phenol compound and aldehyde compound used as the raw material of the novolak resin.

Examples of alkaline catalysts include hydroxides of alkali metals or alkaline earth metals such as sodium hydroxide, lithium hydroxide, potassium hydroxide, and calcium hydroxide; ammonia, triethanolamine, triethylamine, and hexamethylene Amine compounds such as tetraamine; alkaline substances such as sodium carbonate, etc.

(Vinyl resin containing aromatic ring) The aromatic ring-containing vinyl resin is a polymer having a structural unit derived from a compound having an aromatic ring and a polymerizable carbon-carbon double bond. In the aromatic ring-containing vinyl resin having the group (I), the group (I) is usually bonded to the aromatic ring derived from the compound.

The aromatic ring-containing vinyl resin having a group (I) has, for example, a structural unit represented by the following formula (2) (hereinafter, also referred to as "structural unit (II)").

[化2]

In the formula (2), R ² is a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms. Ar ² is a (p2+q2+1) valence group obtained by removing (p2+q2+1) hydrogen atoms on the aromatic ring from an aromatic hydrocarbon having 6 to 20 carbon atoms. X ² is the base (I). p2 is an integer of 1-11. When p2 is 2 or more, a plurality of X ² are the same or different from each other. Y ² is a monovalent organic group having 1 to 20 carbon atoms other than the group (I), a halogen atom, or a phenolic hydroxyl group. q2 is an integer of 0-10. When q2 is 2 or more, a plurality of Y ² are the same or different from each other.

Examples of the monovalent organic group having 1 to 10 carbons represented by R ² include groups having 1 to 10 carbons in the monovalent organic group having 1 to 20 carbons exemplified in the item of Y ¹ . . As R ² , a hydrogen atom or a methyl group is preferable, and a hydrogen atom is more preferable.

Examples of the monovalent organic group having 1 to 20 carbons other than the group (I) represented by Y ² include monovalent organic groups having 1 to 20 carbons other than the group (I) as the Y ¹ The exemplified bases are the same bases.

As p2, 1-3 are preferable, 1 or 2 is more preferable, and 1 is still more preferable. As q2, 0-2 is preferable, 0 or 1, and 0 is more preferable.

As the compound providing the structural unit (II), for example, 2-ethylstyrene, 3-ethylstyrene or 4-ethylstyrene, 2-tert-butylstyrene, 3-tert-butyl Styrene or 4-tert-butylstyrene, 2-cyclohexylstyrene, 3-cyclohexylstyrene or 4-cyclohexylstyrene, 2-phenylstyrene, 3-phenylstyrene or 4-benzene Styrene, 2-benzyl styrene, 3-benzyl styrene or 4-benzyl styrene and other styrene having group (I), 2-tert-butyl-4-hydroxystyrene or 3-th Hydroxystyrene with group (I) such as tributyl-4-hydroxystyrene, 2-tert-butyl-1-vinylnaphthalene, 3-tert-butyl-1-vinylnaphthalene, 4-tertiary Butyl-1-vinylnaphthalene, 5-tert-butyl-1-vinylnaphthalene, 6-tert-butyl-1-vinylnaphthalene, 7-tert-butyl-1-vinylnaphthalene or 8- Vinyl naphthalene having group (I) such as tertiary butyl-1-vinylnaphthalene, etc.

The aromatic ring-containing vinyl resin having the structural unit (II) preferably further has a structural unit containing a phenolic hydroxyl group or an alcoholic hydroxyl group (hereinafter, also referred to as "structural unit (A)").

Examples of the compound providing the structural unit (A) include hydroxyalkyl (meth)acrylates such as 2-hydroxystyrene, 3-hydroxystyrene, 4-hydroxystyrene, and hydroxyethyl (meth)acrylate. , (Meth) hydroxyphenyl acrylate, etc. (meth) hydroxyaryl acrylate, etc.

When the aromatic ring-containing vinyl resin has the structural unit (II) and the structural unit (A), the lower limit of the molar ratio of the structural unit (A) to the structural unit (II) is preferably 5/95 , More preferably 10/90, still more preferably 20/80. The upper limit of the molar ratio is preferably 90/10, more preferably 70/30, and still more preferably 40/60.

(Acrylic) Acrylic resin is a polymer having structural units derived from (meth)acrylate. The acrylic resin having the group (I) is usually formed by using the (meth)acrylate of the compound having the group (I) as a single-weight compound.

The acrylic resin having the group (I) has, for example, a structural unit represented by the following formula (3) (hereinafter, also referred to as "structural unit (III)").

[化3]

In the formula (3), R ³ is a hydrogen atom or a methyl group. R ⁴ is a single bond or a divalent organic group having 1 to 20 carbons. Z is the base (I).

As R ³ , a hydrogen atom is preferred.

Examples of the divalent organic group having 1 to 20 carbons represented by R ⁴ include a group obtained by removing one hydrogen atom from the monovalent organic group having 1 to 20 carbons exemplified in the item of Y ¹ . Wait. As R ⁴ , a single bond is preferred.

Examples of the compound providing the structural unit (III) include: ethyl (meth)acrylate, propyl (meth)acrylate, tert-butyl (meth)acrylate, etc. (meth)acrylic acid has a carbon number of 2 or more Alkyl esters, cyclohexyl (meth)acrylate and other cycloalkyl (meth)acrylates, phenyl (meth)acrylate and other aryl (meth)acrylates, benzyl (meth)acrylate (Meth)acrylic acid aralkyl esters, (meth)acrylic acid tertiary butoxyethyl and other (meth)acrylic acid carbon number 2 or more alkoxy-containing alkyl esters, etc.

The acrylic resin having a structural unit (III) preferably further has a structural unit represented by the following formula (4) (hereinafter, also referred to as "structural unit (B)").

[化4]

In the formula (4), R ⁵ is a hydrogen atom or a methyl group. R ⁶ is a divalent organic group having 1 to 20 carbons.

As R ⁵ , a hydrogen atom is preferred.

Examples of the divalent organic group having 1 to 20 carbons represented by R ⁶ include groups obtained by removing one hydrogen atom from the monovalent organic groups having 1 to 20 carbons exemplified in the item of Y ¹ . Wait. R ^{6 is} preferably a divalent hydrocarbon group, more preferably a divalent chain hydrocarbon group, still more preferably an alkanediyl group, and particularly preferably an ethylenediyl group.

Examples of compounds providing the structural unit (B) include hydroxyalkyl (meth)acrylates such as hydroxyethyl (meth)acrylate and hydroxypropyl (meth)acrylate, and hydroxycyclohexyl (meth)acrylate Hydroxycycloalkyl esters of (meth)acrylic acid such as esters, hydroxyaryl (meth)acrylates such as hydroxyphenyl (meth)acrylate, hydroxybenzyl (meth)acrylates, etc. Aralkyl esters and the like. Among these, hydroxyalkyl (meth)acrylate is preferred, and hydroxyethyl (meth)acrylate is more preferred.

In the case where the acrylic resin has the structural unit (III) and the structural unit (B), the lower limit of the molar ratio of the structural unit (B) relative to the structural unit (III) is preferably 5/95, more preferably 10/ 90, more preferably 20/80. The upper limit of the molar ratio is preferably 90/10, more preferably 70/30, and still more preferably 40/60.

(Caixarene resin) The calixarene resin is a cyclic oligomer in which an aromatic ring to which a phenolic hydroxyl group is bonded is cyclically bonded via a hydrocarbon group. In the calixarene resin having the group (I), the group (I) is usually bonded to the aromatic ring to which the phenolic hydroxyl group is bonded and/or the hydrocarbon group.

Examples of the compound that provides the aromatic ring to which the group (I) and the phenolic hydroxyl group are bonded include the same compounds as the phenol compound having the group (I) exemplified as the raw material compound of the novolak resin. Examples of the hydrocarbon group include a methylene group, a methylene group to which the group (I) is bonded, and the like.

[A] The lower limit of the weight average molecular weight (Mw) of the polymer is preferably 1,000, more preferably 2,000, still more preferably 3,000, and particularly preferably 4,000. The upper limit of the Mw is preferably 100,000, more preferably 30,000, further preferably 20,000, and particularly preferably 15,000.

Mw in this manual refers to the use of Tosoh (stocks) Gel Permeation Chromatography (GPC) column (2 "G2000HXL", 1 "G3000HXL" and 1 "G4000HXL"), Measured by gel permeation chromatography (detector: differential refractometer) with monodisperse polystyrene as standard under analytical conditions of flow rate: 1.0 mL/min, dissolution solvent: tetrahydrofuran, column temperature: 40°C Value.

The lower limit of the content of the [A] polymer in all components other than the solvent [B] as the composition for forming a substrate processing film is preferably 70% by mass, more preferably 80% by mass, and still more preferably 90% by mass %, particularly preferably 95% by mass. The upper limit of the content ratio is preferably 99.99% by mass, more preferably 99.9% by mass, and still more preferably 99.0% by mass.

The lower limit of the content of the [A] polymer in the composition for forming a substrate processing film is preferably 1% by mass, more preferably 3% by mass, still more preferably 5% by mass, and particularly preferably 7% by mass. The upper limit of the content ratio is preferably 50% by mass, more preferably 30% by mass, still more preferably 20% by mass, and particularly preferably 15% by mass.

＜[B] Solvent＞ [B] The solvent can be used without particular limitation if it is a solvent that dissolves or disperses the [A] polymer and optional components contained as necessary. [B] The solvent may be used alone or in combination of two or more.

Examples of the [B] solvent include an organic solvent (hereinafter, also referred to as "[b] organic solvent"), water, and the like. In the case where [B] solvent contains [b] organic solvent, the lower limit of the content ratio of [b] organic solvent in [B] solvent is preferably 70% by mass, more preferably 90% by mass, and still more preferably 95% by mass, particularly preferably 99% by mass. [B] The content ratio of the organic solvent may be 100% by mass. When the [B] solvent contains water, the upper limit of the content of water in the [B] solvent is preferably 10% by mass, more preferably 2% by mass, and still more preferably 1% by mass. The lower limit of the water content is, for example, 0.01% by mass.

[B] The organic solvent includes, for example, alcohol-based solvents, ketone-based solvents, ether-based solvents, ester-based solvents, and nitrogen-containing solvents.

Examples of alcohol-based solvents include monoalcohols such as methanol, ethanol, n-propanol, and n-butanol; polyhydric alcohols such as ethylene glycol, 1,2-propanediol and 1,2-butanediol; and propylene glycol monomethyl Polyol partial ethers such as ether and propylene glycol monoethyl ether, and lactate esters such as ethyl lactate and butyl lactate.

Examples of the ketone solvent include chain ketones such as methyl ethyl ketone and methyl isobutyl ketone, and cyclic ketones such as cyclohexanone.

Examples of ether-based solvents include chain ethers such as n-butyl ether and cyclic ethers such as tetrahydrofuran and 1,4-dioxane.

Examples of ester solvents include: carbonates such as diethyl carbonate, acetates such as methyl acetate and ethyl acetate, lactones such as γ-butyrolactone, and diethylene glycol monomethyl ether acetate , Polyol partial ether carboxylates such as propylene glycol monomethyl ether acetate, etc.

Examples of nitrogen-containing solvents include chain nitrogen-containing compounds such as N,N-dimethylacetamide, and cyclic nitrogen-containing compounds such as N-methylpyrrolidone.

[B] The organic solvent is preferably an alcohol-based solvent and/or an ester-based solvent, more preferably polyol partial ethers, lactate esters, and/or polyol partial ether carboxylates, and more preferably propylene glycol monoethyl ether , Ethyl lactate and/or propylene glycol monomethyl ether acetate.

[B] The lower limit of the content of the solvent is preferably 100 parts by mass relative to 100 parts by mass of the polymer [A], more preferably 300 parts by mass, still more preferably 500 parts by mass, particularly preferably 700 parts by mass. The upper limit of the content is preferably 10,000 parts by mass, more preferably 5,000 parts by mass, still more preferably 3,000 parts by mass, and particularly preferably 2,000 parts by mass.

The lower limit of the content of the solvent [B] in the composition for forming a substrate processing film is preferably 50% by mass, more preferably 70% by mass, still more preferably 80% by mass, and particularly preferably 85% by mass. The upper limit of the content ratio is preferably 99% by mass, more preferably 97% by mass, still more preferably 95% by mass, and particularly preferably 93% by mass.

＜[C] Compound＞ [C] The compound is a compound having at least one of a carboxyl group and an alcoholic hydroxyl group (except for the compound corresponding to [B] the solvent). If the composition for forming a substrate processing film further contains a [C] compound, the film removability can be further improved.

Examples of [C] compounds include organic acids that are not polymers (hereinafter also referred to as "[c1] organic acids"), alcoholic hydroxyl-containing compounds (hereinafter, also referred to as "[c2] hydroxyl-containing Compounds”) (excluding compounds equivalent to [c1] organic acids), etc. [C] The compound can be used alone or in combination of two or more.

[c1] Organic acids are organic acids that are not polymers. [C1] The upper limit of the molecular weight of the organic acid is, for example, 500, preferably 400, and more preferably 300. [C1] The lower limit of the molecular weight of the organic acid is, for example, 50, and preferably 55. [C1] The number of carboxyl groups in the organic acid is preferably 1 to 4, and more preferably 1 or 2.

[C1] The organic acid is preferably a carboxylic acid, and more specifically, for example, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, cyclohexanecarboxylic acid, cyclohexylacetic acid, 1-adamantane Carboxylic acids containing aliphatic saturated hydrocarbon groups and/or aromatic hydrocarbon groups and carboxyl groups, such as carboxylic acid, benzoic acid, and phenylacetic acid; Difluoroacetic acid, trifluoroacetic acid, pentafluoropropionic acid, heptafluorobutyric acid, fluorophenylacetic acid, difluorobenzoic acid and other monocarboxylic acids containing fluorine atoms; 10-hydroxydecanoic acid, 5-oxohexanoic acid, 3-methoxycyclohexanecarboxylic acid, camphor carboxylic acid, dinitrobenzoic acid, nitrophenylacetic acid, lactic acid, glycolic acid, glyceric acid, salicylic acid Acid, anisic acid, gallic acid, and furan carboxylic acid are monocarboxylic acids whose parts other than the carboxyl group contain heteroatoms other than fluorine atoms; (Meth) acrylic acid, crotonic acid, cinnamic acid, sorbic acid and other monocarboxylic acid compounds containing double bond; Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, dodecane dicarboxylic acid, propane tricarboxylic acid, butane tetracarboxylic acid, cyclohexane hexacarboxylic acid, 1,4-naphthalene Dicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, 1,2,3,4-cyclobutanetetracarboxylic acid, etc. contain single bonds, aliphatic Saturated hydrocarbon group and/or aromatic hydrocarbon group and polycarboxylic acid with multiple carboxyl groups; Partial esterification of the polycarboxylic acid; Polycarboxylic acids containing fluorine atoms such as difluoromalonic acid, tetrafluorophthalic acid, and hexafluoroglutaric acid; Tartaric acid, citric acid, malic acid, hydroxymalonic acid, oxydiacetic acid, iminodiacetic acid are equal to polycarboxylic acids whose parts other than the carboxyl group contain heteroatoms other than fluorine atoms; Polycarboxylic acid compounds such as maleic acid, fumaric acid, ornithic acid and other polycarboxylic acids containing double bonds.

[C1] The organic acid is preferably a carboxylic acid or a polycarboxylic acid containing an aliphatic saturated hydrocarbon group and a carboxyl group, and more preferably acetic acid or malic acid, from the viewpoint of further improving the film removability.

[C2] The lower limit of the number of alcoholic hydroxyl groups in the hydroxyl group-containing compound is preferably 2, more preferably 3, and still more preferably 4. The upper limit of the number is 20, for example.

[C2] The hydroxyl group-containing compound includes, for example, polyol compounds and sugar compounds.

Examples of the polyol compound include glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, adamantanediol, adamantane triol, adamantane tetraol, 1,3-dimethyladamantane-5,7 -Glycol, polyethylene glycol, polyvinyl alcohol, etc.

Examples of sugar compounds include: molasses, waste molasses, glucose, galactose, xylose, lactose, mannose, talose, and rhamnose ), arabinose, glycosylmannose, lyxose, allose, altrose, gulose, idose , Ribose, erythrose, threose, psicose, fructose, sorbose, tagatose, pentulose ), tetrose, erythritol, mesoerythritol, sucrose, maltose, isomaltose, cellobiose, lactose, Trehalose, kojibiose, sophorose, nigerose, laminaribiose, isomaltose, gentiobiose, melibiose ), planteobiose, turanose, viciabiose, agarobiose, scillabiose, rutinose, primrose ( primeverose, xylobiose, rhodimenabiose, maltitol, lactitol, D-threitol, D-arabinitol ), ribitol (ribitol), xylitol (xylitol), sorbitol, galactitol (galactitol), D-mannitol (D-mannitol), allitol (allitol), higher alditol (alditol) , Aldonic acid, glucitol, maltotriose, alginic acid and its salts, cyclodextrins, cellulose, starch, dextran, mannan, pectin, pectic acid, chitosan Sugar, hyaluronic acid, chondroitin sulfate, heparan sulfate, keratan sulfate, etc.

[C2] The hydroxyl-containing compound is preferably a sugar compound, more preferably erythritol, ribitol, sucrose or trehalose.

The lower limit of the solubility of the [C] compound in water at 25°C is preferably 5 mass%, more preferably 7 mass%, and still more preferably 10 mass%. The upper limit of the solubility is preferably 50% by mass, more preferably 40% by mass, and still more preferably 30% by mass. By setting the solubility to the above range, the film removability can be further improved.

[C] The compound is preferably a solid at 25°C. If the [C] compound is solid at 25°C, it is considered that the solid [C] compound precipitates in the film formed from the composition for forming a substrate processing film, and the film removability can be further improved.

When the composition for forming a substrate treatment film contains the [C] compound, the lower limit of the content of the [C] compound is preferably 0.01 parts by mass, more preferably 0.1, relative to 100 parts by mass of the [A] polymer Part by mass, more preferably 1 part by mass, particularly preferably 2 parts by mass. The upper limit of the content is preferably 100 parts by mass, more preferably 50 parts by mass, still more preferably 20 parts by mass, and particularly preferably 10 parts by mass. By setting the content of the [C] compound in the above range, the film removability and particle removability can be further improved.

＜Other optional ingredients＞ Examples of other optional components include surfactants. Other optional components can be used alone or in combination of two or more.

When the composition for forming a substrate treatment film further contains a surfactant, the coating properties can be further improved. Examples of surfactants include nonionic surfactants, cationic surfactants, and anionic surfactants.

Examples of the nonionic surfactant include: ether type nonionic surfactants such as polyoxyethylene alkyl ethers; ether ester type nonionic surfactants such as polyoxyethylene ethers of glycerides; polyethylene glycol fats Ester-type nonionic surfactants such as acid esters, glycerides, and sorbitan esters.

As said cationic surfactant, aliphatic amine salt, aliphatic ammonium salt, etc. are mentioned, for example.

Examples of the anionic surfactant include carboxylates such as fatty acid soaps and alkyl ether carboxylates; sulfonates such as alkylbenzene sulfonates, alkylnaphthalene sulfonates, and α-olefin sulfonates. ; Sulfuric acid ester salts such as higher alcohol sulfate ester salts and alkyl ether sulfate salts; Phosphate ester salts such as alkyl phosphate esters, etc.

When the composition for forming a substrate treatment film contains a surfactant, the upper limit of the content of the surfactant is, for example, 2 parts by mass with respect to 100 parts by mass of the [A] polymer. The lower limit of the content is, for example, 0.01 part by mass. By setting the content of the surfactant in the above range, coating properties can be further improved.

<Method for preparing composition for forming substrate processing film> The composition for forming a substrate processing film can be prepared, for example, by mixing arbitrary components such as [A] polymer, [B] solvent, and optionally [C] compound in a predetermined ratio, preferably using pores. Filter the obtained mixed liquid with a filter of 0.1 μm to 5 μm.

＜How to clean semiconductor substrate＞ The method for cleaning a semiconductor substrate includes: a step of supplying a composition for forming a substrate treatment film, supplying a composition for forming a substrate treatment film containing a volatile component and forming a film on a substrate to the substrate; and supplying a peeling treatment liquid A step of supplying a treatment film formed by curing or hardening the composition for forming a substrate treatment film on the substrate due to the volatilization of the volatile component, and a peeling treatment liquid for peeling the treatment film from the substrate. In the method for cleaning a semiconductor substrate, the composition for forming a substrate treatment film is used as the composition for forming a substrate treatment film.

According to the cleaning method of the semiconductor substrate, since the composition for forming the substrate processing film is used, a processing film (hereinafter, also referred to as "processing film (B)") is formed on the surface of the semiconductor substrate and the substrate surface is removed In the manufacturing process of foreign matter, the minute particles on the substrate surface can be efficiently removed, and the formed treatment film (B) can be easily removed from the substrate surface.

An application example of the cleaning method of the semiconductor substrate will be described in detail with reference to the drawings. Hereinafter, each step will be described.

[Supply Step of Composition for Forming Substrate Treatment Film] In this step, a composition for forming a substrate treatment film containing a volatile component and for forming a film on a substrate is supplied to the substrate. As the composition for forming a substrate processing film, the composition for forming a substrate processing film is used.

The substrate may be a substrate without a pattern, or a substrate with a pattern.

Examples of substrates that are not patterned include: silicon substrates, aluminum substrates, nickel substrates, chromium substrates, molybdenum substrates, tungsten substrates, copper substrates, tantalum substrates, titanium substrates and other metal substrates or semi-metal substrates; silicon nitride substrates , Alumina substrate, silicon dioxide substrate, tantalum nitride substrate, titanium nitride and other ceramic substrates. Among these, a silicon substrate, a silicon nitride substrate or a titanium nitride substrate is preferred, and a silicon substrate is more preferred.

As the pattern of the patterned substrate, for example, a line-and-space pattern or a groove pattern having a line width of 2,000 nm or less, 1,000 nm or less, 500 nm or less, and 50 nm or less, or a diameter of 300 nm or less can be cited. , 150 nm or less, 100 nm or less, and then 50 nm or less hole patterns, etc.

In addition, as the size of the pattern formed on the substrate, for example, a height of 100 nm or more, 200 nm or more, and then 300 nm or more, a width of 50 nm or less, 40 nm or less, and 30 nm or less, aspect ratio (pattern The height/pattern width) is a fine pattern of 3 or more, 5 or more, and further 10 or more.

In addition, the coating film (hereinafter, also referred to as “coating film (A)”) formed by supplying the substrate processing film forming composition to the substrate is preferably one that embeds the concave portion of the pattern. By embedding the coating film (A) in the recesses of the pattern, particles adhering to the recesses of the pattern can be removed more efficiently, and a more excellent particle removal effect can be exerted.

As a method of supplying the composition for forming a substrate processing film to the substrate, for example, a spin coating method (spin coating), a cast coating method, a roll coating method, etc. can be cited. Thereby, the coating film (A) of the composition for substrate processing film formation is formed.

As shown in FIG. 1A, first, a composition for forming a substrate processing film is supplied on a wafer W. As shown in FIG. Thereby, the coating film (A) of the composition for substrate processing film formation is formed.

Next, as shown in FIG. 1B, by volatilizing part or all of volatile components such as [B] solvent from the formed coating film (A), the substrate processing film forming composition is cured or hardened on the substrate, thereby A treatment film (B) is formed. The so-called "curing" means solidification, and the so-called "hardening" means that molecules are connected to each other to increase the molecular weight (for example, cross-linking or polymerization). At this time, the particles attached to the pattern or wafer W, etc. are wrapped in the processing film (B) and separated from the pattern or wafer W, etc.

In this case, by heating and/or reducing the pressure of the coating film (A), the curing or hardening of the coating film (A) can be promoted.

The lower limit of the heating temperature for curing and/or curing is preferably 30°C, and more preferably 40°C. The upper limit of the heating temperature is preferably 200°C, more preferably 100°C, and still more preferably 90°C. The lower limit of the heating time is preferably 5 seconds, more preferably 10 seconds, and still more preferably 30 seconds. The upper limit of the heating time is preferably 10 minutes, more preferably 5 minutes, and still more preferably 2 minutes.

The lower limit of the average thickness of the formed treatment film (B) is preferably 10 nm, more preferably 20 nm, and still more preferably 50 nm. The upper limit of the average thickness is preferably 1,000 nm, and more preferably 500 nm.

[Peeling treatment liquid supply step] In this step, the treatment film (B) obtained by curing or hardening the composition for forming a substrate treatment film on the substrate by the volatilization of the volatile component is supplied so that the treatment film (B) is free The peeling treatment liquid for peeling the substrate.

As shown in FIG. 1C, the peeling treatment liquid is supplied on the treatment film (B). Thereby, the processing film (B) is completely removed from the wafer W. As a result, the particles are removed from the wafer W together with the processing film (B).

As the peeling treatment liquid, water, organic solvents, alkaline aqueous solutions, etc. can be used. The peeling treatment liquid is preferably a liquid containing water, more preferably water or an alkaline aqueous solution, and still more preferably an alkaline aqueous solution. As the alkaline aqueous solution, an alkaline developer can be used. Known ones can be used for the alkaline developer. As a specific example, an aqueous solution containing at least one of ammonia, tetramethyl ammonium hydroxide (Tetra Methyl Ammonium Hydroxide, TMAH), and choline, etc. are mentioned, for example. As an organic solvent, for example, diluent, isopropyl alcohol (Isopropyl Alcohol, IPA), 4-methyl-2-pentanol (Methyl Isobutyl Carbinol (MIBC)), toluene, acetate can be used Classes, alcohols, glycols (propylene glycol monomethyl ether, etc.), etc. In addition, the removal of the treatment film (B) may be performed by first supplying water as a peeling treatment liquid to the treatment film (B), and then supplying an alkaline developer, etc., using different types of peeling treatment liquids in sequence. By sequentially using different types of peeling treatment liquids, the film removal properties can be further improved.

By supplying a peeling treatment solution such as an alkaline developer, as shown in FIG. 1C, a zeta potential of the same polarity (here, negative) is generated on the surface of the wafer W or the pattern and the surface of the particles. The particles separated from the wafer W and the like are charged to a zeta potential having the same polarity as the wafer W and the like, thereby repelling each other with the wafer W and the like. This can further suppress the reattachment of particles to the wafer W and the like.

In this way, according to the cleaning method of the semiconductor substrate, the particles can be removed with a weak force compared to the conventional particle removal using physical force, and therefore the pattern collapse can be suppressed. In addition, since no chemical action is used to remove particles, it is also possible to suppress the erosion of the wafer W or the pattern caused by the etching action or the like. Furthermore, it is also possible to easily remove particles with small particle diameters that are difficult to remove in a substrate cleaning method using physical force or particles that have entered the gaps of the pattern.

The substrate processing film forming composition supplied to the wafer W is finally completely removed from the wafer W. Therefore, the washed wafer W is in a state before the substrate processing film forming composition is supplied, specifically, the circuit formation surface is exposed.

The method for cleaning the semiconductor substrate can be performed by various known devices, storage media, and the like. As an example of a preferable device, for example, a substrate cleaning device disclosed in Japanese Patent Laid-Open No. 2014-99583 can be cited. Specifically, a semiconductor substrate cleaning device including: a first liquid supply unit for supplying a substrate processing film forming composition to a semiconductor substrate; and a second liquid supply unit for A removal liquid is supplied on the film, and the removal liquid dissolves the film formed from the substrate processing film formation composition supplied on the substrate by the first liquid supply unit. In addition, as the storage medium, the following storage medium can be cited. The storage medium operates on a computer, stores a program for controlling the substrate cleaning device and can be read by the computer, and when the program is executed, it can perform all operations. The method of the semiconductor substrate cleaning method allows a computer to control the substrate cleaning device. [Example]

Hereinafter, the present invention will be further described in detail through examples, but the present invention is not limited to these examples. The physical properties in the examples are measured by the following methods.

[Weight average molecular weight (Mw)] The Mw of the polymer uses GPC columns (Tosoh (stock)’s 2 "G2000HXL", 1 "G3000HXL", 1 "G4000HXL"), at flow rate: 1.0 mL/min, dissolution solvent: tetrahydrofuran, Column temperature: Measured by gel permeation chromatography (detector: differential refractometer) using monodisperse polystyrene as a standard under analysis conditions of 40°C.

＜[A] Synthesis of polymer＞ The polymer represented by the following formula (A-1) to formula (A-6) and formula (a-1) to formula (a-3) (hereinafter also referred to as "polymerization") was synthesized in the order shown below. (A-1) to polymer (A-6) and polymer (a-1) to polymer (a-3)").

[化5]

In the formula (A-6), the numerical value appended to each structural unit indicates the content ratio (mol %) of each structural unit with respect to all the structural units constituting the polymer (A-6).

[Synthesis Example 1] (Synthesis of polymer (A-1)) In a reaction vessel, 100 g of 2-ethylphenol, 66.43 g of 37% by mass formaldehyde, and 282.94 g of methyl isobutyl ketone were added and dissolved in a nitrogen atmosphere. After heating the resulting solution to 40°C, 1.59 g of p-toluenesulfonic acid was added, and the reaction was carried out at 85°C for 4 hours. The reaction liquid was cooled to 30° C. or lower, and the reaction liquid was poured into a methanol/water (50/50 (mass ratio)) mixed solution to perform reprecipitation. The precipitate was collected with filter paper and dried to obtain the polymer (A-1). The Mw of the polymer (A-1) was 8,000.

[Synthesis Example 2-Synthesis Example 5] (Synthesis of Polymer (A-2)-Polymer (A-5)) The raw material compounds are appropriately selected, and the same procedure as in Synthesis Example 1 is carried out to synthesize the aforementioned polymers (A-2) to (A-5). The Mw of the polymer (A-2) is 7,000, the Mw of the polymer (A-3) is 6,000, the Mw of the polymer (A-4) is 6,000, and the Mw of the polymer (A-5) is 7,000.

[Synthesis Example 6] (Synthesis of polymer (A-6)) Put 19.44 g of methyl ethyl ketone into the reaction vessel under a nitrogen atmosphere, and raise the temperature of the liquid to 80°C. To the liquid, 20.00 g of tert-butyl acrylate, 7.77 g of 2-hydroxyethyl acrylate, 2.64 g of 2,2-azobisisobutyrate, and methyl were added dropwise over 3 hours while maintaining 80°C. 36.10 g of ethyl ketone separately prepared solution. Furthermore, after dripping, it was aged at 80 degreeC for 3 hours, and the said polymer (A-6) was obtained by this. The Mw of the polymer (A-6) was 8,000.

[Comparative Synthesis Example 1 and Comparative Synthesis Example 2] (Synthesis of polymer (a-1) and polymer (a-2)) The raw material compounds are appropriately selected, and the same procedure as in Synthesis Example 1 is carried out to synthesize the above-mentioned polymer (a-1) and polymer (a-2). The Mw of the polymer (a-1) is 10,000, and the Mw of the polymer (a-2) is 10,000.

[Comparative Synthesis Example 3] (Synthesis of Polymer (a-3)) The monomer compound is appropriately selected, and the same procedure as in Synthesis Example 6 is carried out to synthesize the polymer (a-3). The Mw of the polymer (a-3) was 8,000.

<Preparation of composition for forming substrate processing film> Each component used in the preparation of the composition for forming a substrate processing film is shown below.

([A] component) The polymer (A-1) to polymer (A-6) and polymer (a-1) to polymer (a-3) synthesized in the synthesis example were used.

([B] solvent) B-1: Propylene glycol monoethyl ether B-2: Propylene glycol monomethyl ether acetate B-3: Ethyl lactate B-4: Water

([C] compound) C-1: Erythritol C-2: Ribitol C-3: Sucrose C-4: Trehalose C-5: Malic acid C-6: Acetic acid

[Example 1] 10 parts by mass of (A-1) as a polymer of [A] are dissolved in 100 parts by mass of (B-1) as a solvent for [B]. The obtained solution was filtered with a membrane filter with a pore diameter of 0.1 μm to prepare a substrate treatment membrane forming composition (J-1).

[Example 2 to Example 15 and Comparative Example 1 to Comparative Example 3] Except that the types and contents of each component shown in Table 1 below were used, the same procedure as in Example 1 was carried out to prepare a substrate treatment film forming composition (J-2) to a substrate treatment film forming composition (J- 15) And composition (j-1) for forming substrate processing film-composition (j-3) for forming substrate processing film. The "-" in Table 1 indicates that the corresponding ingredients are not used.

[Table 1] Composition for forming substrate processing film [A] Polymer [B] Solvent [C] Compound species Content (parts by mass) species Content (parts by mass) species Content (parts by mass) Example 1 J-1 A-1 10 B-1 100 - - Example 2 J-2 A-2 10 B-1 100 - - Example 3 J-3 A-3 10 B-1 100 - - Example 4 J-4 A-4 10 B-1 100 - - Example 5 J-5 A-5 10 B-1 100 - - Example 6 J-6 A-6 10 B-1 100 - - Example 7 J-7 A-2 10 B-1/B-2 70/30 - - Example 8 J-8 A-2 10 B-1/B-3 70/30 - - Example 9 J-9 A-2 10 B-1/B-4 99/1 - - Example 10 J-10 A-2 10 B-1 100 C-1 0.5 Example 11 J-11 A-2 10 B-1 100 C-2 0.5 Example 12 J-12 A-2 10 B-1 100 C-3 0.5 Example 13 J-13 A-2 10 B-1 100 C-4 0.5 Example 14 J-14 A-2 10 B-1 100 C-5 0.5 Example 15 J-15 A-2 10 B-1 100 C-6 0.5 Comparative example 1 j-1 a-1 10 B-1 100 - - Comparative example 2 j-2 a-2 10 B-1 100 - - Comparative example 3 j-3 a-3 10 B-1 100 - -

＜Cleaning of semiconductor substrate＞ Using the substrate treatment film forming composition of Example 1 to Example 15 and Comparative Example 1 to Comparative Example 3, the semiconductor substrate was cleaned by the following method.

Silicon dioxide particles with a particle size of 80 nm are attached to an 8-inch silicon wafer with a line and space pattern (1L1S, aspect ratio of 1) with a line width of 1,000 nm and a space formed thereon. On the silicon wafer, each composition for forming a substrate processing film was supplied, and a substrate on which the processing film was formed was obtained by a spin coating method under conditions of 1,500 rpm and 30 seconds. After the treatment film is formed, a liquid coating developing device is used to form a liquid film of a 2.38% by mass tetramethylammonium hydroxide aqueous solution as a peeling treatment liquid on the treatment film, thereby starting the immersion in the peeling treatment liquid. After 30 seconds from the start of immersion, the semiconductor substrate was washed with water and dried by a spin drying method.

＜Evaluation＞ Regarding the cleaned semiconductor substrate, the entire surface of the semiconductor substrate was analyzed using a dark field defect device ("KLA2800" of KLA-TENCOR) to evaluate the film removability and particle removability. The evaluation results are shown in Table 2 below.

Regarding film removability, the case where the residual defects other than silicon dioxide particles are less than 10/cm ² is evaluated as "A" (extremely good), and the case is more than 10/cm ² and less than 50/cm ² It was evaluated as "B" (good), and the case of 50 pieces/cm ² or more was evaluated as "C" (bad). Regarding particle removability, the case where the removal rate of silicon dioxide particles is 90% or more is evaluated as "A" (very good), and the case where the removal rate of silicon dioxide particles is more than 50% and less than 90% is evaluated as "B" (good). The case of less than 50% is evaluated as "C" (bad).

[Table 2] Composition for forming substrate processing film Membrane removability Particle removal Example 1 J-1 A B Example 2 J-2 A A Example 3 J-3 A A Example 4 J-4 A A Example 5 J-5 B B Example 6 J-6 B B Example 7 J-7 A A Example 8 J-8 A A Example 9 J-9 A A Example 10 J-10 A A Example 11 J-11 A A Example 12 J-12 A A Example 13 J-13 A A Example 14 J-14 A A Example 15 J-15 A A Comparative example 1 j-1 C C Comparative example 2 j-2 C C Comparative example 3 j-3 C C

As shown in Table 2, according to the composition for forming a substrate processing film of Examples, both the film removability and the particle removability are good or extremely good. On the other hand, in the composition for forming a substrate processing film of the comparative example, both the film removability and the particle removability were poor. [Industrial availability]

According to the composition for forming a substrate treatment film and the method for cleaning a semiconductor substrate of the present invention, in the process of forming a treatment film on the surface of a semiconductor substrate and removing minute particles attached to the surface of the substrate, it is possible to easily remove all materials from the surface of the substrate. The particles and the formed treatment film. Therefore, the present invention can be suitably used in the manufacturing steps of semiconductor elements that are expected to develop more and more miniaturized in the future.

1: Film forming treatment liquid 2: Volatile ingredients 3: pattern 4: particles 5: Stripping treatment liquid 6: Zeta potential B: Treatment membrane W: Wafer

FIG. 1A is an explanatory diagram showing a substrate processing film forming composition supply step in a semiconductor substrate cleaning method using the substrate processing film forming composition of the present invention. FIG. 1B is an explanatory diagram showing the formation of a treatment film in the semiconductor substrate cleaning method of the present invention. FIG. 1C is an explanatory diagram showing the step of supplying the peeling treatment liquid in the semiconductor substrate cleaning method of the present invention.

1: Film forming treatment liquid

2: Volatile ingredients

3: pattern

4: particles

W: Wafer

Claims (7)

A composition for forming a substrate treatment film, which is used in a cleaning method of a semiconductor substrate, and the cleaning method of the semiconductor substrate includes: The step of applying a composition for forming a substrate treatment film on a substrate; and A step of bringing the substrate treatment film removal liquid into contact with the substrate treatment film formed by the application step of the composition for forming the substrate treatment film, and The composition for forming a substrate processing film is characterized by containing: Polymer and solvent, and The polymer has a monovalent hydrocarbon group having 2 to 20 carbon atoms. The composition for forming a substrate treatment film according to claim 1, wherein the solvent includes an organic solvent, and the content of the organic solvent in the solvent is 90% by mass or more. The composition for forming a substrate processing film according to claim 1 or 2, wherein the monovalent hydrocarbon group having 2 to 20 carbon atoms is a monovalent aliphatic hydrocarbon group having 2 to 20 carbon atoms. The composition for forming a substrate treatment film according to claim 3, wherein the monovalent aliphatic hydrocarbon group having 2 to 20 carbon atoms is a monovalent aliphatic hydrocarbon group having 2 to 10 carbon atoms. The composition for forming a substrate treatment film according to claim 1 or 2, wherein the polymer is a novolak resin. The composition for forming a substrate processing film according to claim 1 or 2, which further contains a compound having at least one of a carboxyl group and an alcoholic hydroxyl group. A method for cleaning a semiconductor substrate includes: The step of applying a composition for forming a substrate treatment film on a substrate; and The step of bringing the substrate treatment film removal liquid into contact with the substrate treatment film formed by the coating step, and the substrate treatment film forming composition used in the semiconductor substrate cleaning method is characterized by: The composition for forming a substrate processing film contains: Polymer and solvent, and The polymer has a monovalent hydrocarbon group having 2 to 20 carbon atoms.

Images