Composition, method for treating substrate, method for producing semiconductor device, and compound

Abstract

The present invention provides a composition for semiconductor devices which has the excellent ability to remove dry-etching residues and is more inhibited from causing the dissolution of tungsten and which, when works are treated therewith and then rinsed, is less apt to leave a residue. This composition for semiconductor devices comprises water and a resin comprising repeating unit A, which has a hydroxy group and a specific group selected from the group consisting of a primary amino group, secondary amino group, tertiary amino group, and salts of these, and repeating unit B, which has a functional group having a pKa of 10.0 or less or has a salt thereof.

Description

Composition, substrate processing method, semiconductor device manufacturing method, and compound

[0001] The present invention relates to a composition, a method for treating a substrate, a method for manufacturing a semiconductor device, and a compound.

[0002] As semiconductor devices become increasingly miniaturized, there is an increasing demand for a highly efficient and accurate process for removing unwanted metal inclusions from a substrate during the semiconductor product manufacturing process.Semiconductor devices are manufactured, for example, by arranging a laminate having a metal layer, which will serve as a wiring material, an etching stop film, and an insulating film on a substrate, forming a resist film on this laminate, and then performing photolithography and dry etching processes.

[0003] In photolithography processes, a method for etching or removing foreign matter attached to the surface of a substrate using a composition that dissolves metal-containing materials is widely known. For example, in photolithography processes, a metal layer and / or an insulating film on a substrate may be etched by dry etching using a resist film as a mask. During this process, residues derived from the metal layer and / or the insulating film may adhere to the substrate, the metal layer, and the insulating film. Cleaning using a composition is often performed to remove the attached residues.

[0004] In addition, the resist film used as a mask during etching is removed from the laminate by a dry ashing method (dry ashing) or a wet ashing method. Residues derived from the resist film may adhere to the laminate from which the resist has been removed using the dry ashing method. Furthermore, in recent years, to achieve even greater miniaturization of semiconductor devices, metallic material-based resist films (so-called metal hard masks) such as TiN and AlOx have also been used as the resist film. When a metal hard mask is used as the resist film, a dry etching process (e.g., plasma etching) is typically performed using the metal hard mask as a mask to form holes based on the pattern shape of the metal hard mask and expose the metal film surface that will become the wiring film. Etching residues and / or ashing residues accumulate on the substrate after the dry etching process or dry ashing process. When a metal hard mask is used as the resist film, the residual components contain a large amount of metal components, such as titanium-based metals, while when a photoresist film is used, the residual components contain a large amount of organic components. To prevent these adhered residues from interfering with the next process, a cleaning process using a composition to remove the residues is often performed. Also, a wet method for removing a resist film can be exemplified by a method for removing a resist film using a composition. The above-described compositions for semiconductor devices are used in processes for removing metal-containing materials (etching residues and ashing residues) and / or resist films on substrates in semiconductor device manufacturing processes.

[0005] For example, Patent Document 1 describes a cleaning liquid used in a cleaning step of a semiconductor device substrate, which contains an organic acid, a sulfonic acid-type anionic surfactant, at least one polymer flocculant selected from polyvinylpyrrolidone and a polyethylene oxide-polypropylene oxide block copolymer, and water.

[0006] JP 2012-094852 A

[0007] The present inventors have used a cleaning solution containing polyvinylpyrrolidone as a composition for removing etching residues from a tungsten (W)-containing workpiece after dry etching, with reference to Patent Document 1. However, the cleaning solution was found to be insufficient in removing dry etching residues and in suppressing the dissolution of tungsten. Furthermore, even after cleaning the workpiece with the composition and then performing a rinsing process as described above, residues were likely to remain.

[0008] Therefore, an object of the present invention is to provide a composition for semiconductor devices that has excellent dry etching residue removal properties, further suppresses tungsten dissolution, and is less likely to leave residue when applied to a workpiece and then rinsed.Another object of the present invention is to provide a substrate processing method using the composition, a semiconductor device manufacturing method, and a compound.

[0009] The present inventors have conducted extensive research to solve the above problems and have completed the present invention. That is, they have found that the above problems can be solved by the following configuration.

[0010] [1] A composition for semiconductor devices, comprising: a resin containing a repeating unit A having a specific group selected from the group consisting of a primary amino group, a secondary amino group, a tertiary amino group, and salts thereof, and a hydroxy group; and a repeating unit B having a functional group having a pKa of 10.0 or less or a salt thereof; and water. [2] The composition for semiconductor devices according to [1], wherein the repeating unit A is a repeating unit derived from a compound represented by formula (A) described below, a repeating unit derived from a compound represented by formula (B) described below, or a repeating unit represented by formula (C) described below. [3] The composition for semiconductor devices according to [1] or [2], wherein at least one of the specific groups is a primary amino group or a salt thereof. [4] The composition for semiconductor devices according to [1] or [2], wherein the repeating unit A is selected from the group consisting of L ａ a repeating unit derived from the compound represented by the formula (A) above, wherein L is a (na+2)-valent linking group containing an aromatic ring; ｂ１ and L ｂ２The composition for a semiconductor device according to [2] or [3], wherein the repeating unit A is a repeating unit derived from a compound represented by formula (B) above, or a repeating unit represented by formula (C), wherein at least one of the repeating units A and B is a divalent linking group containing an aromatic ring. [5] The composition for a semiconductor device according to [1] or [3], wherein the repeating unit A is a repeating unit derived from a compound represented by formula (D) described below, or a repeating unit represented by formula (E) described below. [6] The composition for a semiconductor device according to any one of [1] to [5], wherein the pKa of the functional group is 5.0 or less. [7] The composition for a semiconductor device according to any one of [1] to [6], wherein the functional group is a carboxy group. [8] The composition according to any one of [1] to [7], further comprising at least one selected from the group consisting of a remover, an oxidizer, a corrosion inhibitor, a surfactant, an antifoaming agent, and an organic solvent. [9] The composition according to any one of [1] to [8], further comprising a remover.

[10] A method for treating a substrate, comprising step A of contacting a substrate having metal inclusions with the composition according to any one of [1] to [9].

[11] The method for treating a substrate according to

[10] , further comprising step B of rinsing the substrate obtained in step A with a rinse liquid after step A.

[12] A method for producing a semiconductor device, comprising the method for treating a substrate according to

[10] or

[11] .

[13] A compound represented by formula (F) described later.

[0011] According to the present invention, there is provided a composition for semiconductor devices that has excellent dry etching residue removal properties, further suppresses tungsten dissolution, and is less likely to leave residue when applied to a substrate and then rinsed. The present invention also provides a substrate processing method, a semiconductor device manufacturing method, and a compound using the composition.

[0012] 1 is a cross-sectional view showing an example of a laminate that is a processing target of a substrate processing method.

[0013] The present invention will be described in detail below. The following description of the components may be based on representative embodiments of the present invention, but the present invention is not limited to such embodiments.

[0014] The following describes the meaning of each description in this specification. In this specification, a numerical range expressed using "to" means a range that includes the numerical values ​​before and after "to" as the lower and upper limits. In this specification, when two or more types of a component are present, the "content" of that component means the total content of those two or more components. In this specification, "total solids" means the total content of all components contained in the composition other than solvents such as water and organic solvents. In this specification, "preparation" includes providing a specified item by processing such as synthesizing or blending raw materials, as well as procuring a specified item by purchasing, etc.

[0015] Unless otherwise specified, the compounds described herein may contain structural isomers, optical isomers, and isotopes. Furthermore, the structural isomers, optical isomers, and isotopes may be present alone or in combination with one or more other types. Unless otherwise specified herein, the bonding direction of a divalent group (e.g., —COO—) is not limited. For example, when Y is —COO— in a compound represented by the formula "X-Y-Z," the compound may be either "X-O-CO-Z" or "X-CO-O-Z." Unless otherwise specified herein, the symbol "*" in a chemical formula indicates a bonding position.

[0016] As used herein, "ppm" stands for "parts-per-million (10 －６ ) and "ppb" stands for "parts-per-billion (10 －９ ) and "ppt" stands for "parts-per-trillion (10 －１２ In this specification, 1 Å (angstrom) corresponds to 0.1 nm.

[0017] Unless otherwise specified, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) are values ​​measured by a gel permeation chromatography (GPC) analyzer using TSKgel GMHxL, TSKgel G4000HxL, or TSKgel G2000HxL (all manufactured by Tosoh Corporation) as a column, tetrahydrofuran as an eluent, a differential refractometer as a detector, and polystyrene as a standard substance, converted using polystyrene as a standard substance. Unless otherwise specified, the molecular weight of a compound having a molecular weight distribution is a weight-average molecular weight.

[0018] [Composition] The composition of the present invention (hereinafter also referred to as "the composition") will be described in detail below. The composition is a composition for semiconductor devices that contains a resin (hereinafter also referred to as "the specific resin") that includes a repeating unit A having a hydroxyl group and a specific group selected from the group consisting of a primary amino group, a secondary amino group, a tertiary amino group, and salts thereof, and a repeating unit B having a functional group having a pKa of 10.0 or less or a salt thereof, and water.

[0019] The present inventors discovered that the present composition containing the specific resin and water can further suppress tungsten dissolution, provide excellent residue removal, and leave little residue even after a rinsing process, and thus completed the present invention. Hereinafter, the term "excellent effects of the present invention" refers to the superiority of at least one of the following: the suppression of tungsten dissolution, the excellent residue removal, and the low residue even after a rinsing process. The mechanism by which the present composition can solve the problems of the present invention by adopting the above-described configuration is not necessarily clear, but the present inventors speculate as follows. Note that the following speculation does not limit the mechanism by which the problems can be solved. In other words, even if the problems can be solved by a mechanism other than those described below, it is still within the scope of the present invention.

[0020] When this composition is used to treat a tungsten-containing workpiece, the repeating unit A contains both a hydroxyl group and a specific group, which are easily adsorbed to tungsten, and therefore easily forms a suitable protective film composed of a specific resin on the tungsten surface. While a sufficient effect is not obtained with resins such as polyethyleneimine, which only contains the specific group, or resins in which the hydroxyl group and the specific group are present in different repeating units, tungsten dissolution is suppressed in resins in which the hydroxyl group and the specific group are present in the same repeating unit, as in the case of specific resins. While the detailed mechanism is unknown, the inventors speculate that the proximity of the hydroxyl group and the specific group results in the effective formation of the protective film, thereby further suppressing tungsten elution. Furthermore, the presence of the repeating unit B in this composition provides excellent affinity with rinse solutions. Therefore, the composition also exhibits excellent removability of residues (e.g., residues derived from the resin in this composition) when applied to a workpiece and then rinsed. Below, each component of this composition is described in detail.

[0021] [Specific Resin] The present composition contains a resin containing repeating units A and B (specific resin).

[0022] <Repeating Unit A> The repeating unit A is a repeating unit having a specific group selected from the group consisting of a primary amino group, a secondary amino group, a tertiary amino group, and salts thereof, and a hydroxy group. The primary amino group is a group represented by -NH ２ A secondary amino group is a group represented by -NHR Ａ１ (R Ａ１ represents a monovalent aliphatic hydrocarbon group or a monovalent aromatic ring group. Ａ２ ) ２ (R Ａ２ each independently represents a monovalent aliphatic hydrocarbon group or a monovalent aromatic ring group.

[0023] R Ａ１ or R Ａ２The monovalent aliphatic hydrocarbon group represented by the formula (I) may be linear, branched, or cyclic. The aliphatic hydrocarbon group may further have a substituent. When the aliphatic hydrocarbon group further has a substituent, it preferably has a specific group, a hydroxy group, or a halogen atom. The aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6, and even more preferably 1 or 2 carbon atoms. Examples of the aliphatic hydrocarbon group include alkyl groups, alkenyl groups, and alkynyl groups, and among these, alkyl groups having 1 to 6 carbon atoms are preferred, and alkyl groups having 1 or 2 carbon atoms are more preferred.

[0024] R Ａ１ or R Ａ２ The aromatic ring constituting the monovalent aromatic ring group represented by the formula (I) may be either a monocyclic or polycyclic ring. The number of ring-member atoms in the aromatic ring constituting the monovalent aromatic ring group is preferably 5 to 20, more preferably 5 to 10, and even more preferably 5 or 6. The monovalent aromatic ring group may be an aryl group or a heteroaryl group. The heteroatom contained in the heteroaryl group is preferably an oxygen atom, a nitrogen atom, or a sulfur atom.

[0025] The salt is a salt containing at least one group (specific group) selected from the group consisting of primary amino groups, secondary amino groups, and tertiary amino groups. The compound that forms the salt is not particularly limited, but examples include acidic compounds. That is, the salt is preferably a salt formed between at least one group selected from the group consisting of primary amino groups, secondary amino groups, and tertiary amino groups and an acidic compound. The acidic compound may be either an inorganic acid or an organic acid. Examples of inorganic acids include hydrochloric acid, sulfuric acid, phosphoric acid, and nitric acid. Examples of organic acids include acetic acid, propionic acid, methanesulfonic acid, ethanesulfonic acid, allylglycine, maleic acid, citraconic acid, fumaric acid, and itaconic acid. When a primary amino group, secondary amino group, or tertiary amino group forms a salt, the acid is preferably hydrochloric acid, acetic acid, propionic acid, methanesulfonic acid, or ethanesulfonic acid, and more preferably hydrochloric acid, acetic acid, or ethanesulfonic acid.

[0026] The number of specific groups contained in the repeating unit A is not particularly limited, but is preferably 1 to 5, more preferably 1 or 2, and even more preferably 1. When the repeating unit A contains multiple specific groups, it is preferable that at least one of the specific groups is a primary amino group or a salt thereof. Furthermore, the number of hydroxy groups contained in the repeating unit A is not particularly limited, but is preferably 1 to 5, more preferably 1 or 2, and even more preferably 1. The hydroxy group contained in the repeating unit A is preferably a hydroxy group (a hydroxy group that is not a phenolic hydroxy group) bonded to a carbon atom in an aliphatic hydrocarbon. It is also preferable that the repeating unit A contains an aromatic ring.

[0027] In terms of achieving better effects of the present invention, the repeating unit A is preferably a repeating unit derived from a compound represented by formula (A), a repeating unit derived from a compound represented by formula (B), or a repeating unit represented by formula (C).

[0028]

[0029] In formula (A), R ａ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ａ Examples of the alkyl group having 1 to 4 carbon atoms represented by the formula (R) include a methyl group, an ethyl group, an isopropyl group, and a t-butyl group. ａ is preferably a hydrogen atom or a methyl group.

[0030] In formula (A), X ａ represents a specific group selected from the group consisting of a primary amino group, a secondary amino group, a tertiary amino group, and salts thereof. ａ Specific and preferred embodiments of the specific group are as described above for the specific group.

[0031] In formula (A), L ａ represents a (na+2)-valent linking group, and na represents an integer of 1 to 5. na is preferably 1 to 3, more preferably 1 or 2, and even more preferably 1. L ａExamples of the (na+2)-valent linking group represented by the formula (1) include an (na+2)-valent aliphatic hydrocarbon group, an (na+2)-valent aromatic ring group, —O—, —CO— (carbonyl group), —SO ２ -, -N<, -NR Ｌ - (R Ｌ represents a hydrogen atom or a monovalent aliphatic hydrocarbon group, and groups formed by combining these groups.

[0032] The (na+2)-valent aliphatic hydrocarbon group is a group obtained by removing (na+2) hydrogen atoms from an aliphatic hydrocarbon. The aliphatic hydrocarbon may be linear, branched, or cyclic, but linear is preferred. The aliphatic hydrocarbon preferably has 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms, and even more preferably 1 or 2 carbon atoms. Examples of aliphatic hydrocarbons include alkanes, alkenes, and alkynes.

[0033] The (na+2)-valent aromatic ring group is a group obtained by removing (na+2) hydrogen atoms from an aromatic hydrocarbon ring or an aromatic heterocycle. The aromatic hydrocarbon ring and aromatic heterocycle may be either a monocycle or a polycycle. The number of ring-member atoms in the aromatic ring constituting the monovalent aromatic ring group is preferably 5 to 20, more preferably 5 to 10, and even more preferably 5 or 6. Examples of the aromatic ring include a benzene ring.

[0034] Examples of the aromatic hydrocarbon ring include a benzene ring, a naphthalene ring, an anthracene ring, a fluorene ring, and a phenanthrene ring. Examples of the aromatic heterocycle include a pyridine ring, a pyrimidine ring, a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, an oxazole ring, a thiazole ring, a benzofuran ring, a benzothiophene ring, a benzimidazole ring, a benzoxazole ring, a benzothiazole ring, and a benzothiadiazole ring.

[0035] Above -NR Ｌ In the group represented by -, R Ｌ Examples of the monovalent aliphatic hydrocarbon group represented by the formula (I) include alkyl groups having 1 to 10 carbon atoms. Ｌis preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 2 carbon atoms.

[0036] L ａ is also preferably a (na+2)-valent linking group containing an aromatic ring. The aromatic ring may be either an aromatic hydrocarbon ring or an aromatic heterocycle. Examples of the aromatic hydrocarbon ring include a benzene ring and a naphthalene ring, with a benzene ring being preferred. Examples of the aromatic heterocycle include an imidazole ring, a pyrazole ring, a thiazole ring, a triazole ring, a tetrazole ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, and a triazine ring, with an imidazole ring, a pyridine ring, or a triazine ring being preferred among these rings.

[0037] L when na is 1 ａ Examples of the (na+2)-valent linking group represented by the formula (A) include *-divalent aromatic ring group-O-trivalent aliphatic hydrocarbon group<, *-CO-O-trivalent aliphatic hydrocarbon group<, trivalent aromatic ring group, *-CO-NH-divalent aromatic ring group-O-trivalent aliphatic hydrocarbon group<, *-O-trivalent aliphatic hydrocarbon group<, *-divalent aromatic ring group-CO-O-trivalent aliphatic hydrocarbon group<, *-divalent aromatic ring group-divalent aliphatic hydrocarbon group-O-trivalent aliphatic hydrocarbon group<, and *-CO-O-trivalent aliphatic hydrocarbon group-NH-divalent aliphatic hydrocarbon-. Note that the * represents R ａ The group represented by *-CO-O-trivalent aliphatic hydrocarbon group-NH-divalent aliphatic hydrocarbon group- is a group represented by the following formula (L), and R ａｌ３ represents a trivalent aliphatic hydrocarbon group, R ａｌ２ represents a divalent aliphatic hydrocarbon group.

[0038]

[0039] In the above formula (B), R ｂ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ｂ Specific and preferred embodiments of the alkyl group having 1 to 4 carbon atoms represented by the above R ａThe specific and preferred embodiments are the same as those of the alkyl group having 1 to 4 carbon atoms which may have a substituent and is represented by the following formula: ｂ is preferably a hydrogen atom or a methyl group.

[0040] In the above formula (B), R Ｎ represents a hydrogen atom or an alkyl group which may have a substituent. The alkyl group which may have a substituent may be linear, branched, or cyclic. The alkyl group which may have a substituent preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 or 2 carbon atoms. R Ｎ When the alkyl group represented by the formula (I) further has a substituent, it preferably has a specific group or a hydroxy group.

[0041] In the above formula (B), L ｂ１ and L ｂ２ each independently represents a single bond or a divalent linking group. ｂ１ and L ｂ２ Examples of the divalent linking group represented by the formula (I) include a divalent aliphatic hydrocarbon group, a divalent aromatic ring group, -O-, -CO- (carbonyl group), and a group formed by combining these groups.

[0042] The divalent aliphatic hydrocarbon group may be linear, branched, or cyclic, but is preferably linear. The number of carbon atoms in the divalent aliphatic hydrocarbon group is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 or 2. Examples of the divalent aliphatic hydrocarbon group include alkylene groups and alkenylene groups.

[0043] The divalent aromatic ring group may be either an arylene group or a heteroarylene group, and the aromatic ring constituting the divalent aromatic ring group may be either a monocyclic or polycyclic ring. The number of ring member atoms in the aromatic ring constituting the divalent aromatic ring group is preferably 5 to 20, more preferably 5 to 10, and even more preferably 5 or 6. Examples of the aromatic ring include a benzene ring.

[0044] L ｂ１ and L ｂ２Among these, an alkylene group is preferable, an alkylene group having 1 to 6 carbon atoms is more preferable, and a methylene group or an ethylene group is even more preferable. ｂ１ and L ｂ２ It is also preferred that at least one of the aromatic rings is a divalent linking group containing an aromatic ring. ａ The specific and preferred embodiments of the aromatic ring that can be contained in the above are the same as those of the above.

[0045] In formula (C), R ｃ represents a hydrogen atom or a methyl group. ｃ represents a specific group selected from the group consisting of a primary amino group, a secondary amino group, a tertiary amino group, and salts thereof. ｃ Specific and preferred embodiments of the specific group are as described above for the specific group.

[0046] In formula (C), L ｃ represents a (nc+2)-valent linking group, and nc represents an integer of 1 to 5. nc is preferably 1 to 3, more preferably 1 or 2, and even more preferably 1. L ｃ Examples of the (nc+2)-valent linking group represented by the formula (I) include an (nc+2)-valent aliphatic hydrocarbon group, an (nc+2)-valent aromatic ring group, —O—, —CO— (carbonyl group), —SO ２ -, -N<, -NR Ｌ - (R Ｌ represents a hydrogen atom or a monovalent aliphatic hydrocarbon group.) and groups formed by combining these groups. Specific and preferred embodiments of these linking groups include L ａ The (na+2)-valent linking group represented by the formula: ｃ Among these, the (nc+2)-valent linking group represented by the formula (I) is preferably an (nc+2)-valent aliphatic hydrocarbon group. Examples of the aliphatic hydrocarbon include alkanes, alkenes, and alkynes. The aliphatic hydrocarbon preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 3 carbon atoms.

[0047] It is also preferable that the repeating unit A is a repeating unit derived from a compound represented by formula (D) or a repeating unit represented by formula (E).

[0048]

[0049] In formula (D), R ｄ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ｄ Examples of the alkyl group having 1 to 4 carbon atoms represented by the formula (I) include a methyl group, an ethyl group, and an isopropyl group.

[0050] In formula (D), L ｄ represents a single bond or a divalent linking group. ｄ Examples of the divalent linking group represented by the formula (I) include a divalent aliphatic hydrocarbon group, a divalent aromatic ring group, —O—, —CO— (carbonyl group), —NR Ｌ - (R Ｌ represents a hydrogen atom or a monovalent aliphatic hydrocarbon group. ), and groups formed by combining these groups. Specific and preferred embodiments of the divalent aliphatic hydrocarbon group and the divalent aromatic ring group are described in detail in the section on L in formula (B). ｂ１ or L ｂ２ The specific and preferred embodiments are the same as those of the divalent aliphatic hydrocarbon group and the divalent aromatic ring group represented by the following formula:

[0051] Above -NR Ｌ In the group represented by -, R Ｌ Examples of the monovalent aliphatic hydrocarbon group represented by the formula (I) include alkyl groups having 1 to 10 carbon atoms. Ｌ is preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 2 carbon atoms.

[0052] L ｄ Examples of the divalent linking group represented by the formula (I) include -divalent aliphatic hydrocarbon group-, -COO- (ester bond)-divalent aliphatic hydrocarbon group-, -CONH- (amide bond)-divalent aliphatic hydrocarbon group-, -divalent aromatic ring group -O-, and -divalent aromatic ring group -CH ２ -O-, -divalent aromatic ring group -C≡C-CH ２-O-, and a divalent aromatic ring group -COO-.

[0053] In formula (D), R ｄ２ represents a group represented by formula (X) or a group represented by formula (Y). In formulas (X) and (Y), X represents a primary amino group or a salt thereof. Specific and preferred embodiments of the salt of the primary amino group are as described above.

[0054] In formula (E), R ｅ１ represents a hydrogen atom or a methyl group.

[0055] In formula (E), L ｅ represents a divalent linking group. ｅ Examples of the divalent linking group represented by the formula (I) include a divalent aliphatic hydrocarbon group, a divalent aromatic ring group, —O—, —CO— (carbonyl group), —NR Ｌ - (R Ｌ represents a hydrogen atom or a monovalent aliphatic hydrocarbon group. ), and groups formed by combining these groups. Specific and preferred embodiments of the divalent aliphatic hydrocarbon group and the divalent aromatic ring group are described in detail in the section on L in formula (B). ｂ１ or L ｂ２ The specific embodiments and preferred embodiments are the same as those of the divalent aliphatic hydrocarbon group and the divalent aromatic ring group represented by the following formula: ｅ The divalent linking group represented by the formula (I) is preferably a divalent aliphatic hydrocarbon group.

[0056] In formula (E), R ｅ２ represents a group represented by the above formula (X) or a group represented by the above formula (Y).

[0057] The compound represented by formula (D) is preferably a compound represented by formula (F) in that the effects of the present invention are more excellent.

[0058]

[0059] In formula (F), X ｆ represents a specific group selected from the group consisting of a primary amino group, a secondary amino group, a tertiary amino group, and salts thereof. ｆSpecific and preferred embodiments of the primary amino group, secondary amino group, tertiary amino group, and salts thereof are described in the section of X in formula (A). ａ The specific and preferred embodiments are the same as those of the salts mentioned above. Of these, hydrochlorides, sulfates, acetates, and carbonates are preferred.

[0060] L ｆ is -CH ２ O-, -COO-, -C≡C-CH ２ It represents O- or -O-.

[0061] The specific resin may have only one type of repeating unit A, or two or more types. The content of repeating unit A in the specific resin is preferably 1 mol% or more, more preferably 5 mol% or more, more preferably 10 mol% or more, and even more preferably 25 mol% or more, based on the total repeating units in the specific resin, in order to achieve better effects of the invention. The upper limit of the content of repeating unit A is not particularly limited, but is preferably 99 mol% or less, more preferably 95 mol% or less, even more preferably 80 mol% or less, and particularly preferably 70 mol% or less, based on the total repeating units in the specific resin. When the specific resin has two or more types of repeating unit A, it is preferable that the total content be within the above range.

[0062] The structure and composition ratio (molar fraction) of each repeating unit contained in the specific resin may be, for example, １３ It can be measured by C-NMR.

[0063] <Repeating Unit B> The repeating unit B is a repeating unit having a functional group or a salt thereof having a pKa of 10.0 or less. The pKa of the functional group is not particularly limited as long as it is 10.0 or less, but is preferably 7.0 or less, and more preferably 5.0 or less. The lower limit of the pKa of the functional group is not particularly limited, but is preferably -3.0 or more, and more preferably 1.0 or more. The functional group having a pKa of 10.0 or less is not particularly limited, but examples thereof include acid groups. More specific examples of functional groups having a pKa of 10.0 or less include carboxy groups, phosphonic acid groups, sulfo groups, and phenolic hydroxy groups. Carboxy groups or sulfo groups are preferred, and carboxy groups are more preferred in terms of providing better solubility of the specific resin in post-treatment solutions (such as the rinse solution described below). Examples of the salt include salts of acid groups. A salt of an acid group refers to a salt in which the hydrogen ion of the acid group is replaced with another cation such as a metal ion (e.g., a sodium ion). The number of functional groups having a pKa of 10.0 or less that the repeating unit B has is not particularly limited, but is preferably 1 to 4, more preferably 1 to 3, and even more preferably 1 or 2.

[0064] Examples of the repeating unit B include a repeating unit represented by formula (G) and a repeating unit represented by formula (H).

[0065]

[0066] In formula (G), R ｇ１ , R ｇ２ and R ｇ３ each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an acid group. ｇ represents a single bond or a (k+1)-valent linking group. ｇ represents a functional group or a salt thereof having a pKa of 10.0 or less, and k represents an integer of 1 to 4. In formula (G), A ｇ If there are multiple A's, ｇ may be the same or different.

[0067] R ｇ１ , R ｇ２ and R ｇ３is preferably a hydrogen atom, a methyl group, an ethyl group, a carboxymethyl group, or a carboxy group, and more preferably a hydrogen atom, a methyl group, or a carboxy group. ｇ１ , R ｇ２ and R ｇ３ It is preferred that one of represents a hydrogen atom, a methyl group or a carboxy group, and the remaining two each represent a hydrogen atom.

[0068] L ｇ Examples of the (k+1)-valent linking group represented by the formula: ｇ There are no particular limitations on the group as long as it has a valence corresponding to the number of groups. Examples of the group include an optionally substituted di- to pentavalent aliphatic hydrocarbon group, an optionally substituted di- to pentavalent aromatic ring group, -O-, -CO-, -SO ２ -, -NR Ｌ -, -N<, and groups formed by combining these. Ｌ When k is 1, the divalent linking group may be a divalent aliphatic hydrocarbon group, a divalent aromatic ring group, —O—, —CO—, —SO ２ -, -NR Ｌ -, and groups formed by combining these. The divalent aliphatic hydrocarbon group may be linear, branched, or cyclic. As the divalent aliphatic hydrocarbon group, an alkylene group having 1 to 6 carbon atoms (preferably 1 to 3 carbon atoms) is preferred. When k is 1, L ｇ is a single bond, an alkylene group, a divalent aromatic group, or an -alkylene group -NR Ｌ An alkylene group is preferred, and a single bond, a methylene group, a phenylene group, or a methylene group -NH-methylene group is preferred.

[0069] A ｇ The preferred embodiments of the functional group or salt thereof having a pKa of 10.0 or less are as described above. k is preferably an integer of 1 to 3, and more preferably 1 or 2.

[0070] In formula (H), R ｈ represents a hydrogen atom or a methyl group. ｈ represents a single bond or an (m+1)-valent linking group.ｈ represents a functional group or a salt thereof having a pKa of 10.0 or less. m represents an integer of 1 to 4. In formula (H), A ｈ If there are multiple A's, ｈ may be the same or different.

[0071] L ｈ Specific and preferred embodiments of the (m+1)-valent linking group represented by the formula: ｇ When m is 1, L ｈ is preferably a divalent aliphatic hydrocarbon group, a divalent aromatic group, or an -O-divalent aliphatic hydrocarbon group -OCO-divalent aliphatic hydrocarbon group. The divalent aliphatic hydrocarbon group may be linear, branched, or cyclic. Furthermore, a hydrogen atom in the divalent aliphatic hydrocarbon group may be substituted with a substituent such as a hydroxy group. Among these, the divalent aliphatic hydrocarbon group is preferably an alkylene or alkenylene group having 1 to 6 carbon atoms, and more preferably an alkylene or alkenylene group having 1 to 3 carbon atoms.

[0072] A ｈ The preferred embodiments of the functional group or salt thereof having a pKa of 10.0 or less are as described above. m is preferably an integer of 1 to 3, and more preferably 1 or 2.

[0073] The specific resin may have only one type of repeating unit B, or may have two or more types. In order to improve the solubility of the specific resin in the post-treatment liquid, the content of repeating unit B is preferably 1 mol% or more, more preferably 5 mol% or more, even more preferably 20 mol% or more, and particularly preferably 30 mol% or more, based on the total repeating units in the specific resin. There is no particular upper limit, but it is preferably 99 mol% or less, more preferably 95 mol% or less, even more preferably 90 mol% or less, and particularly preferably 75 mol% or less, based on the total repeating units in the specific resin.

[0074] The ratio of repeating units A to repeating units B in the specific resin is not particularly limited, but the ratio (a / b) of the number of moles a of repeating units A to the number of moles b of repeating units B is preferably 1 / 99 or more, more preferably 5 / 95 or more, even more preferably 10 / 90 or more, and particularly preferably 25 / 75 or more. The lower limit of the ratio (a / b) is not particularly limited, but in terms of better solubility of the specific resin in the post-treatment liquid, the ratio a / b is preferably 99 / 1 or less, more preferably 95 / 5 or less, even more preferably 80 / 20 or less, and particularly preferably 70 / 30 or less.

[0075] In the specific resin, the repeating units A and B may be bonded randomly (so-called random copolymer), alternately (so-called alternating copolymer), or block-like (so-called block copolymer).

[0076] The specific resin may have a repeating unit different from both the repeating unit A and the repeating unit B. The content of the repeating unit different from both the repeating unit A and the repeating unit B in the specific resin is preferably 25 mol % or less, more preferably 0 to 10 mol %, and even more preferably 0 to 5 mol %, based on the total repeating units in the specific resin. It is preferable that the specific resin does not have a repeating unit different from both the repeating unit A and the repeating unit B.

[0077] The weight-average molecular weight Mw of the specific resin is not particularly limited, and is preferably 500 to 1,000,000. Among these, the Mw of the specific resin is more preferably 1,000 or more, even more preferably 2,000 or more, and particularly preferably 5,000 or more, in terms of achieving better effects of the present invention. Furthermore, the weight-average molecular weight Mw is more preferably 500,000 or less, even more preferably 100,000 or less, and particularly preferably 50,000 or less, in terms of achieving better solubility of the specific resin in the post-treatment liquid.

[0078] The specific resin may be used alone or in combination of two or more. The content of the specific resin is preferably 1 ppm by mass to 10% by mass, more preferably 10 to 10,000 ppm by mass (1% by mass), even more preferably 50 to 5,000 ppm by mass, and most preferably 50 to 2,000 ppm by mass, relative to the total mass of the composition. Furthermore, when the composition contains optional components described below in addition to the specific resin and solvent, the content of the specific resin is preferably 0.1 to 10.0% by mass, more preferably 0.3 to 3.0% by mass, relative to the total solid content in the composition.

[0079] [Water] The present composition contains water. The water content is not particularly limited, but is preferably 1 to 99.9999% by mass, more preferably 50 to 98% by mass, and even more preferably 80 to 97% by mass, relative to the total mass of the present composition. Ultrapure water used in the manufacture of semiconductor devices is preferred. Water with reduced inorganic anions and metal ions is particularly preferred. Water with reduced ion concentrations of Fe, Co, Na, K, Ca, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn is particularly preferred. Water adjusted to the order of ppt or less (in one embodiment, the metal content is less than 0.001 ppt by mass) before use in preparing the present composition is even more preferred. The preferred adjustment method is purification using a filtration membrane or ion exchange membrane, or purification by distillation. Examples of the adjustment method include the method described in paragraphs

[0074] to

[0084] of JP-A No. 2011-110515 and the method described in JP-A No. 2007-254168.

[0080] It is preferable that the water be water in which the content of each ion has been adjusted. Furthermore, in order to significantly obtain the desired effects of the present invention, it is more preferable that the above-mentioned water be used not only for the present composition but also for cleaning containers. Furthermore, it is preferable that the above-mentioned water be used in the production process of the present composition, for measuring the components of the present composition, and for measuring the evaluation of the present composition.

[0081] [Optional Components] The composition may further contain components other than the above components, such as a remover, an oxidizing agent, a corrosion inhibitor, a surfactant, an antifoaming agent, and an organic solvent.

[0082] <Removing Agent> The present composition may contain a removing agent, and preferably contains a removing agent in that it has better residue removal properties. The removing agent is not particularly limited as long as it is a compound that has the function of removing residues such as etching residues and ashing residues, and examples of the removing agent include fluorine-containing compounds, hydroxylamine compounds, basic compounds, and acidic compounds.

[0083] (Fluorine-containing compound) The fluorine-containing compound is not particularly limited as long as it is a compound containing a fluorine atom, and may be an inorganic compound containing a fluorine atom or an organic compound containing a fluorine atom. Examples of fluorine-containing compounds include hydrofluoric acid (hydrofluoric acid), ammonium fluoride, tetramethylammonium fluoride, and tetrabutylammonium fluoride. The fluorine-containing compound has the function of removing residues in the composition. As a result, when the composition contains a fluorine-containing compound, the residue removability is more excellent. As the fluorine-containing compound, hydrofluoric acid, ammonium fluoride, or tetramethylammonium fluoride is preferred, and hydrofluoric acid or ammonium fluoride is more preferred.

[0084] The fluorine-containing compound may be used alone or in combination of two or more. When the composition contains a fluorine-containing compound, the content of the fluorine-containing compound is preferably 0.01 to 15.0 mass%, more preferably 0.1 to 10.0 mass%, based on the total mass of the composition.

[0085] (Hydroxylamine Compound) The present composition may contain a hydroxylamine compound as a remover. The hydroxylamine compound is hydroxylamine (NH ２The remover is at least one compound selected from the group consisting of hydroxylamine derivatives, hydroxylamine derivatives, and salts thereof. The hydroxylamine compound has the function of promoting the decomposition and solubilization of residues and removing residues such as etching residues and ashing residues. Therefore, the present composition preferably contains a hydroxylamine compound as a remover.

[0086] The hydroxylamine derivative is not particularly limited, and examples thereof include O-methylhydroxylamine, O-ethylhydroxylamine, N-methylhydroxylamine, N,N-dimethylhydroxylamine, N,O-dimethylhydroxylamine, N-ethylhydroxylamine, N,N-diethylhydroxylamine, N,O-diethylhydroxylamine, O,N,N-trimethylhydroxylamine, N,N-dicarboxyethylhydroxylamine, and N,N-disulfoethylhydroxylamine.

[0087] Salts of hydroxylamine and hydroxylamine derivatives include inorganic acid salts or organic acid salts, with inorganic acid salts formed by the bonding of non-metallic atoms such as Cl, S, N, and P with hydrogen atoms being preferred, and salts of any of hydrochloric acid, sulfuric acid, and nitric acid being more preferred. Preferred inorganic acid salts of hydroxylamine and hydroxylamine derivatives include hydroxylamine nitrate, hydroxylamine sulfate, hydroxylamine hydrochloride, hydroxylamine phosphate, N,N-diethylhydroxylamine sulfate, N,N-diethylhydroxylamine nitrate, or mixtures thereof. Examples of organic acid salts of hydroxylamine and hydroxylamine derivatives include hydroxylammonium citrate, hydroxylammonium oxalate, and hydroxylammonium fluoride. Preferred hydroxylamine compounds are hydroxylamine and hydroxylamine sulfate due to their superior residue removal properties.

[0088] The hydroxylamine compound may be used alone or in combination of two or more. When the composition contains a hydroxylamine compound, the content of the hydroxylamine compound is preferably 0.01 to 30% by mass, more preferably 0.5 to 25% by mass, based on the total mass of the composition.

[0089] (Basic Compound) The present composition may contain a basic compound as a remover. A basic compound is intended to mean a compound that, when dissolved in water, causes the solution to have a pH of more than 7. The basic compound also functions as a pH adjuster that adjusts the pH of the present composition. In this specification, compounds contained in the corrosion inhibitor described below are not included in the basic compound. The basic compound may form a salt with an acid group contained in the repeating unit B of the specific resin.

[0090] The basic compound is not particularly limited, and examples thereof include ammonium hydroxide, water-soluble amines, and quaternary ammonium compounds. The ammonium hydroxide, water-soluble amines, and quaternary ammonium compounds are each described in detail below.

[0091] The composition contains ammonium hydroxide (NH ４ When the present composition contains ammonium hydroxide, the content of ammonium hydroxide is preferably 0.01 to 15.0 mass %, more preferably 0.05 to 10.0 mass %, based on the total mass of the present composition.

[0092] The present composition may contain a water-soluble amine as a basic compound. In this specification, the term "water-soluble amine" refers to a compound having at least one group selected from the group consisting of a primary amino group, a secondary amino group, and a tertiary amino group in its molecule, and capable of dissolving at least 50 g in 1 L of water. Examples of water-soluble amines include primary amines having a primary amino group in their molecule, secondary amines having a secondary amino group in their molecule, tertiary amines having a tertiary amino group in their molecule, and salts thereof. Examples of salts of the amines include salts with inorganic acids formed by bonding at least one nonmetal selected from the group consisting of Cl, S, N, and P with hydrogen, with hydrochlorides, sulfates, or nitrates being preferred. The water-soluble amine is preferably a low-molecular-weight compound. In this specification, "low-molecular-weight compound" refers to a compound that does not substantially have a molecular weight distribution. The molecular weight of the low-molecular-weight compound is preferably 1,000 or less. All of the specific examples of water-soluble amines listed below are low-molecular-weight compounds having a molecular weight of 1,000 or less. The water-soluble amine may be an alicyclic amine compound having a ring structure in the molecule, or may be an alkanolamine having at least one hydroxyalkyl group in the molecule.

[0093] The water-soluble amine may be used alone or in combination of two or more. When the composition contains a water-soluble amine, the content of the water-soluble amine is preferably 0.01 to 10% by mass, more preferably 0.1 to 5.0% by mass, based on the total mass of the composition.

[0094] The present composition may contain, as a remover, a quaternary ammonium compound having one quaternary ammonium cation group in the molecule. The quaternary ammonium compound is not particularly limited as long as it is a compound having at least one quaternary ammonium cation group in which four hydrocarbon groups (preferably alkyl groups) are substituted on a nitrogen atom. Examples of the quaternary ammonium compound include quaternary ammonium hydroxide, quaternary ammonium fluoride, quaternary ammonium bromide, quaternary ammonium iodide, quaternary ammonium acetate, and quaternary ammonium carbonate.

[0095] The quaternary ammonium compound is preferably a quaternary ammonium hydroxide, and more preferably a compound represented by the following formula (a1):

[0096]

[0097] In the above formula (a1), R ａ１ ~R ａ４ R each independently represents an alkyl group having 1 to 16 carbon atoms, an aryl group having 6 to 16 carbon atoms, an aralkyl group having 7 to 16 carbon atoms, or a hydroxyalkyl group having 1 to 16 carbon atoms. ａ１ ~R ａ４ At least two of these may be bonded to each other to form a ring structure.

[0098] As the compound represented by the above formula (a1), from the viewpoint of availability, at least one selected from the group consisting of tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide (TEAH), tetrapropylammonium hydroxide, tetrabutylammonium hydroxide (TBAH), methyltripropylammonium hydroxide, methyltributylammonium hydroxide, ethyltrimethylammonium hydroxide, dimethyldiethylammonium hydroxide, benzyltrimethylammonium hydroxide (BzTMAH), hexadecyltrimethylammonium hydroxide, (2-hydroxyethyl)trimethylammonium hydroxide, and spiro-(1,1')-bipyrrolidinium hydroxide is preferred; TMAH, TEAH, TBAH, or BzTMAH is more preferred, and TMAH, TEAH, or TBAH is even more preferred.

[0099] The quaternary ammonium compound may be used alone or in combination of two or more. When the composition contains a quaternary ammonium compound, the content of the quaternary ammonium compound is preferably 0.01 to 15% by mass, more preferably 0.1 to 10% by mass, based on the total mass of the composition.

[0100] The basic compound may be used alone or in combination of two or more. When the composition contains a basic compound, the content of the basic compound is preferably 0.01 to 20% by mass, more preferably 0.01 to 10% by mass, based on the total mass of the composition.

[0101] (Acidic Compound) The present composition may contain an acidic compound as a remover. An acidic compound is intended to mean a compound that, when dissolved in water, causes the pH of the solution to be less than 7. The acidic compound also functions as a pH adjuster that adjusts the pH of the present composition. In this specification, compounds contained in either the oxidizing agent or the anionic surfactant described below are not included in the acidic compound. The acidic compound may be an inorganic acid or an organic acid. As described above, the inorganic acid or organic acid may form a salt with the specific group contained in the repeating unit A of the specific resin.

[0102] Examples of inorganic acids include nitric acid, sulfuric acid, hydrochloric acid, and phosphoric acid, with sulfuric acid being preferred. One type of inorganic acid may be used alone, or two or more types may be used in combination. When the composition contains an inorganic acid, the content of the inorganic acid is preferably 0.01 to 20% by mass, more preferably 0.01 to 10% by mass, based on the total mass of the composition.

[0103] An organic acid is an organic compound that has an acidic functional group and exhibits acidity in aqueous solution (a pH of less than 7.0). Examples of the acidic functional group include a carboxyl group, a phosphonic acid group, a sulfo group, and a phenolic hydroxyl group.

[0104] The organic acid is not particularly limited, but examples thereof include carboxylic acids having a carboxy group in the molecule (organic carboxylic acids), phosphonic acids having a phosphonic acid group in the molecule (organic phosphonic acids), and sulfonic acids having a sulfo group in the molecule (organic sulfonic acids), and organic carboxylic acids are preferred.

[0105] The number of acidic functional groups possessed by the organic acid is not particularly limited, but is preferably 1 to 4, and more preferably 1 to 3. The organic acid is preferably a compound having the function of chelating with metals contained in the residue, and is preferably a compound having two or more functional groups (coordinating groups) within the molecule that form coordinate bonds with metal ions. Examples of the coordinating groups include the acidic functional groups and specific groups described above.

[0106] Examples of carboxylic acids include polyaminopolycarboxylic acids, amino acids, polycarboxylic acids, and monocarboxylic acids.

[0107] The phosphonic acid may be a monophosphonic acid having only one phosphonic acid group in the molecule, or a polyphosphonic acid having two or more phosphonic acid groups in the molecule. The number of phosphonic acid groups in the phosphonic acid is preferably 2 to 5, more preferably 2 to 4, and even more preferably 2 or 3.

[0108] The sulfonic acid may be a monosulfonic acid having only one sulfo group in the molecule, or a polysulfonic acid having two or more sulfo groups in the molecule. The number of sulfo groups in the sulfonic acid is preferably 1 or 2, and more preferably 1.

[0109] Sulfonic acids include methanesulfonic acid (MSA), ethanesulfonic acid, isethionic acid (2-hydroxyethanesulfonic acid), benzenesulfonic acid, and p-toluenesulfonic acid (tosylic acid), with methanesulfonic acid or isethionic acid being preferred.

[0110] The organic acid preferably has a low molecular weight. Specifically, the molecular weight of the organic acid is preferably 600 or less, more preferably 450 or less. There is no particular lower limit, but it is preferably 85 or more. The number of carbon atoms in the organic acid is preferably 15 or less, more preferably 12 or less, and even more preferably 8 or less. There is no particular lower limit, but it is preferably 2 or more.

[0111] As the organic acid, the above-mentioned carboxylic acids are preferred, the above-mentioned polyaminopolycarboxylic acids, amino acids or polycarboxylic acids are more preferred, and the above-mentioned amino acids or polycarboxylic acids are even more preferred.

[0112] The organic acid may be used alone or in combination of two or more. When the composition contains an organic acid, the content of the organic acid is preferably 0.001 to 20% by mass, more preferably 0.005 to 10% by mass, based on the total mass of the composition.

[0113] The present composition may contain other removers in addition to those described above. Examples of other removers include compounds having at least two nitrogen-containing groups and no carboxyl group. Specific examples of such compounds include at least one biguanide compound selected from the group consisting of compounds having a biguanide group and salts thereof. Furthermore, the chelating agents described in JP-A-2017-504190 can also be used as removers, and the contents of the above document are incorporated herein by reference.

[0114] The remover is preferably at least one selected from the group consisting of a fluorine-containing compound, a hydroxylamine compound, a basic compound, and an acidic compound, and more preferably at least one selected from the group consisting of hydrofluoric acid, ammonium fluoride, a hydroxylamine compound, ammonium hydroxide, a water-soluble amine, a quaternary ammonium compound, sulfuric acid, and an organic carboxylic acid. Furthermore, in order to further improve the removability of dry etching residues when used as a cleaning solution, the composition preferably contains at least one remover selected from the group consisting of hydrofluoric acid, a hydroxylamine compound, ammonium hydroxide, a water-soluble amine, and a quaternary ammonium compound, and more preferably contains hydroxylamine, ammonium hydroxide, TMAH, or hydrofluoric acid.

[0115] The remover may be used alone or in combination of two or more. When the composition contains a remover, the content of the remover is preferably 0.001 to 20% by mass, more preferably 0.005 to 10% by mass, based on the total mass of the composition. The content of the remover is preferably 0.1 to 98.0% by mass, more preferably 0.3 to 85.0% by mass, based on the total solid content of the composition.

[0116] <Oxidizing Agent> The composition may contain an oxidizing agent. When the composition is an etching solution, it is preferable that the composition contains an oxidizing agent. Examples of oxidizing agents include peroxides such as hydrogen peroxide and peracetic acid, nitric acid, iodic acid, periodic acid, hypochlorous acid, chlorous acid, chloric acid, perchloric acid, persulfuric acid, dichromic acid, permanganic acid, ozone water, silver (II) salts, and iron (III) salts such as iron nitrate. The above oxidizing agents may form salts with counterions. The oxidizing agent contained in the composition is preferably hydrogen peroxide, nitric acid, peracetic acid, periodic acid, perchloric acid, chloric acid, hypochlorous acid, cerium ammonium nitrate, iron nitrate, or ammonium persulfate, and more preferably hydrogen peroxide, nitric acid, peracetic acid, periodic acid, or perchloric acid.

[0117] The oxidizing agent may be used alone or in combination of two or more. When the composition contains an oxidizing agent, the content of the oxidizing agent is preferably 0.1 to 20 mass% and more preferably 0.5 to 15 mass% relative to the total mass of the composition. The content of the oxidizing agent is preferably 10 to 80 mass% and more preferably 30 to 60 mass% relative to the total solid content in the composition.

[0118] <Corrosion inhibitor> The composition may contain, and preferably contains, a corrosion inhibitor. The corrosion inhibitor is not particularly limited as long as it is a compound that has the function of preventing corrosion of the metal-containing layer due to overetching or the like by coordinating with the surface of the metal-containing layer to form a film, and examples of the corrosion inhibitor include heteroaromatic compounds, thiol compounds, and catechol compounds.

[0119] The heteroaromatic compound is not particularly limited as long as it has a heteroaromatic ring structure in the molecule, but a nitrogen-containing heteroaromatic compound in which at least one heteroatom constituting the heteroaromatic ring is a nitrogen atom is preferred. Examples of the nitrogen-containing heteroaromatic compound include azole compounds, pyridine compounds, pyrazine compounds, and pyrimidine compounds, and azole compounds are preferred.

[0120] An azole compound is a compound having one or more nitrogen atoms and a five-membered heterocyclic ring with aromaticity. The number of nitrogen atoms contained in the five-membered heterocyclic ring of the azole compound is preferably 1 to 4, more preferably 1 to 3. The azole compound may have a substituent on the five-membered heterocyclic ring. Examples of the substituent include a hydroxy group, a carboxy group, a mercapto group, an amino group, an alkyl group having 1 to 4 carbon atoms which may have an amino group, and a 2-imidazolyl group. Examples of azole compounds include imidazole compounds in which one of the atoms constituting the azole ring is a nitrogen atom, pyrazole compounds in which two of the atoms constituting the azole ring are nitrogen atoms, thiazole compounds in which one of the atoms constituting the azole ring is a nitrogen atom and the other is a sulfur atom, triazole compounds in which three of the atoms constituting the azole ring are nitrogen atoms, and tetrazole compounds in which four of the atoms constituting the azole ring are nitrogen atoms.

[0121] Examples of imidazole compounds include imidazole, 1-methylimidazole, 2-methylimidazole, 5-methylimidazole, 1,2-dimethylimidazole, 2-mercaptoimidazole, 4,5-dimethyl-2-mercaptoimidazole, 4-hydroxyimidazole, 2,2'-biimidazole, 4-imidazolecarboxylic acid, histamine, and benzimidazole. Examples of pyrazole compounds include 2,4-dimethylthiazole, benzothiazole, and 2-mercaptobenzothiazole. Examples of thiazole compounds include 2,4-dimethylthiazole, benzothiazole, and 2-mercaptobenzothiazole. Examples of triazole compounds include 1,2,4-triazole, 3-methyl-1,2,4-triazole, 5-amino-1H-tetrazole, 3-amino-1,2,4-triazole, 1,2,3-triazole, 1-methyl-1,2,3-triazole, benzotriazole, 1-hydroxybenzotriazole, 1-dihydroxypropylbenzotriazole, 2,3-dicarboxypropylbenzotriazole, 4-hydroxybenzotriazole, 4-carboxybenzotriazole, 5-methyl-1H-benzotriazole, and 2,2'-{[(5-methyl-1H-benzotriazol-1-yl)methyl]imino}diethanol. Among these, benzotriazole, 5-methyl-1H-benzotriazole, and tolyltriazole are preferred, and 5-methyl-1H-benzotriazole is more preferred. Examples of tetrazole compounds include 1H-tetrazole (1,2,3,4-tetrazole), 5-methyl-1,2,3,4-tetrazole, 5-amino-1,2,3,4-tetrazole, 1,5-pentamethylenetetrazole, 5-mercapto-1-phenyltetrazole, and 1-(2-dimethylaminoethyl)-5-mercaptotetrazole. Of these, 5-mercapto-1-phenyltetrazole is preferred.

[0122] A pyridine compound is a compound having a six-membered heterocyclic ring (pyridine ring) that contains one nitrogen atom and has aromaticity, a pyrazine compound is a compound having a six-membered heterocyclic ring (pyrazine ring) that contains two nitrogen atoms located at the para position, and a pyrimidine compound is a compound having a six-membered heterocyclic ring (pyrimidine ring) that contains two nitrogen atoms located at the meta position.

[0123] A thiol compound refers to a compound having at least one thiol group and a hydrocarbon group. The number of thiol groups contained in a thiol compound is not particularly limited, but is preferably 1 or 2, and more preferably 1. Examples of hydrocarbon groups contained in thiol compounds include alkyl groups (preferably having 4 to 20 carbon atoms), alkenyl groups (preferably having 4 to 12 carbon atoms), alkynyl groups (preferably having 4 to 12 carbon atoms), aryl groups (preferably having 6 to 14 carbon atoms), and aralkyl groups (preferably having 7 to 16 carbon atoms). The hydrocarbon group may have a substituent. Examples of the substituent include a hydroxyl group, a carboxy group, and an amino group that may have an alkyl group.

[0124] The catechol compound refers to at least one compound selected from the group consisting of pyrocatechol (benzene-1,2-diol) and catechol derivatives. The catechol derivative refers to a compound in which pyrocatechol is substituted with at least one substituent. Examples of the substituent in the catechol derivative include a hydroxy group, a carboxy group, a carboxylic acid ester group, a sulfo group, a sulfonate ester group, an alkyl group (preferably having 1 to 6 carbon atoms), and an aryl group (preferably a phenyl group). The carboxy group and sulfo group contained as a substituent in the catechol derivative may be a salt with a cation. Furthermore, the alkyl group and aryl group contained as a substituent in the catechol derivative may further have a substituent.

[0125] As the corrosion inhibitor, a heteroaromatic compound or a thiol compound is preferred, and a triazole compound, a tetrazole compound or a thiol compound is more preferred.

[0126] The corrosion inhibitor may be used alone or in combination of two or more. When the composition contains a corrosion inhibitor, the content of the corrosion inhibitor is preferably 0.001 to 10 mass%, more preferably 0.002 to 5 mass%, and even more preferably 0.03 to 1 mass%, based on the total mass of the composition. Furthermore, the content of the corrosion inhibitor is preferably 0.1 to 10.0 mass%, more preferably 0.5 to 10.0 mass%, based on the total solid content in the composition.

[0127] The corrosion inhibitor is preferably a high-purity grade one, and more preferably further purified before use. The method for purifying the corrosion inhibitor is not particularly limited, but known methods such as filtration, ion exchange, distillation, adsorption purification, recrystallization, reprecipitation, sublimation, and purification using a column can be used, and these methods can also be used in combination.

[0128] <Surfactant> The composition may contain the present surfactant. The composition preferably contains a surfactant in that dissolution of the metal film can be further suppressed. The surfactant is not particularly limited as long as it is a compound having a hydrophilic group and a hydrophobic group (lipophilic group) in the molecule, and examples thereof include anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants.

[0129] Surfactants often have a hydrophobic group selected from an aliphatic hydrocarbon group, an aromatic hydrocarbon group, and a combination thereof. The hydrophobic group possessed by a surfactant is not particularly limited, but when the hydrophobic group contains an aromatic hydrocarbon group, it preferably has 6 or more carbon atoms, more preferably 10 or more carbon atoms. When the hydrophobic group does not contain an aromatic hydrocarbon group and is composed only of an aliphatic hydrocarbon group, it preferably has 10 or more carbon atoms, more preferably 12 or more carbon atoms. There is no particular upper limit on the number of carbon atoms in the hydrophobic group, but it is preferably 20 or less.

[0130] (Anionic surfactant) Examples of the anionic surfactant contained in the composition include phosphate ester surfactants, phosphonic acid surfactants, sulfonic acid surfactants, carboxylic acid surfactants, and sulfate ester surfactants. As the anionic surfactant, phosphate ester surfactants, sulfonic acid surfactants, carboxylic acid surfactants, and sulfate ester surfactants are preferred.

[0131] (Cationic Surfactants) Examples of cationic surfactants include primary to tertiary alkylamine salts (e.g., monostearyl ammonium chloride, distearyl ammonium chloride, tristearyl ammonium chloride, etc.), quaternary ammonium salts (e.g., dodecyltrimethylammonium chloride, etc.), and modified aliphatic polyamines (e.g., polyethylene polyamine, etc.).

[0132] (Nonionic Surfactants) Examples of nonionic surfactants include polyoxyalkylene alkyl ethers, polyoxyalkylene alkenyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyalkylene glycols, polyoxyalkylene monoalkylates, polyoxyalkylene dialkylates, bispolyoxyalkylene alkylamides, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene alkylamines, glycerin fatty acid esters, oxyethylene oxypropylene block copolymers, acetylene glycol surfactants, and acetylene polyoxyethylene oxides.

[0133] (Amphoteric Surfactants) Examples of amphoteric surfactants include carboxybetaines (e.g., alkyl-N,N-dimethylaminoacetic acid betaine and alkyl-N,N-dihydroxyethylaminoacetic acid betaine), sulfobetaines (e.g., alkyl-N,N-dimethylsulfoethyleneammonium betaine), and imidazolinium betaines (e.g., 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine).

[0134] As the surfactant, the compounds described in paragraphs

[0092] to

[0096] of JP-A-2015-158662, paragraphs

[0045] to

[0046] of JP-A-2012-151273, and paragraphs

[0014] to

[0020] of JP-A-2009-147389 can also be used, the contents of which are incorporated herein by reference.

[0135] The surfactant may be used alone or in combination of two or more. When the composition contains a surfactant, the content of the surfactant is preferably 0.001 to 3 mass%, more preferably 0.005 to 2 mass%, relative to the total mass of the composition, in terms of more excellent effects of the present invention. Furthermore, the content of the surfactant is preferably 1.0 to 40.0 mass%, more preferably 5.0 to 30.0 mass%, relative to the total solid content in the composition.

[0136] <Antifoaming Agent> The composition may contain an antifoaming agent. Surfactants may cause foaming depending on how they are used. Therefore, it is preferable that a composition containing a surfactant contains an antifoaming agent that suppresses the generation of foaming, shortens the lifespan of the generated foam, and suppresses residual foam. The antifoaming agent is not particularly limited as long as it does not impair the effects of the present invention, and examples thereof include silicone-based antifoaming agents, acetylene diol-based antifoaming agents, fatty acid ester-based antifoaming agents, and long-chain aliphatic alcohol-based antifoaming agents. Among these, silicone-based antifoaming agents are preferred because of their superior effect of suppressing residual foam. It should be noted that the antifoaming agent does not include compounds contained in the above-mentioned surfactants.

[0137] The defoaming agent may be used alone or in combination of two or more. When the composition contains a defoaming agent, the content of the defoaming agent is preferably 0.0001 to 3 mass%, more preferably 0.001 to 2 mass%, relative to the total mass of the composition, in terms of more excellent suppression of residual foam. Furthermore, the content of the defoaming agent is preferably 1.0 to 40.0 mass%, more preferably 5.0 to 30.0 mass%, relative to the total solid content in the composition.

[0138] <Organic Solvent> The present composition may contain an organic solvent, and preferably contains an organic solvent. The organic solvent is preferably a water-soluble organic solvent. The organic solvent being water-soluble means that the organic solvent can be mixed (dissolved) in water at 25°C in any ratio. Examples of organic solvents include alcohol-based solvents, ketone-based solvents, ester-based solvents, ether-based solvents (e.g., glycol diether), sulfone-based solvents, sulfoxide-based solvents, nitrile-based solvents, and amide-based solvents. These solvents may be water-soluble. In particular, the present composition preferably contains one or more organic solvents selected from the group consisting of alcohol-based solvents, ketone-based solvents, ester-based solvents, and ether-based solvents.

[0139] Examples of alcohol-based solvents include alkanediols (including, for example, alkylene glycols), alkoxyalcohols (including, for example, glycol monoethers), saturated aliphatic monohydric alcohols, unsaturated non-aromatic monohydric alcohols, and low-molecular-weight alcohols containing a ring structure.

[0140] Examples of alkanediols include glycol, 2-methyl-1,3-propanediol, 1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 2,3-butanediol, pinacol, and alkylene glycol.

[0141] Examples of alkylene glycols include ethylene glycol, propylene glycol, hexylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, and tetraethylene glycol, with propylene glycol or hexylene glycol being preferred.

[0142] Examples of alkoxy alcohols include 3-methoxy-3-methyl-1-butanol, 3-methoxy-1-butanol, 1-methoxy-2-butanol, and glycol monoethers, with glycol monoethers being preferred. Examples of glycol monoethers include ethylene glycol mono C1-C4 alkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol monoisopropyl ether, and ethylene glycol monobutyl ether; diethylene glycol mono C1-C4 alkyl ethers such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol monobutyl ether; triethylene glycol mono C1-C4 alkyl ethers such as triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, and triethylene glycol monobutyl ether; 1-methoxy-2-propanol, 2-methoxy-1-propanol, 1-ethoxy-2-propanol, 2-ethoxy-1-propanol, propylene glycol mono-n-propyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, ethylene glycol monobenzyl ether, and diethylene glycol monobenzyl ether. Of these, ethylene glycol mono C1-C4 alkyl ethers are preferred, and ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, or ethylene glycol monobutyl ether is more preferred.

[0143] Examples of saturated aliphatic monohydric alcohols include methanol, ethanol, n-propyl alcohol, isopropyl alcohol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, 2-pentanol, t-pentyl alcohol, and hexanol. Examples of unsaturated non-aromatic monohydric alcohols include allyl alcohol, propargyl alcohol, 2-butenyl alcohol, 3-butenyl alcohol, and 4-penten-2-ol. Examples of low molecular weight alcohols containing a ring structure include tetrahydrofurfuryl alcohol, furfuryl alcohol, and 1,3-cyclopentanediol.

[0144] The organic solvent may be used alone or in combination of two or more. When the composition contains an organic solvent, the content of the organic solvent is preferably 0.1 to 30 mass %, more preferably 1 to 15 mass %, based on the total mass of the composition.

[0145] <Metal Component> The composition may contain a metal component. Examples of the metal component include metal particles and metal ions. For example, the content of the metal component refers to the total content of the metal particles and metal ions. The composition may contain either metal particles or metal ions, or both. Examples of metal atoms contained in the metal component include metal atoms selected from the group consisting of Ag, Al, As, Au, Ba, Ca, Cd, Co, Cr, Cu, Fe, Ga, Ge, K, Li, Mg, Mn, Mo, Na, Ni, Pb, Sn, Sr, Ti, and Zn. The metal component may contain one type of metal atom or two or more types of metal atoms. The metal particles may be a simple substance or an alloy, or the metal may exist in a form associated with an organic substance. The metal component may be a metal component that is inevitably contained in each component (raw material) contained in the composition, a metal component that is inevitably contained during the production, storage, and / or transportation of the composition, or a metal component that is intentionally added.

[0146] When the present composition contains a metal component, the content of the metal component is often 0.01 mass ppt to 10 mass ppm, preferably 0.1 mass ppt to 1 mass ppm, and more preferably 0.1 mass ppt to 100 mass ppb, relative to the total mass of the present composition.

[0147] The type and content of metal components in this composition can be measured using SP-ICP-MS (Single Nano Particle Inductively Coupled Plasma Mass Spectrometry). SP-ICP-MS uses the same equipment as conventional ICP-MS (Inductively Coupled Plasma Mass Spectrometry), with the only difference being the data analysis. Data analysis for SP-ICP-MS can be performed using commercially available software. ICP-MS measures the content of the target metal component regardless of its form of existence. Therefore, the total mass of the target metal particles and metal ions is quantified as the content of the metal component. On the other hand, SP-ICP-MS can measure the content of metal particles. Therefore, the content of metal ions in a sample can be calculated by subtracting the content of metal particles from the content of metal components in the sample.

[0148] As a measurement method using the SP-ICP-MS method, for example, Agilent 8800 triple quadrupole ICP-MS (inductively coupled plasma mass spectrometry, for semiconductor analysis, option #200) manufactured by Agilent Technologies can be used, and the measurement can be performed by the method described in the Examples. As an alternative to the above, PerkinElmer NexION350S and Agilent 8900 manufactured by Agilent Technologies can also be used.

[0149] The method for adjusting the content of each metal component in the composition is not particularly limited. For example, the content of metal components in the composition can be reduced by performing a known process for removing metals from the composition and / or from raw materials containing each component used in preparing the composition. Alternatively, the content of metal components in the composition can be increased by adding a compound containing metal ions to the composition.

[0150] The composition may contain additives other than the above components, such as antibacterial agents, anticorrosive agents, and antiseptic agents.

[0151] The contents of the above-described components (excluding metal components) in the composition can be measured by known methods such as gas chromatography-mass spectrometry (GC-MS), liquid chromatography-mass spectrometry (LC-MS), and ion-exchange chromatography (IC).

[0152] [Physical Properties of the Composition] <pH> The pH of the composition is not particularly limited, and is preferably 2.0 to 12.0. When the composition is used as a cleaning liquid, the pH of the composition is more preferably 3.0 to 10.0, and even more preferably 8.0 to 10.0. This is because compositions with a pH in the above range provide better effects of the present invention. The pH of the composition is a value obtained by measurement at 25°C using a pH meter (for example, Model "F-74" manufactured by Horiba, Ltd.) in accordance with JIS Z8802-1984.

[0153] <Coarse Particles> The present composition is preferably substantially free of coarse particles. Coarse particles refer to particles with a diameter of 0.2 μm or more, assuming a spherical shape. Furthermore, "substantially free of coarse particles" means that, when the composition is measured using a commercially available measuring device for liquid-borne particle measurement using light scattering, there are 10 or fewer particles of 0.2 μm or more per mL of the composition. The coarse particles contained in the present composition include particles such as dust, dirt, organic solids, and inorganic solids contained as impurities in raw materials, as well as particles such as dust, dirt, organic solids, and inorganic solids introduced as contaminants during the preparation of the composition, which ultimately remain undissolved in the composition. The amount of coarse particles present in the present composition can be measured in the liquid phase using a commercially available measuring device for liquid-borne particle measurement using light scattering with a laser as a light source. Methods for removing coarse particles include, for example, filtering.

[0154] [Kit and Concentrated Solution] The present composition may be prepared as a kit by dividing the raw materials thereof into a plurality of parts. Although not particularly limited, a specific method for preparing the present composition as a kit may include, for example, preparing a composition containing water and a remover as a first liquid and preparing a composition containing a specific resin as a second liquid.

[0155] The contents of each component contained in the first and second liquids provided in the kit are not particularly limited, but it is preferable that the contents of each component in the present composition prepared by mixing the first and second liquids are the amounts described above as the preferred contents. The pH of the first and second liquids provided in the kit is not particularly limited, as long as the pH of each liquid is adjusted so that the pH of the present composition prepared by mixing the first and second liquids is the desired value.

[0156] The composition may also be prepared as a concentrated solution. In this case, the diluted solution obtained by diluting the composition with a dilution liquid before use is used. That is, the kit may include the composition in the form of a concentrated solution and the dilution liquid. The dilution liquid is preferably a liquid selected from the group consisting of water, isopropanol, a mixture of water and isopropanol, and a solvent containing ammonium hydroxide, more preferably water, isopropanol, or a mixture of water and isopropanol, and even more preferably water. The dilution ratio of the composition is not particularly limited, but is preferably 1 to 2000 times, more preferably 1 to 100 times.

[0157] A composition (hereinafter also referred to as a "diluted solution") containing each component in an amount obtained by dividing the suitable content of each component (excluding water) that can be contained in the present composition by a dilution ratio within the above range (e.g., 100) can also be suitably used. The suitable content of each component (excluding water) relative to the total mass of the diluted solution is, for example, the amount described as the suitable content of each component relative to the total mass of the composition before dilution divided by a dilution ratio within the above range (e.g., 100). The specific method for the dilution step of diluting the present composition may be performed in accordance with the composition preparation step described below. The stirring device and stirring method used in the dilution step may also be performed using the known stirring device listed in the composition preparation step described below.

[0158] [Uses] Next, uses of the composition according to the above embodiment will be described. The composition is a composition for semiconductor devices. In this specification, "for semiconductor devices" means that the composition is used in the manufacture of semiconductor devices. The composition can be used in any process for manufacturing semiconductor devices, for example, in the process of treating a semiconductor substrate included in the method of manufacturing a semiconductor device. More specifically, the composition can be used to treat insulating films, resists, antireflective films, etching residues (particularly dry etching residues), ashing residues, and residues derived from resist films such as photoresists and metal hard masks present on a substrate. In this specification, etching residues, ashing residues, and residues derived from resist films are collectively referred to as residues. The composition can also be used in etching processes for removing metal inclusions on a substrate, or in treating a substrate after chemical mechanical polishing.

[0159] The composition can be used, for example, as a pre-wet solution applied to a substrate to improve the coatability of the composition prior to forming a resist film using an actinic ray- or radiation-sensitive composition; a cleaning solution used to remove residues adhering to metal layers; a solution used to remove various resist films for pattern formation (e.g., removers and strippers); and a solution used to remove permanent films (e.g., color filters, transparent insulating films, and resin lenses) from semiconductor substrates (e.g., removers and strippers). Since the semiconductor substrate after removal of the permanent film may be reused in semiconductor devices, removal of the permanent film is considered to be included in the semiconductor device manufacturing process. The composition can also be used as a cleaning solution to remove residues such as metal impurities or fine particles from substrates after chemical mechanical polishing. The composition can also be used as an etching solution for metal-containing materials (including metal oxides and composite oxides consisting of multiple metal oxides) on substrates. Among the above uses, the present composition can be particularly suitably used as a cleaning solution for removing residues, a solution for removing a resist film used in pattern formation, a cleaning solution for removing residues from a substrate after chemical mechanical polishing, or an etching solution. The present composition may be used for only one of the above uses, or for two or more uses. A diluted solution obtained by diluting the present composition can also be used for the above uses. In particular, the present composition can be suitably used as a cleaning solution for removing residues from a substrate (more preferably a substrate that has been subjected to chemical mechanical polishing).

[0160] The present composition can be suitably used for treating a substrate having a metal layer containing tungsten (W) of a semiconductor device, and a substrate having a metal layer containing Mo of a semiconductor device. The present composition can also be used for treating a substrate having a metal layer containing Co of a semiconductor device, and a substrate having a metal layer containing Cu of a semiconductor device. Furthermore, since the present composition has excellent corrosion prevention properties for insulating films, it can be used for treating a semiconductor device having a metal layer containing SiO Ｘ The present invention can also be used to treat a substrate having a layer containing at least one selected from the group consisting of SiN and SiOC (x represents a number from 1 to 3).

[0161] [Methods for producing the composition, concentrate, and kit] <Composition preparation step> The method for producing the composition is not particularly limited, and the composition can be produced by a known production method. Examples of methods for producing the composition include a method that includes at least a composition preparation step of mixing the above-mentioned components to prepare a composition. In the composition preparation step, the order in which the components are mixed is not particularly limited. It is preferable that the concentrate and each liquid included in the kit are also produced by the same method as above. The method for producing the kit is not particularly limited, and for example, a kit for preparing a composition can be produced by preparing the above-mentioned first liquid and second liquid, respectively, and then placing the first liquid and second liquid in different containers.

[0162] <Filtration Step> The above production method preferably includes a filtration step of filtering the liquid to remove foreign matter, coarse particles, etc. from the liquid. The filtration method is not particularly limited, and any known filtration method can be used. Among these, filtering using a filter is preferred.

[0163] The filter used for filtering can be any filter that has been conventionally used for filtering purposes, without any particular limitations. Examples of materials constituting the filter include fluororesins such as PTFE (polytetrafluoroethylene), polyamide resins such as nylon, and polyolefin resins (including high-density and ultra-high molecular weight) such as polyethylene and polypropylene (PP). Among these, polyamide resins, PTFE, and polypropylene (including high-density polypropylene) are preferred. Using a filter made of these materials can more effectively remove highly polar foreign matter, which is likely to cause defects, from the composition.

[0164] The lower limit of the critical surface tension of the filter is preferably 70 mN / m or more, and the upper limit is preferably 95 mN / m or less. In particular, the critical surface tension of the filter is preferably 75 to 85 mN / m. The critical surface tension value is the nominal value provided by the manufacturer. By using a filter with a critical surface tension within the above range, highly polar foreign matter that is likely to cause defects can be more effectively removed from the composition.

[0165] The pore size of the filter is preferably about 0.001 to 1.0 μm, more preferably about 0.02 to 0.5 μm, and even more preferably about 0.01 to 0.1 μm. By setting the pore size of the filter within the above range, it is possible to reliably remove fine foreign matter contained in the composition while suppressing filtration clogging. When using filters, different filters may be combined.

[0166] Furthermore, the filter to be used is preferably treated before filtering the composition. The liquid to be used for this treatment is not particularly limited, but is preferably the composition, a concentrate, or a liquid containing the components contained in the composition.

[0167] When filtering is performed, the upper limit of the temperature during filtering is preferably room temperature (25° C.) or lower, more preferably 23° C. or lower, and even more preferably 20° C. or lower. The lower limit of the temperature during filtering is preferably 0° C. or higher, more preferably 5° C. or higher, and even more preferably 10° C. or higher. Filtering can remove particulate foreign matter and / or impurities, and when filtering is performed at the above temperatures, the amount of particulate foreign matter and / or impurities dissolved in the composition is reduced, so filtering is performed more efficiently.

[0168] <Static Charge Elimination Step> The above production method may further include a static charge elimination step of eliminating static charge from at least one selected from the group consisting of the present composition, the concentrate, and the kit.

[0169] All steps of the above manufacturing method are preferably carried out in a clean room. The clean room preferably meets the 14644-1 clean room standard. The clean room preferably meets any one of ISO (International Organization for Standardization) Class 1, ISO Class 2, ISO Class 3, and ISO Class 4, more preferably ISO Class 1 or ISO Class 2, and even more preferably ISO Class 1.

[0170] <Container> The container for housing the composition, concentrate, or kit described above is not particularly limited, and any known container can be used as long as corrosiveness by the liquid is not a problem. The container is preferably one with a high level of cleanliness within the container and low impurity elution for semiconductor applications. Specific examples of the container include the "Clean Bottle" series manufactured by Aicello Chemical Co., Ltd. and the "Pure Bottle" manufactured by Kodama Resin Industry Co., Ltd. Furthermore, to prevent impurities from being mixed into the raw materials and composition (contamination), it is also preferable to use a multilayer container whose inner wall has a six-layer structure made of six types of resin, or a multilayer container whose inner wall has a seven-layer structure made of six types of resin. Examples of such containers include, but are not limited to, the containers described in JP 2015-123351 A. Furthermore, the containers exemplified in paragraphs

[0121] to

[0124] of WO 2022 / 004217 can also be used, and the contents of these containers are incorporated herein by reference.

[0171] It is preferable to wash the inside of these containers before filling them. The liquid used for washing may be selected appropriately depending on the application, but is preferably the present composition, a liquid obtained by diluting the present composition, or a liquid containing at least one of the components added to the present composition.

[0172] To prevent changes in the components of the composition during storage, the container may be filled with an inert gas (such as nitrogen or argon) with a purity of 99.99995% by volume or higher. Gases with low water content are particularly preferred. The liquid container may be transported or stored at room temperature, but the temperature may be controlled to a range of -20°C to 20°C to prevent deterioration.

[0173] [Substrate Treatment Method] In a substrate treatment method using the present composition (hereinafter also simply referred to as "the present treatment method"), the present composition can typically be used by contacting it with a workpiece containing a metal-containing material (particularly, a substrate having a metal-containing material that is a metal-containing material) (hereinafter also referred to as "workpiece"). In this case, the workpiece may contain multiple types of metal-containing materials.

[0174] [Substrate] The substrate to be treated using the present composition is preferably a substrate having metal inclusions. In this specification, "on the substrate" includes, for example, the front and back surfaces, sides, and grooves of the substrate. Furthermore, "metal inclusions on the substrate" refers not only to cases where the metal inclusions are present directly on the surface of the substrate, but also to cases where the metal inclusions are present on the substrate via another layer. Furthermore, "substrate" in this specification includes, for example, a semiconductor substrate consisting of a single layer and a semiconductor substrate consisting of a multilayer.

[0175] The metal inclusion is a material containing a metal (metal atom) as a main component. Examples of the metal contained in the metal inclusion include at least one metal M selected from the group consisting of Cu (copper), Co (cobalt), W (tungsten), Ti (titanium), Ta (tantalum), Ru (ruthenium), Cr (chromium), Hf (hafnium), Os (osmium), Pt (platinum), Ni (nickel), Mn (manganese), Zr (zirconium), Mo (molybdenum), La (lanthanum), and Ir (iridium).

[0176] The metal-containing material may be any material containing a metal (metal atom), such as a material composed of at least one selected from the group consisting of a simple substance of metal M, an alloy containing metal M, an oxide of metal M, a nitride of metal M, and an oxynitride of metal M. More specific examples of the metal-containing material include metal-containing materials containing at least one component selected from the group consisting of copper, cobalt, cobalt alloys, tungsten, tungsten alloys, ruthenium, ruthenium alloys, tantalum, tantalum alloys, aluminum oxide, aluminum nitride, aluminum nitride oxide, titanium aluminum, titanium, titanium nitride, titanium oxide, zirconium oxide, hafnium oxide, tantalum oxide, lanthanum oxide, and yttrium alloys. The metal-containing material may also be a mixture containing two or more of these compounds.

[0177] The form of the metal inclusion is not particularly limited, and may be, for example, a film (layer), a wire, or a particle. The metal inclusion may be disposed on only one main surface of the substrate, or on both main surfaces. The metal inclusion may be disposed over the entire main surface of the substrate, or may be disposed over a portion of the main surface of the substrate.

[0178] The substrate preferably has a metal M inclusion containing metal M, more preferably has a metal inclusion containing at least one metal selected from the group consisting of W, Mo, Cu, Co, Ti, Ta, and Ru, still more preferably has a metal inclusion containing at least one metal selected from the group consisting of W, Mo, Cu, and Co, and particularly preferably has a metal inclusion containing at least one of W and a W alloy (W inclusion).

[0179] Among these, the substrate preferably has a W-containing film, Mo-containing film, copper-containing film, Co-containing film, or Ti-containing film, and more preferably has a W-containing film or Mo-containing film. Examples of W-containing films include a metal film made of tungsten only (W metal film) and a metal film made of an alloy of tungsten and another metal (W alloy metal film). Specific examples of W alloy metal films include a WTi alloy metal film and a WCo alloy metal film. Tungsten-containing films are often used as wiring films or barrier metals.

[0180] Examples of Mo-containing films include a metal film made of only molybdenum (Mo metal film) and a metal film made of an alloy of molybdenum and another metal (Mo alloy metal film). A specific example of the Mo alloy metal film is a MoCo alloy metal film.

[0181] Examples of copper-containing films include wiring films (copper wiring films) made only of metallic copper, and wiring films (copper alloy wiring films) made of alloys of metallic copper and other metals. Specific examples of copper alloy wiring films include wiring films made of alloys of copper and one or more metals selected from Al, Ti, Cr, Mn, Ta, and W. More specifically, CuAl alloy wiring films, CuTi alloy wiring films, CuCr alloy wiring films, CuMn alloy wiring films, CuTa alloy wiring films, and CuW alloy wiring films are included.

[0182] Examples of Co-containing films include metal films made only of metallic cobalt (Co metal films) and metal films made of alloys of metallic cobalt and other metals (Co alloy metal films). Specific examples of Co alloy metal films include metal films made of alloys of cobalt and one or more metals selected from Ti, Cr, Fe, Ni, Mo, Pd, Ta, and W. More specifically, CoTi alloy metal films, CoCr alloy metal films, CoFe alloy metal films, CoNi alloy metal films, CoMo alloy metal films, CoPd alloy metal films, CoTa alloy metal films, and CoW alloy metal films are included. Among Co-containing films, Co metal films are often used as wiring films, and Co alloy metal films are often used as barrier metals.

[0183] The Ti-containing film may be, for example, a Ti alloy metal film, which is a metal film containing an alloy of Ti and other metals such as Al, and may further contain the above-mentioned dopants. Specific examples of the Ti alloy metal film include a TiAl film, a TiAlC film, and a TiAlN film. The Ti alloy metal film is often used in gates and their surrounding structures.

[0184] A more specific example of the workpiece is a laminate comprising a substrate and, in this order, a metal layer, an insulating film, and a metal hard mask. The laminate may further have holes formed from the surface (opening) of the metal hard mask toward the substrate, exposing the surface of the metal layer, by performing a dry etching process or the like. The method for producing such a laminate having holes is not particularly limited. Typically, a method involves performing a dry etching process using the metal hard mask as a mask on a pre-processed laminate comprising, in this order, a substrate, a metal layer, an insulating film, and a metal hard mask, thereby etching the insulating film to expose the surface of the metal layer, thereby forming holes penetrating the metal hard mask and the insulating film. The method for producing a metal hard mask is not particularly limited. For example, a metal layer containing a predetermined component is first formed on an insulating film, and a resist film with a predetermined pattern is then formed thereon. Next, the resist film is used as a mask to etch the metal layer, thereby producing a metal hard mask (i.e., a film with a patterned metal layer). The laminate may also have layers other than those described above, such as an etching stop film or an anti-reflective film.

[0185] Fig. 1 is a schematic cross-sectional view showing an example of a laminate that is a workpiece of this processing method. The laminate 10 shown in Fig. 1 includes a substrate 1, a metal layer 2, an etching stop layer 3, an insulating film 4, and a metal hard mask 5, in this order, and a hole 6 that exposes the metal layer 2 at a predetermined position formed by a dry etching process or the like. That is, the workpiece shown in Fig. 1 is a laminate that includes the substrate 1, the metal layer 2, the etching stop layer 3, the insulating film 4, and the metal hard mask 5, in this order, and includes a hole 6 that penetrates from the surface of the metal hard mask 5 to the surface of the metal layer 2 at the position of the opening. The inner wall 11 of the hole 6 is composed of a cross-sectional wall 11a consisting of the etching stop layer 3, the insulating film 4, and the metal hard mask 5, and a bottom wall 11b consisting of the exposed metal layer 2, and has dry etching residue 12 attached thereto.

[0186] This processing method can be suitably used for removing these dry etching residues 12. That is, it is excellent in removing the dry etching residues 12 (residue removal property) and also in preventing corrosion of the inner wall 11 (e.g., metal layer 2, etc.) of the processing target object. The above-mentioned substrate processing method may also be performed on a laminate that has been subjected to a dry ashing step after the dry etching step. The materials constituting each layer of the above-mentioned laminate will be described below.

[0187] <Metal Hard Mask> The metal hard mask preferably contains at least one component selected from the group consisting of copper, cobalt, cobalt alloy, tungsten, tungsten alloy, ruthenium, ruthenium alloy, tantalum, tantalum alloy, aluminum oxide, aluminum nitride, aluminum nitride oxide, titanium aluminum, titanium aluminum carbide, titanium, titanium nitride, titanium oxide, zirconium oxide, hafnium oxide, tantalum oxide, lanthanum oxide, and yttrium alloy (preferably YSiOx). Here, x and y are preferably numbers expressed as x = 1 to 3 and y = 1 to 2, respectively. Examples of materials for the metal hard mask include TiN, TiAl, TiAlC, WO ２ and ZrO ２ Examples include:

[0188] <Insulating Film> The insulating film material is not particularly limited, and examples thereof include those preferably having a dielectric constant k of 3.0 or less, more preferably 2.6 or less. Specific insulating film materials include SiOx, SiN, SiOC, and organic polymers such as polyimide. Preferably, x is a number expressed as 1 to 3. The insulating film may be composed of a plurality of films. An example of an insulating film composed of a plurality of films is an insulating film formed by combining a film containing silicon oxide and a film containing silicon oxide carbide.

[0189] <Etching Stop Layer> The material of the etching stop layer is not particularly limited, but specific examples of the material of the etching stop layer include SiN, SiON, SiOCN-based materials, and metal oxides such as AlOx.

[0190] <Metal Layer> The material forming the metal layer serving as the wiring material and / or plug material is not particularly limited, but preferably includes one or more selected from the group consisting of cobalt, tungsten, and copper. The material forming the metal layer may also be an alloy of cobalt, tungsten, or copper with another metal. The metal layer may further include a metal nitride and / or alloy other than cobalt, tungsten, and copper. Examples of metals other than cobalt, tungsten, and copper that may be included in the metal layer include titanium, titanium-tungsten, titanium nitride, tantalum, tantalum compounds, chromium, chromium oxide, and aluminum. The metal layer may include at least one dopant selected from the group consisting of carbon, nitrogen, boron, and phosphorus in addition to one or more selected from the group consisting of cobalt, tungsten, and copper.

[0191] <Substrate> Specific examples of wafers constituting the substrate include wafers made of silicon-based materials such as silicon (Si) wafers, silicon carbide (SiC) wafers, silicon-containing resin wafers (glass epoxy wafers), gallium phosphide (GaP) wafers, gallium arsenide (GaAs) wafers, and indium phosphide (InP) wafers. Silicon wafers may be n-type silicon wafers doped with pentavalent atoms (e.g., phosphorus (P), arsenic (As), and antimony (Sb)), and p-type silicon wafers doped with trivalent atoms (e.g., boron (B), and gallium (Ga)). The silicon in the silicon wafer may be, for example, amorphous silicon, single crystal silicon, or polycrystalline silicon (polysilicon).

[0192] The workpiece may contain various layers and / or structures as desired, in addition to those described above. For example, the substrate may contain metal wiring, gate electrodes, source electrodes, drain electrodes, insulating layers, ferromagnetic layers, and / or nonmagnetic layers. The substrate may also contain exposed integrated circuit structures, such as interconnect mechanisms, such as metal wiring and dielectric materials. Examples of metals and alloys used for interconnect mechanisms include aluminum, copper-aluminum alloys, copper, titanium, tantalum, cobalt, silicon, titanium nitride, tantalum nitride, and tungsten. The substrate may also contain layers of silicon oxide, silicon nitride, silicon carbide, and / or carbon-doped silicon oxide.

[0193] The method for manufacturing the workpiece is not particularly limited as long as it is a method commonly used in this field. Examples of methods for forming the insulating film on a wafer constituting a substrate include a method in which a silicon oxide film is formed by heat treating the wafer constituting the substrate in the presence of oxygen gas, and then a silicon nitride film is formed by chemical vapor deposition (CVD) using silane and ammonia gases. Examples of methods for forming the metal-containing layer on a wafer constituting a substrate include a method in which a circuit is formed on a wafer having the insulating film by a known method such as resist, and then a metal-containing layer is formed by plating, sputtering, CVD, molecular beam epitaxy (MBE), or the like.

[0194] The workpiece may be a substrate that has been subjected to a planarization process such as CMP after forming an insulating film, a barrier metal, and a metal-containing film on a wafer. CMP is a process that flattens the surface of a substrate having a metal-containing film, a barrier metal, and an insulating film through a combined chemical and mechanical polishing action using a polishing slurry containing abrasive particles (abrasive grains). Impurities such as metal impurities (metal residues) derived from the abrasive grains (e.g., silica and alumina) used in the CMP process and the polished metal-containing film and barrier metal may remain on the surface of the substrate that has been subjected to CMP. These impurities may, for example, short-circuit wiring and deteriorate the electrical properties of the substrate. Therefore, the substrate that has been subjected to CMP is subjected to a cleaning process to remove these impurities from the surface. Specific examples of substrates that have been subjected to CMP include, but are not limited to, the substrates that have been subjected to CMP described in Journal of the Japan Society for Precision Engineering, Vol. 84, No. 3, 2018.

[0195] [Step A] The present treatment method includes, for example, a treatment method having Step A in which the present composition is brought into contact with a substrate having metal inclusions. By carrying out Step A, the metal inclusions on the substrate can be removed. The present composition used in Step A is as described above. The substrate having metal inclusions, which is the object to be treated in Step A, is also as described above. As the substrate having metal inclusions, a substrate having W inclusions or a substrate having Mo inclusions is preferred.

[0196] The method for contacting the workpiece (substrate having metal inclusions) with the composition is not particularly limited, and examples thereof include a method of immersing the workpiece in the composition contained in a tank, a method of spraying the composition onto a substrate, a method of pouring the composition onto a substrate, or any combination thereof. Among these, the method of immersing the workpiece, i.e., a substrate having metal inclusions, in the composition is preferred.

[0197] Furthermore, to further enhance the processing capacity of the present composition, a mechanical stirring method may be used. Examples of mechanical stirring methods include a method of circulating the present composition over a substrate, a method of flowing or spraying the present composition over a substrate, and a method of stirring the present composition using ultrasonic waves or megasonics. Furthermore, the immersion treatment may be a batch method in which multiple workpieces are immersed and processed in a treatment tank, or a single-wafer method.

[0198] The treatment time in step A can be adjusted depending on the method for contacting the composition with the substrate, the temperature of the composition, and the like. The treatment time (contact time between the composition and the object to be treated) is not particularly limited, but is preferably 0.25 to 10 minutes, and more preferably 0.5 to 2 minutes. The temperature of the composition during treatment is not particularly limited, but the lower limit is preferably 15°C or higher, more preferably 20°C or higher, and even more preferably 30°C or higher. The upper limit of the temperature is preferably 90°C or lower, more preferably 80°C or lower, and even more preferably 70°C or lower.

[0199] Specific embodiments of step A include step A1, in which the composition is used to recess-etch wiring formed on a substrate and made of metal inclusions; step A2, in which the composition is used to remove a film on the outer edge of a substrate on which a film made of metal inclusions is disposed; step A3, in which the composition is used to remove metal inclusions adhering to the back surface of a substrate on which a film made of metal inclusions is disposed; step A4, in which the composition is used to remove metal inclusions on a substrate after dry etching; and step A5, in which the composition is used to remove metal inclusions on a substrate after chemical mechanical polishing. For steps A1 to A5 above, the description in paragraphs

[0049] to

[0072] of WO 2019 / 138814 can be used by reference, and the contents of these are incorporated herein by reference.

[0200] [Rinsing Step] The present processing method may further include a step (hereinafter referred to as "Step B") of performing a rinse treatment on the object to be processed (substrate having metal inclusions) using a rinse liquid (rinsing and cleaning with a solvent) after Step A. Step B is preferably performed consecutively to Step A, and is a step of performing a rinse treatment with the rinse liquid for 5 seconds to 5 minutes. Step B may be performed using the mechanical stirring method described above.

[0201] Examples of the solvent for the rinse solution include deionized (DI) water, methanol, ethanol, isopropanol, N-methylpyrrolidinone, γ-butyrolactone, dimethyl sulfoxide, ethyl lactate, and propylene glycol monomethyl ether acetate. Preferred examples of the solvent for the rinse solution include DI water, methanol, ethanol, isopropanol, and mixtures thereof, and more preferred examples are DI water, isopropanol, and mixtures of DI water and isopropanol.

[0202] The method of contacting the rinse solution with the object to be treated can be the same as the method of contacting the present composition with the object to be treated described above. The temperature of the rinse solvent in step B is preferably 16 to 27°C.

[0203] [Drying Step] This processing method may include a step C of drying the workpiece (substrate having metal-containing material) after step B. The drying method is not particularly limited, and examples thereof include spin drying, a method of passing a dry gas over the workpiece, a method of heating the substrate with a heating means such as a hot plate or an infrared lamp, Marangoni drying, Rotagoni drying, IPA (isopropanol) drying, and any combination thereof. The drying time in step C depends on the drying method, but is preferably 20 seconds to 5 minutes.

[0204] In step C, the substrate is preferably dried by heating it with a heating means, from the viewpoint of excellent removability of the composition in the SiOx layer. In this case, the heating temperature is not particularly limited, but is preferably 50 to 350°C, more preferably more than 100°C and less than 400°C, from the viewpoint of excellent balance between removability of the composition in the SiOx layer and film loss in the Co film and the SiOx layer, and further preferably 150 to 250°C, from the viewpoint of excellent removability of the composition in the Co film and the SiOx layer.

[0205] [Method for Manufacturing a Semiconductor Device] The present invention also includes a method for manufacturing a semiconductor device. The method for manufacturing a semiconductor device of the present invention preferably includes a substrate processing method having the step A described above.

[0206] [Compound] The present invention also includes the invention of a compound. The compound of the present invention is a compound represented by the above formula (F).

[0207] The present invention will be described in more detail below with reference to examples. The materials, amounts used, ratios, treatment contents, treatment procedures, etc. shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the examples shown below.

[0208] [Synthesis of Specific Resin E-1 (Synthesis Example 1)] Specific Resin E-1 was synthesized according to the following scheme.

[0209]

[0210] [Synthesis of Intermediate E-1A] Under a nitrogen flow (50 mL / min), 4-acetoxystyrene (50.0 g, 0.3 mol, Tokyo Chemical Industry Co., Ltd.) and methanol (500 mL, Fujifilm Wako Pure Chemical Industries, Ltd.) were added to a 1.0 L three-neck flask, and the resulting reaction solution was stirred at 25 ° C. Subsequently, sodium methoxide (48.6 g, 0.9 mol, Fujifilm Wako Pure Chemical Industries, Ltd.) was added to the reaction solution, and the resulting reaction solution was heated to reflux for 24 hours. Next, the solvent was distilled off from the resulting reaction solution under a reduced pressure of 40 ° C. / 10 hPa. To the resulting crude product, tert-butyl methyl ether (300 mL, Fujifilm Wako Pure Chemical Industries, Ltd.) and 3 M hydrochloric acid (400 mL) were added, and the resulting solution was transferred to a 1 L separatory funnel and stirred. After stirring, the lower phase (aqueous phase) was removed, and the upper phase (organic phase) was recovered. Distilled water (300 mL) was added to the obtained organic phase and stirred, and the resulting solution after stirring was allowed to stand, the lower phase (aqueous phase) was removed, and the upper phase (organic phase) was recovered. Distilled water (300 mL) was added to the obtained organic phase and stirred, and the resulting solution after stirring was allowed to stand, the lower phase (aqueous phase) was removed, and the upper phase (organic phase) was recovered. Thereafter, the solvent was distilled off from the resulting organic phase under a reduced pressure of 40 ° C. / 10 hPa to obtain intermediate E-1A.

[0211] [Synthesis of Intermediate E-1B] Under a nitrogen flow (50 mL / min), intermediate E-1A (35.0 g, 0.29 mol), triphenylphosphine (98.8 g, 0.38 mol, FUJIFILM Wako Pure Chemical Industries, Ltd.), glycidol (28.2 g, 0.38 mol, Tokyo Chemical Industry Co., Ltd.), and tetrahydrofuran (THF, 245 mL, FUJIFILM Wako Pure Chemical Industries, Ltd.) were added to a 0.5 L three-neck flask, and the resulting reaction solution was cooled to 0°C. Next, a solution was prepared separately by dissolving bis(2-methoxyethyl) azodicarboxylate (DMEAD (registered trademark), 88.9 g, 0.38 mol, FUJIFILM Wako Pure Chemical Industries, Ltd.) in THF (105 mL). The solution was added dropwise to the reaction solution obtained above over 2 hours while maintaining the internal temperature of the reaction solution at 5°C or below. After completion of the dropwise addition, the resulting reaction solution was stirred at 0 ° C. for 2 hours. Next, the solvent was distilled off from the resulting reaction solution under a reduced pressure of 40 ° C. / 10 hPa. To the resulting crude product, tert-butyl methyl ether (300 mL, Fujifilm Wako Pure Chemical Industries, Ltd.) and distilled water (400 mL) were added, and the resulting solution was transferred to a 1 L separatory funnel and stirred. After stirring, the lower phase (aqueous phase) was removed, and the upper phase (organic phase) was recovered. Distilled water (400 mL) was added to the resulting organic phase and stirred, and the resulting solution was allowed to stand after stirring, the lower phase (aqueous phase) was removed, and the upper phase (organic phase) was recovered. The solvent was distilled off from the resulting organic phase under a reduced pressure of 40 ° C. / 10 hPa. The resulting crude product was purified by silica gel column chromatography to obtain intermediate E-1B.

[0212] [Synthesis of Intermediate E-1C] E-1B (60.0 g, 0.3 mol) and methanol (1.5 L, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were added to a 5.0 L three-neck flask, and the resulting reaction solution was stirred at 25°C. Thereafter, 28% aqueous ammonia (1.8 L, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added to the reaction solution, and the resulting reaction solution was stirred at 25°C for 4 hours. The resulting reaction solution was cooled to 0°C, and a precipitate (Precipitate 1) was filtered. While the resulting filtrate was kept cooled to 0°C, 6.0 L of distilled water was added, and a precipitate (Precipitate 2) was filtered. The resulting Precipitates 1 and 2 were combined and washed twice with 0.5 L of distilled water. Thereafter, the mixture was dried by blowing air at 40°C to obtain Intermediate E-1C.１ The H-NMR (Nuclear Magnetic Resonance) data is shown below. １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 7.38 (d, J = 8.7Hz, 2H), 6.90 (d, J = 8.7Hz, 2H), 6.65 (dd, J = 10.9Hz , 17.7Hz, 1H), 5.67 (d, J = 17.6Hz, 1H), 5.10 (d, J = 10.9Hz, 1H), 3.60-3.98 (m, 3H), 2.52-2.72 (m, 2H).

[0213] [Synthesis of Specific Resin E-1] Under a nitrogen flow (50 mL / min), intermediate E-1C (25.1 g, 0.13 mol) and distilled water (120 g) were added to a 0.5 L three-neck flask and cooled to 0°C. 1 M hydrochloric acid (130 mL) and methacrylic acid (11.2 g, 0.13 mol, Fujifilm Wako Pure Chemical Industries, Ltd.) were added to the resulting reaction solution, and the resulting reaction solution was stirred at 70°C for 30 minutes. Next, a solution was prepared separately by dissolving VA-044 (2.1 g, 6.5 mmol, Fujifilm Wako Pure Chemical Industries, Ltd.) in distilled water (10.5 mL). The above solution was added to the reaction solution obtained above, and the resulting reaction solution was further stirred at 70°C for 3 hours. １ After confirming that the signals derived from Intermediate E-1C and methacrylic acid had disappeared by H-NMR, the solution was filtered to remove dust, thereby obtaining an aqueous solution containing Specific Resin E-1 (solid content concentration: 13.1% by mass). １ The H-NMR data is shown below. １ H-NMR (400MHz, D ２ O): δ (ppm) = 6.50-8.00 (broad, 4H), 4.08-4.24 (broad, 1H), 3.86-4.08 (broa d, 3H), 3.12-3.24 (broad, 1H), 2.94-3.12 (broad, 1H), 0.70-2.90 (broad, 7H)

[0214] [Synthesis of Specific Resin E-16 (Synthesis Example 2)] Specific Resin E-16 was synthesized according to the following scheme.

[0215]

[0216] [Synthesis of Intermediate E-16C] Intermediate E-16C was synthesized according to the procedures described in [Synthesis of Intermediate E-1B] and [Synthesis of Intermediate E-1C] above, except that E-16A was used instead of E-1A in [Synthesis of Intermediate E-1B] above. １ The H-NMR data is shown below. １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 8.00 (d, J = 8.7Hz, 2H), 7.47 (d, J = 8.7Hz, 2H), 6.76 (dd, J = 10.9Hz , 17.7Hz, 1H), 5.89 (d, J = 17.6Hz, 1H), 5.60 (d, J = 10.9Hz, 1H), 3.80-4.18 (m, 3H), 2.72-2.92 (m, 2H).

[0217] [Synthesis of Specific Resin E-16] Specific Resin E-16 was synthesized according to the procedure described in [Synthesis of Specific Resin E-1] above, except that E-16C was used instead of E-1C and 4-carboxystyrene was used instead of methacrylic acid. １ The H-NMR data is shown below. １ H-NMR (400MHz, D ２ O): δ (ppm) = 6.50-8.00 (broad, 8H), 4.28-4.44 (broad, 1H), 4.06-4.28 (broa d, 4H), 3.22-3.44 (broad, 1H), 2.94-3.12 (broad, 1H), 0.70-2.90 (broad, 4H)

[0218] [Synthesis of Specific Resin E-17 (Synthesis Example 3)] Specific Resin E-17 was synthesized according to the following scheme.

[0219]

[0220] [Synthesis of Intermediate E-17A] Under a nitrogen flow (50 mL / min), glycidol (37.0 g, 0.5 mol), triphenylphosphine (157.2 g, 0.6 mol, FUJIFILM Wako Pure Chemical Industries, Ltd.), phthalimide (88.2 g, 0.6 mol, FUJIFILM Wako Pure Chemical Industries, Ltd.), and THF (259 mL, FUJIFILM Wako Pure Chemical Industries, Ltd.) were added to a 0.5 L three-neck flask, and the resulting mixture was cooled to 0°C. Next, a solution was prepared separately by dissolving DMEAD (registered trademark) (40.4 g, 0.6 mol, FUJIFILM Wako Pure Chemical Industries, Ltd.) in THF (111 mL). While maintaining the internal temperature of the resulting mixture at 5°C or below, the solution was added dropwise to the mixture over 2 hours. After completion of the dropwise addition, the resulting reaction mixture was stirred at 0°C for 2 hours. Next, the solvent was distilled off from the resulting reaction solution under a reduced pressure of 40 ° C. / 10 hPa. To the obtained crude product, tert-butyl methyl ether (300 mL, Fujifilm Wako Pure Chemical Industries, Ltd.) and distilled water (400 mL) were added, and the resulting solution was transferred to a 1 L separatory funnel and stirred. After stirring, the lower phase (aqueous phase) was removed, and the upper phase (organic phase) was recovered. Distilled water (400 mL) was added to the obtained organic phase and stirred, and the solution obtained after stirring was allowed to stand, the lower phase (aqueous phase) was removed, and the upper phase (organic phase) was recovered. Under a reduced pressure of 40 ° C. / 10 hPa, the solvent was distilled off from the resulting organic phase. The obtained crude product was purified by silica gel column chromatography to obtain intermediate E-17A.

[0221] [Synthesis of Intermediate E-17B] Intermediate E-17B was synthesized using methyl 4-vinylbenzoate as a starting material according to the method described in J. Org. Chem. 2002, 67, 5838.

[0222] [Synthesis of Intermediate E-17C] Under a nitrogen flow (50 mL / min), intermediate E-17B (13.4 g, 0.1 mol) and THF (400 mL, Fujifilm Wako Pure Chemical Industries, Ltd.) were placed in a 0.5 L three-neck flask and cooled to 0°C. 60% NaH (4.0 g, 0.1 mol) was then added portionwise, followed by stirring at 0°C for an additional 1 hour. Intermediate E-17A (20.3 g, 0.1 mol) was then added, and the resulting reaction solution was stirred under reflux for 24 hours. After cooling the reaction solution to 0°C, water was added to terminate the reaction, and the solvent was distilled off from the resulting reaction solution at 40°C / 10 hPa under reduced pressure. To the obtained crude product, tert-butyl methyl ether (300 mL, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and distilled water (400 mL) were added, and the obtained solution was transferred to a 1 L separatory funnel and stirred. After stirring, the lower phase (aqueous phase) was removed, and the upper phase (organic phase) was recovered. Distilled water (400 mL) was added to the obtained organic phase and stirred, and the solution obtained after stirring was allowed to stand, the lower phase (aqueous phase) was removed, and the upper phase (organic phase) was recovered. The solvent was distilled off from the obtained organic phase under a reduced pressure of 40 ° C. / 10 hPa. The obtained crude product was purified by silica gel column chromatography to obtain intermediate E-17C.

[0223] [Synthesis of Intermediate E-17D] Under a nitrogen flow (50 mL / min), intermediate E-17C (27.0 g, 0.08 mol) and ethanol (250 mL, FUJIFILM Wako Pure Chemical Industries, Ltd.) were added to a 1.0 L three-neck flask and stirred. Hydrazine monohydrate (23.3 g, 0.47 mmol, FUJIFILM Wako Pure Chemical Industries, Ltd.) was added to the resulting reaction solution, and the mixture was heated to reflux for 3 hours. The resulting reaction solution was then cooled to 0°C, and the precipitate was filtered. The filtered product was washed with THF (60 mL) cooled to 0°C, and the washings were recovered. The resulting filtrate and the recovered washings were mixed, and the mixture was concentrated. Dichloromethane (300 mL, FUJIFILM Wako Pure Chemical Industries, Ltd.) and a 20% by weight aqueous sodium hydroxide solution (300 mL) were added to the resulting crude product, and the resulting solution was transferred to a 1 L separatory funnel and stirred. After stirring, the lower phase (aqueous phase) was removed and the upper phase (organic phase) was collected. The obtained organic phase was concentrated to obtain intermediate E-17D. １ The H-NMR data is shown below.１ H-NMR (400MHz, DMSO-d6): δ (ppm) = 7.38 (d, J = 8.7Hz, 2H), 6.90 (d, J = 8.7Hz, 2H), 6.65 (dd, J = 10.9Hz, 17.7H z, 1H), 5.67 (d, J = 17.6Hz, 1H), 5.10 (d, J = 10.9Hz, 1H), 4.42 (s, 2H), 3.60-3.98 (m, 3H), 2.52-2.72 (m, 2H).

[0224] [Synthesis of specific resin E-17] Specific resin E-17 was synthesized according to the procedure described in [Synthesis of specific resin E-1] above, except that E-17D was used instead of E-1C and vinyl sulfonic acid was used instead of methacrylic acid. １ The H-NMR data is shown below. １ H-NMR (400MHz, D ２ O): δ (ppm) = 6.50-8.00 (broad, 4H), 4.08-4.24 (broad, 3H), 3.86-4.08 (broa d, 3H), 3.12-3.24 (broad, 1H), 2.94-3.12 (broad, 1H), 0.70-2.90 (broad, 4H)

[0225] [Synthesis of Specific Resin E-18 (Synthesis Example 4)] Specific Resin E-18 was synthesized according to the following scheme.

[0226]

[0227] [Synthesis of Intermediate E-18A] Intermediate E-18A was synthesized using 4-bromostyrene as a starting material according to the method described in Org. Lett. 2000, 2, 1729.

[0228] [Synthesis of Intermediate E-18B] Intermediate E-18B was synthesized according to the procedure described in [Synthesis of Intermediate E-1C] above, except that E-18A was used instead of Intermediate E-1B. １ The H-NMR data is shown below. １H-NMR (400MHz, DMSO-d6): δ (ppm) = 8.00 (d, J = 8.7Hz, 2H), 7.47 (d, J = 8.7Hz, 2H), 6.76 (dd, J = 10.9Hz, 17.7H z, 1H), 5.89 (d, J = 17.6Hz, 1H), 5.60 (d, J = 10.9Hz, 1H), 4.40 (s, 2H), 3.80-4.18 (m, 3H), 2.72-2.92 (m, 2H).

[0229] [Synthesis of Specific Resin E-18] Specific Resin E-18 was synthesized according to the procedure described in [Synthesis of Specific Resin E-1] above, except that E-18B was used instead of E-1C and maleic acid was used instead of methacrylic acid. １ The H-NMR data is shown below. １ H-NMR (400MHz, D ２ O): δ (ppm) = 6.50-8.00 (broad, 4H), 4.08-4.24 (broad, 3H), 3.86-4.08 (broa d, 3H), 3.12-3.24 (broad, 1H), 2.94-3.12 (broad, 3H), 0.70-2.90 (broad, 2H)

[0230] [Raw Materials for Compositions] The following compounds were used to prepare the compositions. Note that all of the components used in the examples were classified as semiconductor grade or equivalent high purity grade.

[0231] <Specific Resins and Other Resins> Specific resins E-1 to E-19, and resins (resins not falling under the specific resins) CE-1 to CE-2 were used. In the structural formulas below, the repeating unit in the leftmost column corresponds to repeating unit A, and the repeating unit in the rightmost column corresponds to repeating unit B. However, for specific resin E-7, the repeating unit in the center column corresponds to repeating unit A, and the repeating unit in the rightmost column corresponds to repeating unit B. In the structural formulas below, "Mw" is the weight-average molecular weight of each resin measured by the method described above. Furthermore, the numbers attached to the repeating units indicate the composition ratio (molar fraction) of each repeating unit in the resin. The composition ratio of each repeating unit in the resin is １３Measurement was performed by C-NMR.

[0232]

[0233]

[0234] <Removing agents> ・Hydroxylamine (corresponding to a hydroxylamine compound.) ・Ammonium hydroxide (corresponding to a basic compound.) ・Tetramethylammonium hydroxide (TMAH) (corresponding to a basic compound.) ・Hydrogenous acid (corresponding to a fluorine-containing compound.) ・Sulfuric acid (corresponding to an inorganic acid.) ・Citric acid (corresponding to an organic acid.) ・Tartaric acid (corresponding to an organic acid.) ・Succinic acid (corresponding to an organic acid.) ・Ethylenediaminetetraacetic acid (EDTA) (corresponding to an organic acid.) ・Trishydroxymethylaminomethane (Tris) (corresponding to a basic compound.) ・Monoethanolamine (corresponding to a basic compound.) ・Tris(2-hydroxyethyl)methylammonium hydroxide (corresponding to a basic compound.) ・2-Dimethylamino-2-methyl-1-propanol (corresponding to a basic compound.)

[0235] <Oxidizing agent> Hydrogen peroxide

[0236] <Corrosion inhibitors> ・5-methyl-1H-benzotriazole ・5-mercapto-1-phenyl-1H-tetrazole (corresponding to a tetrazole compound) ・n-dodecyl mercaptan (corresponding to a thiol compound)

[0237] <Surfactants> Persoft (registered trademark) SF-T (alkyl sulfate ester triethanolamine salt, anionic surfactant, manufactured by NOF Corporation) NissanCation (registered trademark) BB (dodecyltrimethylammonium chloride, cationic surfactant, manufactured by NOF Corporation) Nonion K-220 (polyoxyethylene lauryl ether, nonionic surfactant, manufactured by NOF Corporation) NissanAnon (registered trademark) BL (lauryldimethylaminoacetic acid betaine, amphoteric surfactant, manufactured by NOF Corporation)

[0238] <Antifoaming agent> KF-6701 (silicone-based antifoaming agent, manufactured by Shin-Etsu Chemical Co., Ltd.)

[0239] <Solvent> ・Propylene glycol ・Water (ultrapure water)

[0240] <pH adjuster> Citric acid Monoethanolamine Nitric acid (HNO ３ ) Potassium hydroxide (KOH)

[0241] [Example A] [Preparation of Composition] The preparation method for each of the compositions of Examples A1 to A21 and Comparative Examples A1 to A2 will be described using Example A1 as an example. Hydroxylamine, 5-methyl-1H-benzotriazole, Persoft SF-T, and ultrapure water were mixed in the amounts shown in Table 2 below to obtain a mixed solution C-1. Then, the mixed solution C-1, specific resin E-1, and at least one of citric acid and monoethanolamine as a pH adjuster were thoroughly stirred using a stirrer to prepare the composition (cleaning treatment liquid) of Example A1. The contents of specific resin E-1 and mixed solution C-1 in the resulting composition, as well as the pH of the composition, are shown in Table 1 below. Regarding the type and amount of pH adjuster, the pH of the mixed solution of specific resin E-1 and mixed solution C-1 was measured, and if the pH of the mixed solution was higher than the value shown in Table 1, citric acid was added; if the pH of the mixed solution was lower, monoethanolamine was added in an amount that would result in the pH of the mixed solution shown in Table 1.

[0242] Compositions of each Example and Comparative Example having the formulations shown in Tables 1 and 2 below were prepared in accordance with the method for preparing the composition of Example A1.

[0243] [Evaluation of Compositions] The following tests were carried out using each of the prepared compositions.

[0244] <Solubility> Substrates (Si) were prepared on which a W film made of elemental tungsten (W) and a TiAlC film made of titanium aluminum carbide (TiAlC) were laminated to a thickness of 100 nm. These substrates were then cut into 2 cm x 2 cm squares to prepare test specimens. Each of the obtained test specimens was immersed in each composition (liquid temperature: 80°C) for 10 minutes. The film thickness of each film was measured before and after the immersion test using a thin film evaluation X-ray fluorescence analyzer (XRF AZX-400, manufactured by Rigaku Corporation). The dissolution rate (Å / min) of each film when using each composition was calculated from the measured film thickness before and after immersion. The solubility of the W film and the TiAlC film was evaluated from the calculated dissolution rate based on the following evaluation criteria. The evaluation results of the solubility of the obtained W film and the TiAlC film are shown in Table 1 below. The slower the dissolution rate, the more suppressed the dissolution of each film, with "S" representing the highest solubility rating.

[0245] (Evaluation criteria for W film solubility) S: The dissolution rate of the W film is 0.5 Å / min or less. A: The dissolution rate of the W film is more than 0.5 Å / min and less than 0.7 Å / min. B: The dissolution rate of the W film is more than 0.7 Å / min and less than 1.0 Å / min. C: The dissolution rate of the W film is more than 1.0 Å / min and less than 3.0 Å / min. D: The dissolution rate of the W film is more than 3.0 Å / min and less than 5.0 Å / min. E: The dissolution rate of the W film is more than 5.0 Å / min.

[0246] (Evaluation criteria for solubility of TiAlC film) S: The dissolution rate of the TiAlC film is 0.5 Å / min or less. A: The dissolution rate of the TiAlC film is more than 0.5 Å / min and less than 0.7 Å / min. B: The dissolution rate of the TiAlC film is more than 0.7 Å / min and less than 1.0 Å / min. C: The dissolution rate of the TiAlC film is more than 1.2 Å / min and less than 1.5 Å / min. D: The dissolution rate of the TiAlC film is more than 1.5 Å / min and less than 1.7 Å / min. E: The dissolution rate of the TiAlC film is more than 1.7 Å / min.

[0247] <Residue removal> A W film, SiO ２ A laminate (corresponding to a pre-processing laminate) including, in this order, a W film, a metal hard mask (TiN) having a predetermined opening, and a SiO 2 film was formed. The obtained laminate was used to perform dry etching using the metal hard mask as a mask, and the SiO 2 film was removed until the W film surface was exposed. ２The film was etched to form holes, thereby producing Sample 1 (see FIG. 1). When the cross section of this laminate was observed with a scanning electron microscope (SEM), dry etching residues were observed on the wall surfaces of the holes.

[0248] The removability of dry etching residues (residue removability) was evaluated according to the following procedure. First, a prepared piece of Sample 1 (approximately 2.0 cm x 2.0 cm square) was immersed in each composition whose temperature had been adjusted to 80°C. Immediately after 3 minutes had elapsed since the start of immersion, the piece of Sample 1 was removed and immediately washed with ultrapure water and then dried with N ２ The surface of the immersed slice of Sample 1 was then observed with an SEM to confirm the presence or absence of dry etching residues. Similarly, the slice of Sample 1 that had been immersed for 5 minutes was washed with ultrapure water and dried. ２ After drying, the surfaces of the slices were observed with an SEM to check for the presence or absence of dry etching residues. From the observation results of the slices of each sample 1, the residue removability was evaluated according to the following criteria.

[0249] (Evaluation criteria for residue removability) A: Dry etching residue was completely removed by immersion for 3 minutes. B: Dry etching residue was not completely removed by immersion for 3 minutes, but was completely removed by immersion for 5 minutes. C: Dry etching residue was not completely removed by immersion for 5 minutes.

[0250] <Evaluation of Residual Properties of Composition After Rinse Treatment> SiO ２ A substrate (Si) having a film was prepared, and this SiO ２ The film-coated substrate was immersed for 10 minutes in each composition adjusted to 80° C. The immersion-treated substrate was then immersed for 0.5 minutes in a rinse solution of isopropanol to remove the SiO ２ The membrane was then rinsed.

[0251] Rinse-treated SiO ２ The surface of the film was analyzed by X-ray photoelectron spectroscopy. ２The ratio (unit: atom %) of the number of nitrogen atoms derived from each composition (particularly, the specific resin) to the number of all atoms on the surface of the film was measured. The measurement conditions for X-ray photoelectron spectroscopy are shown below.

[0252] (Measurement conditions) Apparatus: Quantera SXM™ manufactured by ULVAC-PHI, Inc. X-ray source: monochromatic Al Kα ray X-ray beam diameter: φ200 μm Signal acquisition angle: 45°

[0253] SiO ２ The residual property of the composition after the rinsing treatment (post-rinsing residual property) was evaluated from the measurement results of the ratio of the number of nitrogen atoms to all atoms on the surface of the film. The obtained evaluation results are shown in Table 1 below. The ratio of the number of nitrogen atoms to all atoms is preferably smaller. The smaller the ratio of the number of nitrogen atoms to all atoms, the higher the solubility of each component of the composition (particularly the specific resin) in the rinsing solution, and the lower the SiO after the rinsing treatment. ２ This means that the amount of the composition remaining on the film surface is small.

[0254] (Evaluation criteria for post-rinse survivability) A: SiO ２ The ratio of the number of nitrogen atoms to the total number of atoms on the film surface is 0.1 atom % or less. B: SiO ２ The ratio of the number of nitrogen atoms to the total atoms on the film surface is more than 0.1 atom % and 1.0 atom % or less. C:SiO ２ The ratio of the number of nitrogen atoms to the total atoms on the film surface is more than 1.0 atom % and 3.0 atom % or less. D: SiO ２ The ratio of the number of nitrogen atoms to the total number of atoms on the film surface is more than 3.0 atom %

[0255] Tables 1 and 2 show the compositions of the compositions used in each Example and Comparative Example, and Table 1 shows the evaluation results for each Example and Comparative Example. Table 2 shows the formulations of the components of mixed solutions C-1 to C-6 used to prepare each of the compositions. Table 1 shows the contents of the resin and mixed solution contained in each composition, as well as the pH of each composition, and Table 2 shows the type and content of each component contained in each mixed solution.

[0256] In Table 1, the "Ratio a / b" column for "Specific Resin" indicates the ratio a / b of the number of moles a of repeating unit A to the number of moles b of repeating unit B in a specific resin having repeating units A and repeating units B. In Table 1, the "Amount (Parts by Mass)" column for "Specific Resin" indicates the content of the specific resin when the total mass of the composition is 100 parts by mass. In Table 1, the "pKa" column for "Specific Resin" indicates the pKa of a functional group in repeating unit B having a pKa of 10.0 or less. In Table 1, the "Amount (Parts by Mass)" column for "Mixture" indicates the content of the mixture when the total mass of the composition is 100 parts by mass. In Table 1, the "pH" column indicates the pH of the composition at 25°C measured using the pH meter described above. In Table 2, the numerical values ​​shown in each column indicate the content (unit: "parts by mass") of each component when the total mass of each mixture is 100 parts by mass.

[0257]

[0258]

[0259]

[0260] The results in Table 1 confirm that the present composition is excellent in all of the following: solubility in W films, solubility in TiAlC films, removability of etching residues, and remaining properties of the composition after rinsing. On the other hand, the comparative composition, although containing a resin having a repeating unit with a pyrrolidone skeleton or a resin having a repeating unit with a specific group and a repeating unit with a hydroxyl group, did not achieve sufficient effects in all of the solubility in W films, solubility in TiAlC films, removability of etching residues, and remaining properties of the composition after rinsing.

[0261] Furthermore, from the results in Table 1, it was confirmed that the specific resin has better solubility in a W film when the repeating unit A is a repeating unit derived from a compound represented by formula (A), a repeating unit derived from a compound represented by formula (B), or a repeating unit represented by formula (C) (e.g., comparison between Example A9 and Example A13). It was confirmed that the specific resin has better solubility in a TiAlC film when at least one of the specific groups is a primary amino group or a salt thereof (e.g., comparison between Examples A6 to A8). It was confirmed that the specific resin has better solubility in a TiAlC film when the repeating unit A is a repeating unit derived from a compound represented by formula (A), a repeating unit derived from a compound represented by formula (B), or a repeating unit represented by formula (C) (e.g., comparison between Examples A9 and A13). ａ is a (n+2)-valent linking group containing an aromatic ring; L ｂ１ and L ｂ２ It has been confirmed that when the repeating unit A is a repeating unit derived from a compound represented by formula (B), or a repeating unit represented by formula (C), at least one of which is a divalent linking group containing an aromatic ring, the solubility in the W film is better (e.g., comparison between Examples A6 and A10). It has been confirmed that when the repeating unit A is a repeating unit derived from a compound represented by formula (D), or a repeating unit represented by formula (E), the solubility in the W film is better (e.g., comparison between Examples A1 and A10). It has been confirmed that when the repeating unit B has a functional group with a pKa of 5.0 or less, the remnants of the composition after rinsing are better (e.g., comparison between Examples A1 and A12).

[0262] Instead of the specific resin E-1 used in Example A1 in Table 1, 0.025 parts each of specific resin E-14 and specific resin E-18 were used in combination, so that the total amount of specific resin E-14 and specific resin E-18 was 0.05 parts, and when the above evaluation was performed, it was confirmed that the same evaluation results as those of the composition described in Example A1 were shown. Furthermore, instead of the specific resin E-1 used in Example A1, 0.025 parts each of specific resin E-15 and polymethacrylic acid as a resin were used in combination, so that the total amount of specific resin E-15 and polymethacrylic acid was 0.05 parts, and when the above evaluation was performed, it was confirmed that the same evaluation results as those of Example A1 were shown.

[0263] [Example B] [Preparation of Composition] The preparation method of each composition of Examples B1 to B5 and Comparative Examples B1 to B2 will be described using Example B1 as an example. Specific resin E-1, citric acid, trishydroxymethylaminomethane (Tris), and ultrapure water were mixed in the amounts shown in Table 3 below, and then potassium hydroxide or nitric acid was added as a pH adjuster so that the pH of the prepared composition was 6.0. The resulting mixture was thoroughly stirred using a stirrer to prepare the composition of Example B1.

[0264] Compositions of each Example and Comparative Example having the formulations shown in Table 3 below were prepared in accordance with the method for preparing the composition of Example B1.

[0265] [Evaluation of Compositions] <Residue Removal Ability> Each of the prepared compositions was used to evaluate the residue removal ability (cleaning performance) when cleaning a metal film that had been subjected to CMP treatment. Specifically, a FREX-300SII (polishing device, manufactured by Ebara Corporation) was used, and a polishing liquid (W2000, manufactured by Cabot Corporation) was used at a supply rate of the polishing liquid of 0.28 mL / (min cm ２ A wafer (12 inches in diameter) having a metal film made of tungsten on its surface was subjected to CMP under the conditions of 2.0 psi, a polishing pressure of 2.0 psi, and a polishing time of 60 seconds. The temperature of each composition was then adjusted to room temperature (23°C), and the wafer was scrubbed for 60 seconds using each composition, followed by a drying process. The number of defects on the polished surface of the resulting wafer was detected using a defect detection device, and each defect was observed with a SEM (scanning electron microscope) and classified. If necessary, the constituent elements were analyzed with an EDAX (energy dispersive X-ray analyzer) to identify the components. The number of defects due to residues from the CMP process was determined, and the cleaning performance was evaluated according to the following evaluation criteria (with a rating of 6 indicating the best cleaning performance).

[0266] (Evaluation criteria for residue removability) 6: Number of target defects is less than 20 5: Number of target defects is 20 or more but less than 50 4: Number of target defects is 50 or more but less than 100 3: Number of target defects is 100 or more but less than 200 2: Number of target defects is 200 or more but less than 300 1: Number of target defects is 300 or more

[0267] <Solubility> Each composition was used to evaluate the solubility of a metal film when the metal film was cleaned. Specifically, wafers (12 inches in diameter) having a W film made of elemental tungsten (W) on the surface were cut to prepare 2 cm x 2 cm square wafer coupons. The W film had a thickness of 200 nm. The wafer coupons were immersed in each composition (liquid temperature: 23°C) for 30 minutes under stirring at a rotation speed of 250 rpm. Before and after the immersion test, the film thickness of the W film was measured using an optical film thickness meter, Ellipsometer M-2000 (manufactured by JA Woollam). The dissolution rate (Å / min) of the W film when each composition was used was calculated from the measured film thickness before and after immersion. The solubility of the W film (the ability to inhibit dissolution of the W film) was evaluated from the calculated dissolution rate based on the following evaluation criteria. A slower dissolution rate indicates that the composition more effectively inhibits dissolution of the W film (e.g., a rating of 6 indicates the most excellent solubility).

[0268] (Evaluation criteria for W film solubility) 6: The dissolution rate of the W film is 0.5 Å / min or less. 5: The dissolution rate of the W film is more than 0.5 Å / min and less than 0.7 Å / min. 4: The dissolution rate of the W film is more than 0.7 Å / min and less than 1.0 Å / min. 3: The dissolution rate of the W film is more than 1.0 Å / min and less than 3.0 Å / min. 2: The dissolution rate of the W film is more than 3.0 Å / min and less than 5.0 Å / min. 1: The dissolution rate of the W film is more than 5.0 Å / min.

[0269] Table 3 shows the composition and evaluation results of each composition used in each example and each comparative example. In Table 3, the "Amount (%)" column for each component indicates the content (unit: mass %) of each component relative to the total mass of the composition. In Table 3, the numerical value in the "Organic Acid / Amine" column indicates the content of organic acid (removal agent) relative to the content of basic compound (removal agent). In Table 3, the "Balance" in the "Water" column indicates that the content of water is the remainder of the composition other than the resin, removal agent, and pH adjuster. In Table 3, the numerical value in the "pH" column indicates the pH of the composition at 25°C measured using the pH meter described above.

[0270]

[0271] The results in Table 3 confirm that the compositions of the examples of the present invention are excellent in both solubility in W films and removability of residues from wafers subjected to CMP processing. On the other hand, the comparative compositions not containing the specific resin were evaluated as having low solubility in W films, and the above-mentioned effects were not obtained.

[0272] In the residue removal evaluation test, a wafer having a metal film made of W on its surface was subjected to CMP, and then the polished surface of the CMP-treated wafer was subjected to buffing. In the buffing, each composition adjusted to room temperature (23°C) was used as a buffing cleaning liquid. The polishing apparatus used in the CMP treatment was also used, and the polishing pressure was 2.0 psi and the supply rate of the buffing cleaning liquid was 0.28 mL / (min cm). ２ ), and a buffing treatment was performed under the conditions of a polishing time of 60 seconds. Thereafter, the buffed wafer was cleaned for 30 seconds using each composition adjusted to room temperature (23°C), and then dried. The residue removability of the composition was evaluated for the polished surface of the obtained wafer according to the test method described above in <Residue Removability>, and it was confirmed that the composition showed evaluation results similar to those of the compositions of the above examples.

[0273] REFERENCE SIGNS LIST 1 substrate 2 metal layer 3 etching stop layer 4 insulating film 5 metal hard mask 6 hole 10 stacked body 11 inner wall 11a cross-sectional wall 11b bottom wall 12 dry etching residue

Claims

1. A repeating unit A having a specific group selected from the group consisting of a primary amino group, a secondary amino group, a tertiary amino group, and salts thereof, and a hydroxy group, and a repeating unit B having a functional group with a pKa of 10.0 or less or a salt thereof, a resin containing the same, and water, a composition for a semiconductor device.

2. The composition for a semiconductor device according to claim 1, wherein the repeating unit A is a repeating unit derived from a compound represented by formula (A), a repeating unit derived from a compound represented by formula (B), or a repeating unit represented by formula (C). 【Chemical 1】 In formula (A), R ａ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. X ａ represents a specific group selected from the group consisting of a primary amino group, a secondary amino group, a tertiary amino group, and salts thereof. L ａ represents a linking group having a valence of (na + 2). na represents an integer of 1 to 5. In formula (B), R ｂ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R Ｎ represents a hydrogen atom or an alkyl group which may have a substituent. L ｂ１ and L ｂ２ each independently represents a single bond or a divalent linking group. In formula (C), * represents a bonding position. R ｃ represents a hydrogen atom or a methyl group. X ｃ represents a specific group selected from the group consisting of a primary amino group, a secondary amino group, a tertiary amino group, and salts thereof. L ｃ represents a (nc + 2)-valent linking group. nc represents an integer of 1 to 5.

3. The composition for a semiconductor device according to claim 1, wherein at least one of the specific groups is a primary amino group or a salt thereof.

4. wherein the repeating unit A is L ａ is a repeating unit derived from the compound represented by the formula (A) which is the (na + 2)-valent linking group containing an aromatic ring, L ｂ１ and L ｂ２ at least one of which is a repeating unit derived from the compound represented by the formula (B) which is a divalent linking group containing an aromatic ring, or a repeating unit represented by the formula (C), the composition for a semiconductor device according to claim 2.

5. The composition for a semiconductor device according to claim 1, wherein the repeating unit A is a repeating unit derived from a compound represented by formula (D) or a repeating unit represented by formula (E). 【Chemical 2】 In formula (D), R ｄ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. L ｄ represents a single bond or a divalent linking group. R ｄ２ represents a group represented by formula (X) or a group represented by formula (Y). In formula (X) and formula (Y), * represents a bonding position. X represents a primary amino group or a salt thereof. In formula (E), * represents a bonding position. R ｅ１ represents a hydrogen atom or a methyl group. L ｅ represents a divalent linking group. R ｅ２ represents a group represented by the formula (X) or a group represented by the formula (Y).

6. The composition for a semiconductor device according to claim 1, wherein the pKa of the functional group is 5.0 or less.

7. The composition for a semiconductor device according to claim 1, wherein the functional group is a carboxy group.

8. The composition for a semiconductor device according to claim 1, further comprising at least one selected from the group consisting of a remover, an oxidizing agent, a corrosion inhibitor, a surfactant, an antifoaming agent, and an organic solvent.

9. The composition for a semiconductor device according to claim 1, further comprising a remover.

10. A method for treating a substrate, comprising step A of bringing the composition for a semiconductor device according to any one of claims 1 to 9 into contact with a substrate having a metal-containing material.

11. The method for treating a substrate according to claim 10, further comprising step B of rinsing the substrate obtained in step A with a rinsing solution after step A.

12. A method for manufacturing a semiconductor device, comprising the method for treating a substrate according to claim 10.

13. A compound represented by formula (F). [Chemical Formula 3] In formula (F), X ｆ represents a specific group selected from the group consisting of a primary amino group, a secondary amino group, a tertiary amino group, and salts thereof. L ｆ represents -CH ２ O-, -COO-, -C≡C-CH ２ O-, or -O-.

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