TW202414565A - Processing liquid, method for treating object to be treated, and method for manufacturing semiconductor device - Google Patents

Abstract

The present invention provides a processing liquid that is excellent in inhibiting corrosions of Cu and also excellent in removing organic residues. The processing liquid contains a reducing agent, and at least one specific compound selected from the group consisting of dehydroascorbic acid, 2,3-diketogulonic acid, 4-oxalocrotonic acid, and 3,4,5-trioxocyclohexane-1-carboxylic acid.

Description

Processing liquid, processing method of object, and manufacturing method of semiconductor device

The present invention relates to a processing liquid, a processing method for an object and a manufacturing method for a semiconductor device.

Semiconductor devices are manufactured by forming a photoresist film on a laminate having a metal film, an etch stop layer, and an interlayer insulating layer on a substrate and performing a photolithography step. In the photolithography step, a method of etching or removing foreign matter on the surface of the substrate using a treatment solution that dissolves metal and/or organic matter is well known.

In addition, in the manufacture of semiconductor devices, a polishing slurry containing abrasive particles (e.g., silicon dioxide and aluminum oxide) is sometimes used to perform a chemical mechanical polishing (CMP) process to flatten the surface of a semiconductor substrate having a metal wiring film, a barrier metal, and an insulating film. In the CMP process, the abrasive particles and various organic components used in the CMP process and metal components derived from the polished wiring metal film and/or barrier metal are likely to remain on the surface of the semiconductor substrate after polishing. Therefore, after the CMP process, a step of using a treatment liquid to remove such residues is usually performed.

As described above, in the semiconductor manufacturing process, the processing liquid is used to remove unnecessary metal inclusions, anti-etching agents, and residues on the processing substrate.

As a processing liquid as described above, for example, Patent Document 1 discloses a substrate processing liquid for semiconductor devices, which contains specific compounds represented by histidine and histidine derivatives, ascorbic acid, gallic acid and water, and has a pH of 8 or above, wherein the concentration of ascorbic acid in the processing liquid is 0.01 mass % or above, and the concentration of gallic acid in the processing liquid is 0.01 mass % or above.

[Patent Document 1] Japanese Patent Application Publication No. 2019-125810

The inventors of the present invention have studied the treatment liquid described in Patent Document 1 and found that it is difficult to achieve both Cu corrosion inhibition and organic slag removal, and further improvement is required.

Therefore, the subject of the present invention is to provide a treatment liquid that has excellent corrosion inhibition of Cu and excellent organic residue removal. In addition, the subject of the present invention is to provide a method for treating an object using the above-mentioned treatment liquid and a method for manufacturing a semiconductor device.

In order to solve the above problems, the inventors of the present invention conducted intensive research and found that the following structure can solve the problems.

[1] A treatment solution comprising: a reducing agent; and a specific compound selected from the group consisting of dehydroascorbic acid, 2,3-diketogulonic acid, 4-oxalylcrotonic acid, and 3,4,5-trioxane-1-carboxylic acid. [2] The treatment solution as described in [1], wherein the reducing agent comprises at least one selected from the group consisting of ascorbic acid and ascorbic acid derivatives or their salts, and polyphenol compounds. [3] The treatment solution as described in [1] or [2], wherein the reducing agent comprises at least one selected from the group consisting of ascorbic acid and ascorbic acid derivatives or their salts, and gallic acid and its derivatives. [4] The treatment solution as described in any one of [1] to [3], wherein the mass ratio of the content of the above-mentioned specific compound to the content of the above-mentioned reducing agent is 0.01 to 199. [5] The treatment solution as described in any one of [1] to [4], which further contains a quaternary ammonium compound represented by the formula (B) described below. [6] The treatment solution as described in [5], wherein the mass ratio of the content of the above-mentioned quaternary ammonium compound to the content of the above-mentioned specific compound is 0.01 to 100.0. [7] The treatment solution as described in any one of [1] to [6], wherein the pH is 8.0 to 13.0. [8] The treatment solution as described in any one of [1] to [7], which further contains a chelating agent. [9] The treatment solution as described in [8], wherein the above-mentioned chelating agent contains an organic acid. [10] The treatment solution as described in [9], wherein the organic acid contains at least one selected from the group consisting of polycarboxylic acids, hydroxycarboxylic acids and phosphonic acids. [11] The treatment solution as described in [9], wherein the organic acid contains at least one selected from the group consisting of citric acid, formic acid, oxalic acid, tartaric acid, lactic acid, 1-hydroxyethylidene-1,1'-diphosphonic acid and ethylenediaminetetrakis(methylenephosphonic acid). [12] The treatment solution as described in any one of [8] to [11], wherein the mass ratio of the content of the reducing agent to the content of the chelating agent is 0.005 to 5.0. [13] The treatment solution as described in any one of [1] to [12], further containing an amine compound. [14] The treatment solution as described in [13], wherein the amine compound contains a compound represented by the formula (C1) described below. [15] A treatment solution as described in [14], wherein the carbon number of the group represented by R ⁹ in the above formula (C1) is 2 to 4. [16] A treatment solution as described in any one of [1] to [15], which further contains a preservative. [17] A treatment solution as described in any one of [1] to [16], which further contains water, and the content of the water is 60% by mass or more relative to the total mass of the treatment solution. [18] A treatment solution as described in any one of [1] to [17], which is used to clean a Cu-containing object that has been subjected to a chemical mechanical polishing treatment. [19] A method for treating an object, comprising the step of bringing the Cu-containing object that has been subjected to a chemical mechanical polishing treatment into contact with the treatment solution as described in any one of [1] to [18]. [20] A method for manufacturing a semiconductor device, comprising the object cleaning method described in [19]. [Effects of the invention]

According to the present invention, a treatment liquid having excellent Cu corrosion inhibition and excellent organic residue removal can be provided. In addition, according to the present invention, a method for treating an object using the above-mentioned treatment liquid and a method for manufacturing a semiconductor device can also be provided.

The present invention is described in detail below. The description of the constituent elements described below is sometimes based on representative embodiments of the present invention, but the present invention is not limited to such embodiments.

The following is the meaning of each description in this specification. In this specification, the numerical range indicated by "～" refers to the range that includes the numerical values described before and after "～" as the lower limit and upper limit. In addition, in this specification, when there are two or more components, the "content" of the component refers to the total content of the two or more components. In this specification, "the total mass of components other than solvents in the treatment liquid" refers to the total content of all components contained in the treatment liquid other than solvents such as water and organic solvents.

In this specification, when there are multiple substituents and linking groups represented by specific symbols (hereinafter referred to as substituents, etc.), or when multiple substituents, etc. are specified at the same time, it means that each substituent, etc. may be the same or different from each other. The same applies to the number of substituents, etc. The compounds described in this specification may include isomers (compounds with the same number of atoms but different structures), optical isomers, and isotopes unless otherwise specified. In addition, isomers and isotopes may include only one type or multiple types. In this specification, unless otherwise specified, the bonding direction of the divalent group (e.g., -COO-) described is not limited. For example, when Y in the compound represented by the formula "X-Y-Z" is -COO-, the above compound can be "X-O-CO-Z" or "X-CO-O-Z".

In this specification, "psi" means pound-force per square inch; 1 psi = 6894.76 Pa. In this specification, "ppm" means parts-per-million (10 ^-6 ), and "ppb" means parts-per-billion (10 ^-9 ), one billionth. In this specification, 1Å (Angstrom) is equivalent to 0.1nm.

In this specification, the "weight average molecular weight" refers to the weight average molecular weight in terms of polyethylene glycol measured by GPC (gel permeation chromatography).

[Treatment liquid] The following describes in detail the components contained in the treatment liquid of the present invention. The treatment liquid of the present invention (hereinafter, also referred to as "treatment liquid") contains a reducing agent and a specific compound described below.

The reason why the treatment liquid having the above structure can solve the problem of the present invention is not clear, but it can be inferred that the treatment liquid has excellent Cu corrosion inhibition and excellent organic residue removal due to the synergistic effect of the reducing agent and the specific compound. For example, the reducing agent contained in the treatment liquid reduces the redox potential of Cu contained in the object and inhibits the corrosion of Cu. In addition, the reducing agent and the specific compound increase the solubility of organic residue (for example, organic residue from the polishing liquid), thereby facilitating the removal of the organic residue. As a result, it is believed that the treatment liquid has both excellent Cu corrosion inhibition and organic residue removal. Furthermore, the mechanism by which the effect can be obtained by the above speculation is not limited. In other words, even if the effect is obtained by a mechanism other than the above, it is also included in the scope of the present invention. Hereinafter, at least one of Cu corrosion inhibition and organic slag removal is better and is also referred to as "the effect of the present invention is better".

[Reducing agent] The treatment liquid contains a reducing agent. The reducing agent is a compound having a reducing function, and examples thereof include ascorbic acid and ascorbic acid derivatives or salts thereof, polyphenol compounds, reducing sulfur compounds, hydrogen peroxide, hydrazine derivatives, and sugars. The reducing agent does not include the specific compounds described below. Among them, ascorbic acid, ascorbic acid derivatives or salts thereof or polyphenol compounds are preferred as the reducing agent.

<Ascorbic acid and ascorbic acid derivatives or salts thereof> As ascorbic acid, L-ascorbic acid, D-ascorbic acid and isoascorbic acid can be listed. As ascorbic acid derivatives, for example, alkyl glycerol ascorbic acid, ascorbic acid glycerol, ascorbic acid alkyl ether, ascorbic acid alkyl ester, ascorbic acid sulfate and ascorbic acid phosphate can be listed. In addition, salts of ascorbic acid and ascorbic acid derivatives can also be preferably used. As salts, for example, alkaline metal salts such as sodium ascorbate can be listed. It is preferable that the reducing agent contains ascorbic acid.

<Polyphenol compounds> Polyphenol compounds are compounds having at least two phenolic hydroxyl groups. Examples of polyphenol compounds include catechol, resorcinol, hydroquinone, and their derivatives.

As the polyphenol compound, the compound represented by formula (A) is preferred.

[Chemical formula 1]

^RA represents a hydrogen atom or a monovalent organic group. A plurality of ^RAs may be the same or different. As the monovalent organic group, there is no particular limitation, but a carboxyl group, an aldehyde group or a alkyl group which may have a heteroatom may be listed. The alkyl group having a heteroatom is a group having at least one divalent connecting group selected from the group consisting of -O-, -CO-, -COO-, -NR ^N -, -CONR ^N -, -S- and -SO ₂ - between the carbon-carbon bonds of the alkyl group or at the end. Furthermore, ^RN represents a hydrogen atom or an alkyl group. The carbon number of the above alkyl group is preferably 1 to 25, more preferably 1 to 15, and even more preferably 1 to 10. The above alkyl group may be any of a linear, branched and cyclic shape. When the above-mentioned alkyl group has a ring structure, the ring may be monocyclic or polycyclic. The above-mentioned alkyl group may further have a substituent. As the substituent that the above-mentioned alkyl group may further have, for example, halogen atoms such as chlorine atoms, hydroxyl groups, alkoxyl groups, acyl groups, alkyl groups, carboxyl groups, thiol groups, cyano groups and nitro groups can be listed, and hydroxyl groups, alkoxyl groups having 1 to 4 carbon atoms, alkyl groups having 1 to 4 carbon atoms or carboxyl groups are preferred, and hydroxyl groups or carboxyl groups are more preferred. As the alkyl group, alkyl groups, alkenyl groups or aryl groups are preferred. As the alkyl group having heteroatoms, acyl groups, alkoxyl groups, alkoxycarbonyl groups, alkylamide groups or heteroaryl groups are preferred, and alkoxyl groups are more preferred. ^RA is preferably a hydrogen atom, a carboxyl group, an alkyl group, an alkenyl group, an acyl group, an alkoxy group, an alkoxycarbonyl group or a heteroaryl group, more preferably a hydrogen atom, an alkyl group, an alkoxy group or a carboxyl group, and further preferably a hydrogen atom, a methyl group, a methoxy group or a carboxyl group.

A plurality of ^RAs may bond to each other to form a ring. The ring formed by a plurality of ^RAs bonding to each other may further have a substituent. As the substituent, the substituents that the above-mentioned alkyl group may have may be listed, and a hydroxyl group or a carboxyl group is preferred. As the ring structure formed by a plurality of ^RAs bonding to each other, for example, a benzene skeleton, a naphthalene skeleton, a cyclohexanedione skeleton, and an anthracene skeleton may be listed.

k is an integer of 2 to 4, preferably 2 or 3, and more preferably 3. When k is 2 or more, at least two hydroxyl groups in formula (A) are preferably adjacent to each other. That is, as the compound represented by formula (A), catechol or a catechol derivative is preferred. As catechol derivatives, for example, gallic acid, 1,2,4-pyrogallol, gallic acid, gallic acid derivatives, 4-tert-butylcatechol, 3-methylcatechol, catechol-4-acetic acid, urushiol, caffeic acid, 1,2-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, alizarin, quercetin and catechin can be listed.

Among them, gallic acid or a gallic acid derivative is preferred as the compound represented by formula (A). Examples of gallic acid derivatives include gallic acid alkyl esters such as methyl gallate, ethyl gallate, propyl gallate, octyl gallate and lauryl gallate, and gallic acid amides.

As the compound represented by formula (A), flavonoids such as flavonols, anthocyanidins and flavanols are also preferred. For example, flavonols are compounds in which one of ^RA is a thiamethoxam derivative.

Examples of the polyphenol compounds include catechol, hydroquinone, resorcinol, gallol, 1,2,4-pyrogallol, pyrogallol, gallic acid, gallic acid alkyl esters, gallic acid amide, 4-tert-butylcatechol, 3-methylcatechol, catechol-4-acetic acid, urushiol, caffeic acid, 1,2-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 1,3-naphthoresorcinol, alizarin, endorphin, rhein, quercetin, catechins, and anthocyanins.

<Reducing sulfur compound> The reducing sulfur compound contains a sulfur atom and is not particularly limited as long as it is a compound having a function as a reducing agent. Examples thereof include butyl succinic acid, dithiodiglycerol, bis(2,3-dihydroxypropylthio)ethylene, sodium 3-(2,3-dihydroxypropylthio)-2-methyl-propylsulfonate, 1-thioglycerol, sodium 3-butyl-1-propanesulfonate, 2-butylethanol, thioglycolic acid, and 3-butyl-1-propanol. Among them, compounds having an SH group (butyl compound) are preferred, 1-thioglycerol, sodium 3-butyl-1-propanesulfonate, 2-butylethanol, 3-butyl-1-propanol or thioglycolic acid are more preferred, and 1-thioglycerol or thioglycolic acid is further preferred.

<Other reducing agents> As reducing agents, other reducing agents other than those mentioned above may be included. As other reducing agents, for example, hydrogen peroxide; hydrazine derivatives such as hydrazine and hydrazide compounds; sugars such as fructose, glycols and ribose; polyvinyl pyrrolidone; and phenanthroline.

The reducing agent preferably contains at least one selected from the group consisting of ascorbic acid and ascorbic acid derivatives or their salts, polyphenol compounds, hydrogen peroxide and hydrazine, more preferably contains at least one selected from the group consisting of ascorbic acid and ascorbic acid derivatives or their salts and polyphenol compounds, and further preferably contains at least one selected from the group consisting of ascorbic acid and ascorbic acid derivatives or their salts and gallic acid and gallic acid derivatives. The reducing agent preferably contains at least one selected from the group consisting of ascorbic acid, 3-O-ethylglycerol ascorbic acid, sodium ascorbic acid, gallic acid, alkyl gallate, gallol, 1,2,4-pyrogallol, catechol, resorcinol, hydroquinone, caffeic acid, alizarin, endorphin, rhamnol, quercetin, catechin, hydrogen peroxide and hydrazine. It is more preferred that the composition contains at least one selected from the group consisting of gallic acid, ethylglycerol ascorbic acid, sodium ascorbate, gallic acid, methyl gallate, ethyl gallate, propyl gallate, octyl gallate, 1,2,4-pyrogallol, gallic acid and catechol.

The reducing agent may be used alone or in combination of two or more. In order to achieve a better effect of the present invention, the content of the reducing agent relative to the total mass of the treatment liquid is preferably 0.001 mass % or more, more preferably 0.005 mass % or more, more preferably 0.02 mass % or more, and particularly preferably 0.03 mass % or more. There is no particular upper limit, but in terms of reducing the amount used while maintaining the effect of the present invention, 10.0 mass % or less is preferred, 6.0 mass % or less is more preferred, and 0.5 mass % or less is further preferred. From the perspective of achieving a better effect of the present invention, the content of the reducing agent relative to the total mass of the components of the treatment solution other than the solvent is preferably 0.5 mass %, more preferably 2.0 mass %, and more preferably 8.0 mass %. From the perspective of maintaining the effect of the present invention, as the upper limit, 95.0 mass % or less is preferred, 60.0 mass % or less is more preferred, 45.0 mass % or less is more preferred, and 35.0 mass % is particularly preferred.

[Specific compound] The treatment solution contains at least one specific compound selected from the group consisting of dehydroascorbic acid, 2,3-diketogulonic acid, 4-oxalocrotonic acid and 3,4,5-trioxacyclohexane-1-carboxylic acid.

The specific compound may be used alone or in combination of two. In terms of achieving a better effect of the present invention, the content of the specific compound is preferably 0.001 to 15.0 mass % relative to the total mass of the treatment solution, more preferably 0.005 to 10.0 mass %, more preferably 0.02 to 3.0 mass %, and particularly preferably 0.03 to 0.3 mass %. In terms of achieving a better effect of the present invention, the content of the specific compound is preferably 0.1 to 97.0 mass % relative to the total mass of the components of the treatment solution other than the solvent, more preferably 2.0 to 90.0 mass %, more preferably 7.0 to 60.0 mass %, and particularly preferably 10.0 to 55.0 mass %. From the perspective of achieving a more excellent effect of the present invention, the mass ratio of the content of the specific compound to the content of the reducing agent is preferably 0.001 to 200, more preferably 0.01 to 199, further preferably 0.1 to 50, and particularly preferably 0.1 to 5.

The treatment solution may contain other components besides the above components (reducing agent and specific compound). Other components are described in detail below.

[Quaternary ammonium compound represented by formula (B)] The treatment liquid may contain a quaternary ammonium compound represented by formula (B) (hereinafter, also referred to as a "specific quaternary ammonium compound"). When the treatment liquid contains the specific quaternary ammonium compound, the organic residue removal performance is further improved.

[Chemical formula 2]

R ¹ to R ⁴ each independently represent an alkyl group which may have a substituent and may have a linking group represented by -O-. The alkyl group may be any of linear, branched, and cyclic. The alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 4 carbon atoms. The total carbon number of the group represented by R ¹ to R ⁴ is 5 or more, preferably 5 to 22 carbon atoms, more preferably 5 to 16 carbon atoms, and even more preferably 5 to 12 carbon atoms. When the group represented by R ¹ to R ⁴ is an alkyl group having a substituent, the total carbon number of the substituent and the alkyl group is within the above range. When the group represented by R ¹ to R ⁴ is an alkyl group without a substituent, the total carbon number of the alkyl group is within the above range. Examples of the substituent include halogen atoms such as fluorine, chlorine and bromine atoms; alkoxy groups; hydroxyl groups; alkoxycarbonyl groups such as methoxycarbonyl and ethoxycarbonyl; acyl groups such as acetyl, propionyl and benzyl; cyano groups; and nitro groups, preferably hydroxyl groups. As the alkyl group, preferably methyl, ethyl, 2-hydroxyethyl, propyl or butyl groups, more preferably ethyl or butyl groups. A plurality of R ¹ to R ⁴ may be bonded to each other to form a ring.

^X- represents an anion. Examples of the anion include acid anions such as carboxylic acid ions, phosphoric acid ions, phosphonic acid ions, and nitric acid ions, and hydroxide ions, with hydroxide ions being preferred.

Examples of the specific quaternary ammonium compound include tetraethylammonium hydroxide (TEAH), tetrabutylammonium hydroxide (TBAH), tri(2-hydroxyethyl)methylammonium hydroxide (THEMAH), dimethylbis(2-hydroxyethyl)ammonium hydroxide, ethyltrimethylammonium hydroxide (ETMAH), trimethylethylammonium hydroxide (TMEAH), dimethyldiethylammonium hydroxide (DMDEAH), methyltriethylammonium hydroxide (ETMAH), and trimethylethylammonium hydroxide (TMEAH). The present invention relates to a hydroxyethyl ammonium hydroxide (MTEAH), a hydroxyethyl trimethyl ammonium hydroxide (choline), a bis (2-hydroxyethyl) dimethyl ammonium hydroxide, a tri (2-hydroxyethyl) methyl ammonium hydroxide, a tetra (2-hydroxyethyl) ammonium hydroxide and a hexadecyl trimethyl ammonium hydroxide, THEMAH, ETMAH, choline, TBAH or TEAH is preferred, and TEAH or TBAH is more preferred.

The specific quaternary ammonium compound may be used alone or in combination of two or more. In order to achieve a better effect of the present invention, the content of the specific quaternary ammonium compound relative to the total mass of the treatment liquid is preferably 0.01 mass % or more, more preferably 0.05 mass % or more, and even more preferably 0.1 mass %. There is no particular upper limit, but in terms of reducing the amount used while maintaining the effect of the present invention, 20.0 mass % or less is preferred, 15.0 mass % or less is even more preferred, 5.0 mass % or less is even more preferred, and 1.0 mass % or less is particularly preferred. From the perspective of achieving a more excellent effect of the present invention, the content of the specific quaternary ammonium compound relative to the total mass of the components of the treatment solution other than the solvent is preferably 1.0 to 90.0 mass %, 10.0 to 80.0 mass % is more preferably, and 20.0 to 70.0 mass % is further preferably. From the perspective of achieving a more excellent effect of the present invention, the mass ratio of the content of the specific quaternary ammonium compound relative to the content of the specific compound is preferably 0.01 to 150.0, 0.01 to 100.0 is more preferably, 0.1 to 50.0 is further preferably, and 0.5 to 30.0 is particularly preferably.

[Chelating agent] The treatment liquid may contain a chelating agent. A chelating agent is a compound having a functional group (ligand) that can act as a ligand on residues and/or the target object in the treatment step. In addition, the chelating agent does not contain the above-mentioned compounds (reducing agent, specific compound and specific quaternary ammonium compound) that can be contained in the treatment liquid.

As the ligand possessed by the chelating agent, an acid group can be listed. As the acid group, for example, a carboxyl group, a phosphonic acid group, a sulfonic acid group, and a phenolic hydroxyl group can be listed. It is preferred that the chelating agent has a carboxyl group or a phosphonic acid group as a ligand, and it is more preferred that it has a carboxyl group.

As chelating agents, organic chelating agents and inorganic chelating agents can be listed. Organic chelating agents are chelating agents composed of organic compounds, for example, carboxylic acid chelating agents having carboxyl groups as ligands, phosphonic acid chelating agents having phosphonic acid groups as ligands, and sulfonic acid chelating agents having sulfonic acid groups as ligands can be listed. As inorganic chelating agents, condensed phosphoric acid and its salts can be listed.

As the chelating agent, an organic chelating agent is preferred, and it is also preferred to have an acid group as a ligand. In other words, the chelating agent is preferably an organic acid.

<Organic acid> An organic acid is an organic compound having at least one acid group. Examples of organic acids include carboxylic acid, phosphonic acid, and sulfonic acid, with carboxylic acid or phosphonic acid being preferred, and carboxylic acid being more preferred. As for the number of acid groups possessed by the organic acid, 1 to 8 is preferred, 1 to 6 is more preferred, and 1 to 4 is further preferred.

The organic acid is preferably of low molecular weight. Specifically, the molecular weight of the organic acid is preferably 600 or less, more preferably 450 or less, and further preferably 300 or less. The lower limit is preferably 50 or more, and more preferably 100 or more. The number of carbon atoms in the organic acid is preferably 1 to 15, and more preferably 2 to 15.

Examples of carboxylic acids include polycarboxylic acids, hydroxycarboxylic acids, and aminocarboxylic acids. Examples of polycarboxylic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, sebacic acid, butene diacid, and adipic acid, and oxalic acid, malonic acid, or succinic acid is preferred. Examples of hydroxycarboxylic acids include citric acid, apple acid, glycolic acid, gluconic acid, heptonic acid, tartaric acid, lactic acid, phenyllactic acid, hydroxyphenyllactic acid, and phenylsuccinic acid, and citric acid, tartaric acid, or lactic acid is preferred. As aminocarboxylic acids, for example, histidine or its derivatives, alanine (2-aminopropionic acid or 3-aminopropionic acid), arginine, asparagine, aspartic acid, cystine, cysteine, glutamine, glutamine, glycine or its derivatives, isoleucine, leucine, ricin, methionine, phenylalanine, serine, ethionine, threonine, tyrosine, valine, tryptophan, 2-amino-3-aminopropanoic acid and proline can be listed, and histidine or its derivatives are preferred. As carboxylic acids other than the above, for example, formic acid can be listed. As aminocarboxylic acids, compounds described in paragraphs [0021] to [0023] of Japanese Patent Application Publication No. 2016-086094 can also be listed. As histidine derivatives, compounds described in Japanese Patent Application Publication No. 2015-165561 and Japanese Patent Application Publication No. 2015-165562 can be cited. As glycine derivatives, N,N-di(2-hydroxyethyl)glycine can be cited.

Examples of the phosphonic acid include ethylenediphosphonic acid, 1-hydroxyethylidene-1,1'-diphosphonic acid (HEDPO), 1-hydroxypropylene-1,1'-diphosphonic acid, 1-hydroxybutylene-1,1'-diphosphonic acid, ethylaminobis(methylenephosphonic acid), dodecylaminobis(methylenephosphonic acid), nitrogen tris(methylenephosphonic acid) (NTPO), ethylenediaminebis(methylenephosphonic acid) (EDDPO), 1,3-propylenediaminebis(methylenephosphonic acid), ethylenediaminetetra(methylenephosphonic acid), and 1,3-propylenediaminebis(methylenephosphonic acid). 1,3-propylenediaminetetrakis(methylenephosphonic acid) (PDTMP), 1,2-diaminopropanetetrakis(methylenephosphonic acid), 1,6-hexamethylenediaminetetrakis(methylenephosphonic acid), diethylenetriaminepenta(methylenephosphonic acid) (DEPPO), diethylenetriaminepenta(methylenephosphonic acid), triethylenetetraaminehexa(methylenephosphonic acid) and triethylenetetraaminehexa(methylenephosphonic acid), HEDPO or EDTPO is preferred.

As phosphonic acid, for example, the compounds described in paragraphs [0026] to [0036] of International Publication No. 2018/020878 and the compounds ((co)polymers) described in paragraphs [0031] to [0046] of International Publication No. 2018/030006 can also be cited, and these contents are incorporated into this specification.

The chelating agent preferably contains an organic acid, more preferably contains at least one selected from the group including polycarboxylic acid, hydroxycarboxylic acid and phosphonic acid, and further preferably contains at least one selected from the group including polycarboxylic acid and hydroxycarboxylic acid. Among them, the chelating agent preferably contains at least one selected from the group including citric acid, formic acid, oxalic acid, tartaric acid, lactic acid, HEDPO, EDTPO and histidine, and more preferably contains at least one selected from the group including oxalic acid, tartaric acid and citric acid.

The chelating agent may be used alone or in combination of two or more. In terms of the better effect of the present invention, the content of the chelating agent is preferably 0.001 to 5.0 mass % relative to the total mass of the treatment liquid, 0.01 to 3.0 mass % is more preferably, and 0.01 to 2.0 mass % is more preferably. In terms of the better effect of the present invention, the content of the chelating agent is preferably 0.1 to 97.0 mass % relative to the total mass of the components of the treatment liquid other than the solvent, 1.0 to 95.0 mass % is more preferably, 3.0 to 80.0 mass % is more preferably, and 5.0 to 30.0 mass % is particularly preferably. From the perspective of achieving a better effect of the present invention, the mass ratio of the content of the reducing agent to the content of the chelating agent is preferably 0.001 to 300.0, more preferably 0.005 to 5.0, further preferably 0.02 to 5.0, and particularly preferably 0.1 to 3.5. From the perspective of achieving a better effect of the present invention, the mass ratio of the content of the chelating agent to the content of the specific compound is preferably 0.001 to 500, more preferably 0.003 to 100, and further preferably 0.01 to 15.0.

[Amine compound] The treatment liquid may contain an amine compound. An amine compound is a compound in which at least one of the hydrogen atoms of ammonia is replaced by another substituent, and examples thereof include a primary amine compound having a primary amine group ( _-NH2 ) in the molecule, a secondary amine compound having a secondary amine group (>NH) in the molecule, and a tertiary amine compound having a tertiary amine group (>N-) in the molecule. Furthermore, in the case of amine groups of different orders, the amine compound with the highest order is classified. The amine compound does not contain any of the above-mentioned compounds (reducing agents, chelating agents, and specific quaternary ammonium compounds, etc.) and nitrogen-containing heterocyclic compounds that can be contained in the treatment liquid. In terms of excellent organic residue removal performance, it is preferred that the treatment liquid contains an amine compound.

In terms of achieving a more excellent effect of the present invention, it is preferred that the amine compound has two or more amino groups. In terms of achieving a more excellent effect of the present invention, it is also preferred that the amine compound has a hydroxyl group as a substituent.

The pKa of the amine compound is preferably 5.0 to 20.0, more preferably 7.5 to 15.0, and even more preferably 9.0 to 14.5. The above pKa can use the value recorded in SC-Database. In addition, the value measured by a known method such as neutralization titration, absorptiometry, and capillary electrophoresis can also be used.

As the amine compound, a compound represented by formula (C1) is preferred.

[Chemical formula 3]

R ⁵ to R ⁸ each independently represent a hydrogen atom or an alkyl group which may have a substituent or a linking group represented by -O-. The alkyl group may be any of a linear, branched, or cyclic group. The number of carbon atoms in the alkyl group is preferably 1 to 30, more preferably 1 to 15, further preferably 1 to 6, and particularly preferably 1 to 4. As the substituent, there can be cited the substituents which can be substituted by the groups represented by R ¹ to R ⁴ in formula (B), preferably a hydroxyl group or an alkoxy group. In the case where the alkyl group has a linking group represented by -O-, the number of the linking groups represented by -O- in the alkyl group is preferably 1 to 5, more preferably 1 to 3, and further preferably 1. Among them, R ⁵ to R ⁸ are preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group or an isopropyl group, and still more preferably a hydrogen atom, a methyl group or an ethyl group. Plural R ⁵ to R ⁸ may be bonded to each other to form a ring.

^R9 represents an alkylene group having 2 or more carbon atoms which may have a substituent and may have a linking group represented by -O- or -NR ^N -. ^RN represents a hydrogen atom or an alkyl group. The carbon number of the alkylene group is 2 or more, preferably 2 to 10, more preferably 2 to 8, and even more preferably 2 to 4. As the substituent, the substituents which can be substituted by the groups represented by R ¹ to R ⁴ in formula (B) can be listed, and a hydroxyl group or an alkoxy group is preferred. In the case where the alkylene group has a linking group represented by -O-, the number of the linking groups represented by -O- which the alkylene group has is preferably 1 to 5, more preferably 1 to 3, and even more preferably 1. When the alkylene group has a linking group represented by -NR ^N -, the number of linking groups represented by -NR ^N - in the alkylene group is preferably 1 to 5, more preferably 1 to 3, and even more preferably 1 to 2. ^RN represents a hydrogen atom or an alkyl group. The alkyl group may be any of a linear chain, a branched chain, and a ring. The number of carbon atoms in the alkylene group is preferably 1 to 15, more preferably 1 to 6, and even more preferably 1 to 3. Among them, as R ⁹ , an ethylene group, a propylene group, a butylene group, or a hexylene group is preferred, and an ethylene group, a propylene group, or a butylene group is even more preferred.

Examples of the compound represented by formula (C1) include 1,2-diaminopropane, N-methyl-1,3-diaminopropane, 1,2-diaminoethane, 1,3-diaminopropane, 2-methyl-1,3-diaminopropane, 1,4-diaminobutane, 1,3-diaminobutane, 1,3-bis(dimethylamino)butane, 2-(2-aminoethylamino)ethanol (AAE), 1-(2-hydroxyethyl)piperidinium, N,N'-bis( diamine compounds such as tetramethylethylenediamine and tetramethyl-1,4-butanediamine, and polyalkyl polyamines such as diethylenetriamine (DETA), N,N,N’,N’’,N’’-pentamethyldiethylenetriamine (PMDETA), triethylenetetramine (TETA), bis(aminopropyl)ethylenediamine (BAPEDA) and tetraethylenepentamine.

As an amine compound other than the amine compound represented by formula (C1), a monoamine compound having a hydroxyl group is also preferred. As a monoamine compound having a hydroxyl group, a compound represented by formula (C2) is preferred.

[Chemical formula 4]

^R10 and ^R11 each independently represent a hydrogen atom or an alkyl group which may have a substituent. The alkyl group may be any of a linear, branched, or cyclic group. The alkyl group may preferably have 1 to 30 carbon atoms, more preferably 1 to 15 carbon atoms, further preferably 1 to 6 carbon atoms, and particularly preferably 1 to ⁴ carbon atoms. As the substituent, the substituents which can be substituted by the groups represented by ^R1 to R4 in formula (B) may be listed, and a hydroxyl group is preferred. As ^R10 and ^R11 , a hydrogen atom or an alkyl group having 1 to 4 carbon atoms which may have a hydroxyl group is preferred, a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, or a 2-hydroxyethyl group is more preferred, and a hydrogen atom, a methyl group, or an ethyl group is further preferred. R ¹⁰ and R ¹¹ may bond with each other to form a ring.

R ¹² represents an alkylene group which may have a substituent. The alkylene group may be any of a linear, branched, and cyclic group. The number of carbon atoms in the alkylene group is preferably 1 to 12, more preferably 1 to 6, and even more preferably 1 to 4. As the substituent, substituents which can be substituted by the groups represented by R ¹ to R ⁴ in formula (B) can be listed, and a hydroxyl group is preferred. As R ¹² , a methylene group, an ethylene group, a propylene group, a methylethylene group, an ethylethylene group, a 1-methylpropylene group, a 1,1-dimethylethylene group, or a 1,2-dimethylethylene group is preferred, and an ethylene group, a methylethylene group, or a propylene group is more preferred.

Examples of the compound represented by formula (C2) include ethanolamine, propanolamine, isopropanolamine, trihydroxymethylaminomethane (Tris), 2-amino-2-methyl-1-propanol (AMP), 2-dimethylamino-2-methyl-1-propanol (DMAMP), 2-amino-2-methyl-1,3-propanediol (AMPDO), 2-amino-2-ethyl-1,3-propanediol (AEPDO), 2-amino-1,3-propanediol (2-APDO), 3-amino-1,2-propanediol (3-APDO), and 2-amino-2-methyl-1,3-propanediol (AMPDO). DO), 3-methylamino-1,2-propanediol (MAPDO), 2-(methylamino)-2-methyl-1-propanediol (N-MAMP), 2-(aminoethoxy)ethanol (AEE), diethanolamine (DEA), triethanolamine (TEA), N-methylethanolamine, N-butylethanolamine, N-cyclohexylethanolamine, 2-(ethylamino)ethanol, propylaminoethanol, diethylene glycolamine (DEGA), N-tert-butyldiethanolamine, N-butyldiethanolamine, N-methyldiethanolamine and 1-piperidinol.

Examples of other amine compounds than those mentioned above include aliphatic monoamine compounds such as methylamine, ethylamine, propylamine, dimethylamine, diethylamine, n-butylamine, tert-butylamine, n-hexylamine, n-octylamine, 2-ethylhexylamine, 3-methoxypropylamine, trimethylamine and triethylamine.

The amine compound preferably includes at least one selected from the group consisting of compounds represented by formula (C1) and compounds represented by formula (C2), and more preferably includes at least one selected from the group consisting of compounds represented by formula (C1). Among them, the amine compound includes methanolamine, ethanolamine, propanolamine, butanolamine, diethanolamine, triethanolamine, N-methylethanolamine, N-methyl-N,N-diethanolamine, N,N-dimethylethanolamine, N,N-diethylethanolamine, N,N-dibutylethanolamine, N-(β-aminoethyl)ethanolamine, N-ethylethanolamine, dipropanolamine, tripropanolamine, monoisopropanolamine, diisopropanolamine, tri ... At least one of the group consisting of isopropanolamine, 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 2-methyl-1,3-diaminopropane and N-methyl-1,3-diaminopropane is preferred, and at least one of the group consisting of ethanolamine, propanolamine, 1,2-diaminopropane and N-methyl-1,3-diaminopropane is more preferred.

The amine compound may be used alone or in combination of two or more. In terms of achieving a better effect of the present invention, the content of the amine compound is preferably 0.01 to 20.0 mass %, more preferably 0.03 to 15.0 mass %, and even more preferably 0.05 to 5.0 mass % relative to the total mass of the treatment liquid. In terms of achieving a better effect of the present invention, the content of the amine compound is preferably 0.01 to 99.0 mass %, more preferably 3.0 to 50.0 mass %, even more preferably 15.0 to 40.0 mass %, and particularly preferably 15.0 to 35.0 mass % relative to the total mass of the components of the treatment liquid other than the solvent.

[Anti-corrosion agent] The treatment liquid may contain an anti-corrosion agent. The anti-corrosion agent is a compound having the function of preventing corrosion of metal components contained in the object (for example, a metal layer containing Cu or a Cu alloy). In addition, the anti-corrosion agent does not contain any of the above-mentioned compounds (reducing agents, specific compounds, specific quaternary ammonium compounds, chelating agents, and amine compounds) that can be contained in the treatment liquid.

There is no particular limitation on the preservative, but a heterocyclic compound is preferred. As the heterocyclic compound, for example, azole compounds, pyrrole compounds, pyridine compounds, pyrrolium compounds, pyrimidine compounds, indole compounds, indole compounds, indazole compounds, quinoline compounds and oxazole compounds can be listed, and azole compounds or pyrrole compounds are preferred.

Examples of the azole compound include an imidazole compound in which one of the atoms constituting the azole ring is a nitrogen atom, a pyrazole compound in which two of the atoms constituting the azole ring are nitrogen atoms, a thiazole compound in which one of the atoms constituting the azole ring is a nitrogen atom and the other is a sulfur atom, a triazole compound in which three of the atoms constituting the azole ring are nitrogen atoms, and a tetrazole compound in which four of the atoms constituting the azole ring are nitrogen atoms.

Examples of the imidazole compound include imidazole, 1-methylimidazole, 2-methylimidazole, 5-methylimidazole, 1,2-dimethylimidazole, 2-nitrilimidazole, 4,5-dimethyl-2-nitrilimidazole, 4-hydroxyimidazole, 2,2'-biimidazole, 4-imidazolecarboxylic acid, histamine, and benzimidazole.

Examples of the pyrazole compound include pyrazole, 4-pyrazolecarboxylic acid, 1-methylpyrazole, 3-methylpyrazole, 3-amino-5-hydroxypyrazole, 3-aminopyrazole, and 4-aminopyrazole.

Examples of the thiazole compound include 2,4-dimethylthiazole, benzothiazole, and 2-hydroxybenzothiazole.

As triazole compounds, there can be exemplified benzotriazole compounds in which two adjacent substituents on a triazole ring are bonded to each other to form a benzene ring. As benzotriazole compounds, there can be exemplified benzotriazole, 5-methyl-1H-benzotriazole (CAS registration number: 136-85-6), tolyltriazole (CAS registration number: 29385-43-1), 5-aminobenzotriazole, 1-hydroxybenzotriazole, 4-carboxybenzotriazole, 5,6-dimethylbenzotriazole, 1-[N,N-bis(hydroxy) 1-[(methyl-1H-benzotriazole-1-yl)methyl]imino]bisethanol and carboxybenzotriazole. As triazole compounds other than benzotriazole compounds, for example, 1,2,3-triazole, 1,2,4-triazole, 3-methyl-1,2,4-triazole, 3-amino-1,2,4-triazole and 1-methyl-1,2,3-triazole can be listed.

Examples of the tetrazole compound 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, 1-phenyl-5-butyltetrazole, and 1-(2-dimethylaminoethyl)-5-butyltetrazole.

As an azole compound, a triazole compound or a tetrazole compound is preferred. As a preservative, a triazole compound, a tetrazole compound or a pyrrole compound is preferred, and triazole, tetrazole or pyrrole is more preferred. Furthermore, in this specification, the above-mentioned azole compound includes the tautomer.

The preservative may be used alone or in combination of two or more. In order to achieve a better effect of the present invention, the content of the preservative is preferably 0.005 to 20.0 mass %, more preferably 0.01 to 10.0 mass %, and even more preferably 0.03 to 1.0 mass % relative to the total mass of the treatment liquid. In order to achieve a better effect of the present invention, the content of the preservative is preferably 0.01 to 50.0 mass %, more preferably 1.0 to 40.0 mass %, and even more preferably 10.0 to 30.0 mass % relative to the total mass of the components of the treatment liquid other than the solvent.

[Water] The treatment liquid may contain water as a solvent. The type of water used in the treatment liquid may be any water that does not adversely affect the semiconductor substrate. Distilled water, deionized (DI: De Ionized) water, and pure water (ultrapure water) may be used. Pure water (ultrapure water) is preferred because it contains almost no impurities and has less impact on the semiconductor substrate in the manufacturing step of the semiconductor substrate. The water content is preferably 60.0 mass % or more, 80.0 mass % or more, and 90.0 mass % or more relative to the total mass of the treatment liquid. Relative to the total mass of the treatment liquid, the upper limit is preferably below 99.99 mass%, preferably below 99.90 mass%, and even more preferably below 99.50 mass%.

[Other components] In addition to the above compounds, the treatment solution may also contain at least one component selected from the group consisting of surfactants, pH adjusters, organic solvents, polymers, and polyhydroxy compounds with a molecular weight of 500 or more. Other components are described below.

<Surfactant> Surfactants are compounds having a hydrophilic group and a hydrophobic group (lipophilic group) in one molecule, and examples thereof include nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants. In addition, surfactants are compounds different from the above compounds that can be contained in the treatment solution.

Most surfactants have at least one hydrophobic group selected from the group consisting of aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and groups formed by combining these groups. When the hydrophobic group contains an aromatic hydrocarbon group, the number of carbon atoms in the hydrophobic group of the surfactant is preferably 6 or more, and more preferably 10 or more. The number of carbon atoms in the surfactant as a whole is preferably 16 to 100.

Examples of the nonionic surfactant include ester-type nonionic surfactants, ether-type nonionic surfactants, and ester-ether-type nonionic surfactants, with ether-type nonionic surfactants being preferred.

Examples of nonionic surfactants include polyethylene glycol, alkyl polyglucoside (Triton BG-10 and Triton CG-110 surfactants manufactured by Dow Chemical Company), octylphenol ethoxylate (Triton X-114 manufactured by Dow Chemical Company), silane polyoxyalkylene (copolymer) (Y-17112-SGS sample manufactured by Momentive Performance Materials), nonylphenol ethoxylate (Tergitol NP-12 manufactured by Dow Chemical Company and Triton (registered trademark) X-102, X-100, X-45, X-15, BG-10 and CG-119), Silwet (registered trademark) HS-312 (manufactured by Momentive Performance Materials), tristyrylphenol ethoxylate (MAKON manufactured by Stepan Company), TSP-20), polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, alkyl allyl formaldehyde condensation polyoxyethylene ethers, polyoxyethylene polyoxypropylene end-capped polymers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene ethers of glycerol esters, polyoxyethylene ethers of sorbitan esters, polyoxyethylene ethers of sorbitan esters, polyethylene glycol fatty acid esters, glycerol esters, polyglycerol esters, sorbitan esters, propylene glycol esters, BRIJ (registered trademark) 56 (C ₁₆ H ₃₃ (OCH ₂ CH ₂ ) ₁₀ OH), BRIJ (registered trademark) 58 (C ₁₆ H ₃₃ (OCH ₂ CH ₂ ) ₂₀ OH), BRIJ (registered trademark) 35 (C ₁₂ H ₂₅ (OCH ₂ CH ₂ ) ₂₃ OH), alcohol ethoxylates such as propylene glycol, alcohol (primary and secondary) ethoxylates, polyethylene glycol, poly(ethylene glycol-co-propylene glycol), cetyl alcohol, stearyl alcohol, cetyl stearyl alcohol (cetyl wax and stearyl alcohol), oleyl alcohol, octaethylene glycol monododecyl ether, pentaethylene glycol monododecyl ether, polyoxypropylene glycol alkyl ether, decyl glucoside, lauryl glucoside, octyl glucoside, polyoxyethylene glycol octylphenol ether, nonoxynol-9, glyceryl alkyl esters, glyceryl laurate, polyoxyethylene glycol sorbitan alkyl esters, polysorbates, end-capped copolymers of sorbitan alkyl esters and polypropylene glycol, and mixtures thereof.

As surfactants, for example, the compounds exemplified in paragraph [0126] of International Publication No. 2022/044893 can also be used, and the contents are incorporated into this specification.

The surfactant may be used alone or in combination of two or more. In terms of the excellent performance of the treatment liquid, the content of the surfactant is preferably 0.001 to 8.0 mass % relative to the total mass of the treatment liquid, 0.005 to 5.0 mass % is more preferably, and 0.01 to 3.0 mass % is further preferably. In terms of the excellent performance of the treatment liquid, the content of the surfactant is preferably 0.01 to 50.0 mass % relative to the total mass of the components other than the solvent in the treatment liquid, 0.1 to 45.0 mass % is more preferably, and 1.0 to 20.0 mass % is further preferably.

<pH adjuster> In order to adjust and maintain the pH of the treatment liquid, the treatment liquid may contain a pH adjuster. The pH adjuster is an alkaline compound and an acidic compound different from the above-mentioned compounds that can be contained in the treatment liquid. However, it is allowed to adjust the pH of the treatment liquid by adjusting the addition amount of each of the above-mentioned components.

Alkaline compounds are compounds that show alkalinity (pH over 7.0) in aqueous solution. Examples of alkaline compounds include alkaline inorganic compounds, such as alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and alkali earth metal hydroxides.

Acidic compounds are compounds that show acidity (pH less than 7.0) in aqueous solution. As acidic compounds, inorganic acids can be listed, for example, hydrochloric acid, sulfuric acid, sulfurous acid, nitric acid, nitrous acid and boric acid can be listed.

As the acidic compound, any salt of the acidic compound may be used as long as it forms an acid or an acid ion (anion) in an aqueous solution.

The pH adjuster can be used alone or in combination of two or more. The content of the pH adjuster can be selected according to the type and amount of other components and the target pH of the treatment solution. For example, the content of the pH adjuster is preferably 0.01 to 10 mass % relative to the total mass of the treatment solution, and 0.1 to 8 mass % is more preferably. The content of the pH adjuster is preferably 0.01 to 80 mass % relative to the total mass of the components other than the solvent in the treatment solution, and 0.1 to 60 mass % is more preferably.

<Organic solvent> As the organic solvent, there can be listed well-known organic solvents, for example, alcohol-based solvents, glycol-based solvents, glycol-ether-based solvents, and ketone-based solvents. It is preferable to mix the organic solvent and water in any ratio.

As the organic solvent, for example, the compounds exemplified in paragraphs [0135] to [140] of International Publication No. 2022/044893 can be used, and these contents are incorporated into the present specification.

<Polymer> In terms of achieving a more excellent effect of the present invention, it is also preferable that the treatment liquid contains a polymer. As the polymer, for example, the water-soluble polymers described in paragraphs [0043] to [0047] of Japanese Patent Publication No. 2016-171294 can be cited, and these contents are incorporated into this specification. As the polymer, a water-soluble polymer is preferred, and specifically, for example, polyvinyl alcohol, hydroxyethyl cellulose, polyvinyl pyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide and polymethacrylamide and copolymers thereof can be listed. Furthermore, a water-soluble polymer refers to a polymer having a mass of 0.1 g or more dissolved in 100 g of water at 20°C. The weight average molecular weight (Mw) of the above-mentioned water-soluble polymer is preferably 10,000 to 1.5 million, and more preferably 40,000 to 1.2 million. Furthermore, the weight average molecular weight (Mw) of the water-soluble polymer refers to the weight average molecular weight converted to polyethylene glycol measured by GPC (gel permeation chromatography).

The polymer may be used alone or in combination of two or more. The content of the polymer is preferably 0.01 to 5.0 mass % relative to the total mass of the treatment liquid, and more preferably 0.05 to 0.5 mass %. The content of the polymer is preferably 0.1 to 10.0 mass % relative to the total mass of the components in the treatment liquid other than the solvent, and more preferably 0.5 to 5.0 mass %.

<Polyhydroxy compounds with a molecular weight of 500 or more> The polyhydroxy compound with a molecular weight of 500 or more is a compound different from the above-mentioned compound that can be contained in the treatment liquid. The above-mentioned polyhydroxy compound is an organic compound having two or more (e.g., 2 to 200) alcoholic hydroxyl groups in one molecule. The molecular weight (weight average molecular weight in the case of molecular weight distribution) of the above-mentioned polyhydroxy compound is 500 or more, preferably 500 to 100,000, and more preferably 500 to 3,000.

As the above-mentioned polyhydroxy compound, the compounds exemplified in paragraphs [0101] and [0102] of International Publication No. 2022/014287 can also be cited, and these contents are incorporated into this specification.

[Physical properties of treatment liquid] <pH> The treatment liquid may be alkaline or acidic. From the perspective of achieving a more excellent effect of the present invention, the pH of the treatment liquid is preferably 4.0 to 14.0, more preferably 8.0 to 14.0, more preferably 8.0 to 13.0, and particularly preferably 10.5 to 13.0. Among them, when the treatment liquid is used for treating an object containing at least one selected from the group consisting of Cu, Co, and Ru, from the perspective of achieving a more excellent corrosion inhibition of Cu, Co, and Ru, the pH of the treatment liquid is preferably 8.0 to 14.0, more preferably 8.0 to 13.0, and further preferably 10.5 to 13.0. Furthermore, when the treatment liquid is used to treat a treatment object containing W, the pH of the treatment liquid is preferably 4.0 to 13.0, more preferably 5.0 to 9.0, and even more preferably 5.0 to 7.0, from the perspective of W's superior corrosion inhibition. The pH of the treatment liquid can be measured using a known pH meter and by a method based on JIS Z8802-1984. The pH measurement temperature is set to 25°C.

<Metal content> The content (measured as ion concentration) of metals (e.g., Fe, Co, Na, Cu, Mg, Mn, Li, Al, Cr, Ni, Zn, Sn, and Ag) contained as impurities in the treatment solution is preferably 5 mass ppm or less, and 1 mass ppm or less is more preferred. In the manufacture of the most advanced semiconductor components, considering the requirement for a treatment solution of higher purity, the content of the above metals is preferably less than 1 mass ppm, that is, less than the mass ppb level, and less than 100 mass ppb is particularly preferred, and less than 10 mass ppb is the best. As a lower limit, 0 is preferred.

As a method for reducing the metal content, for example, distillation and filtration using ion exchange resin or filter can be cited as a purification process in the stage of manufacturing the raw materials used in the treatment liquid or after the treatment liquid is manufactured. As a method for reducing other metal contents, a container with less elution of impurities described below can be cited as a container for storing raw materials or manufactured treatment liquid. In addition, a fluororesin lining can be implemented on the inner wall of the pipe to prevent the metal component from eluting from the pipe when the treatment liquid is manufactured.

<Insoluble particles> It is preferred that the treatment liquid does not substantially contain insoluble particles. The above-mentioned "insoluble particles" correspond to particles such as inorganic solids and organic solids, which are ultimately insoluble in the treatment liquid and exist in the form of particles. The above-mentioned "does not substantially contain insoluble particles" means that the treatment liquid is diluted 10,000 times in the solvent contained in the treatment liquid to prepare a measurement composition, and the number of particles with a particle size of 50 nm or more contained in 1 mL of the measurement composition is 40,000 or less. In addition, the number of particles contained in the measurement composition can be measured in the liquid phase using a commercially available particle counter. As commercially available particle counter devices, devices manufactured by RION CO., LTD. and PMS can be used. As a representative device of the former, KS-19F can be cited, and as a representative device of the latter, Chem20 can be cited. In order to measure larger coarse particles, devices such as KS-42 series and LiQuilaz II S series can be used. As insoluble particles, for example, inorganic solid substances such as silica (including colloidal silica and fumed silica), alumina, zirconia, tantalum dioxide, titanium dioxide, germanium oxide, manganese oxide and silicon carbide; organic solid substances such as polystyrene, polyacrylic resin and polyvinyl chloride can be cited. As a method of removing insoluble particles from the treatment liquid, for example, refining treatment such as filtration can be cited.

<Coarse particles> The treatment liquid may contain coarse particles, but the content is preferably low. Coarse particles refer to particles with a diameter (particle size) of 1μm or more when the particle shape is regarded as a sphere. The coarse particles contained in the treatment liquid are particles such as dust, argon, organic solids and inorganic solids contained as impurities in the raw materials and particles such as dust, argon, organic solids and inorganic solids brought into the treatment liquid as contaminants, which are equivalent to particles that are not dissolved in the final treatment liquid and exist as particles.

As the content of coarse particles in the treatment liquid, the content of particles with a particle size of 1 μm or more per 1 mL of the treatment liquid is preferably 100 or less, and more preferably 50 or less. The lower limit is preferably 0 or more per 1 mL of the treatment liquid, and more preferably 0.01 or more. The content of coarse particles in the treatment liquid can be measured in the liquid phase using a commercially available measuring device in a light scattering liquid particle measurement method using a laser as a light source. As a method for removing coarse particles, for example, purification treatments such as filtration described below can be listed.

[Manufacturing method] The treatment liquid can be manufactured by a known method. The following is a detailed description of the manufacturing method of the treatment liquid.

[Preparation step] The treatment liquid can be prepared, for example, by mixing the above-mentioned components. As a method for preparing the treatment liquid, for example, the following method can be cited: a reducing agent and a specific compound are sequentially added to a container to which purified pure water is added, and then any component is added as needed, followed by stirring to mix, and a pH adjuster is added as needed to adjust the pH of the mixed solution, thereby preparing the treatment liquid. In addition, when adding each component to the container, it can be added all at once or in multiple times.

In the stirring device and stirring method used in the preparation of the treatment liquid, a known device may be used as a stirrer or a disperser. Examples of stirrers include industrial mixers, portable stirrers, mechanical stirrers, and magnetic stirrers. Examples of dispersers include industrial dispersers, homogenizers, ultrasonic dispersers, and bead mills.

The mixing of the components in the treatment solution preparation step, the purification treatment described below, and the storage of the produced treatment solution are preferably performed at 40°C or lower, more preferably at 30°C or lower. The lower limit is preferably 5°C or higher, more preferably 10°C or higher. The performance of the treatment solution can be stably maintained for a long period of time by preparing the treatment solution, treating it, and/or storing it within the above temperature range.

<Purification> It is preferred to perform purification treatment on any one or more of the raw materials used for the liquid treatment solution in advance. Examples of purification treatment include known methods such as distillation, ion exchange, and filtering. The degree of purification is preferably to purify the raw material to a purity of 99% by mass or more, and more preferably to purify the stock solution to a purity of 99.9% by mass or more. As an upper limit, 99.9999% by mass or less is preferred.

As a method of refining treatment, for example, there can be listed methods such as passing the raw material through an ion exchange resin or an RO membrane (Reverse Osmosis Membrane), distillation and filtration of the raw material. As a refining treatment, a plurality of the above refining methods can be combined to implement. For example, after the raw material is purified once by passing the liquid through an RO membrane, a second purification can be implemented by passing the liquid through a refining device composed of a cation exchange resin, anion exchange resin or a mixed bed ion exchange resin. In addition, the refining treatment can be implemented multiple times.

The filter used for filtering is not particularly limited as long as it has been used for filtering purposes in the past. For example, filters made of fluororesins such as polytetrafluoroethylene (PTFE) and tetrafluoroethylene perfluoroalkyl vinyl ether copolymer (PFA), polyamide resins such as nylon, polyallyl sulfone (PAS), and polyolefin resins such as polyethylene and polypropylene (PP) (including high-density or ultra-high molecular weight) can be cited. Among these materials, materials selected from the group consisting of polyethylene, polypropylene (including high-density polypropylene), fluororesins (including PTFE and PFA) and polyamide resins (including nylon) are preferred, and fluororesin filters are more preferred. By filtering the raw material using a filter formed of these materials, highly polar foreign matter that is likely to cause defects can be effectively removed.

<Container> As long as the corrosiveness etc. is not a problem, the treatment liquid (including the diluted treatment liquid described below) can be filled in any container for storage, transportation and use.

As a container, a container for semiconductor use with high cleanliness and which suppresses the dissolution of impurities from the inner wall of the container's storage part into each liquid is preferred. As such a container, various containers commercially available as containers for semiconductor processing liquids can be listed, for example, the "Clean-Bottle" series manufactured by AICELLO CHEMICAL CO., LTD. and the "Pure bottle" manufactured by KODAMA PLASTICS Co., Ltd. can be listed, but are not limited to them. In addition, as a container, the containers exemplified in paragraphs [0121] to [0124] of International Publication No. 2022/004217 can also be cited, and such contents are incorporated into this specification.

It is preferred that the inside of such containers be cleaned before filling with the treatment liquid. It is preferred that the liquid used for cleaning has a reduced amount of metallic impurities in the solution. The treatment liquid can be bottled in a container such as a gallon bottle or a coating bottle for transportation and storage after manufacture.

In order to prevent the composition of the treatment liquid from changing during storage, the container can be replaced with an inert gas (nitrogen or argon, etc.) with a purity of 99.99995% by volume or more. Gas with a low water content is particularly preferred. In addition, during transportation and storage, it can be at room temperature, but in order to prevent deterioration, the temperature can be controlled within the range of -20°C to 20°C.

<Cleanroom> It is preferred that all operations including the manufacture of treatment fluid, opening and cleaning of containers, filling of treatment fluid, treatment analysis, and measurement be performed in a cleanroom. It is preferred that the cleanroom meet the 14644-1 cleanroom standard. It is preferred that it meet any of ISO (International Organization for Standardization) Class 1, ISO Class 2, ISO Class 3, and ISO Class 4, and it is preferred that it meet ISO Class 1 or ISO Class 2, and it is further preferred that it meet ISO Class 1.

[Dilution step] After the above-mentioned treatment liquid is diluted using a diluent such as water in a dilution step, it can be used as a diluted treatment liquid (diluted treatment liquid) for treating the object. Furthermore, as long as the requirements of the present invention are met, the diluted treatment liquid is also a form of the treatment liquid of the present invention.

It is preferred to purify the dilute solution used in the dilution step in advance. Furthermore, it is more preferred to purify the diluted treatment solution obtained by the dilution step. As the purification treatment, it is preferred to cite the treatment of reducing ion components using ion exchange resin or RO membrane and removing foreign matter using filtration as described as the purification treatment of the treatment solution above.

The dilution rate of the treatment liquid in the dilution step can be appropriately adjusted according to the type and content of each component and the object to be treated. The ratio of the diluted treatment liquid to the treatment liquid before dilution (dilution ratio) is preferably 10 to 10,000 times by mass ratio or volume ratio (volume ratio at 23°C), more preferably 20 to 3,000 times, and even more preferably 50 to 1,000 times. In addition, in terms of better residue removal performance, it is better to dilute the treatment liquid with water.

The change in pH before and after dilution (the difference between the pH of the treatment solution before dilution and the pH of the diluted treatment solution) is preferably 2.0 or less, 1.8 or less is more preferably, and 1.5 or less is further preferably. It is preferred that the pH of the treatment solution before dilution and the pH of the diluted treatment solution are the above-mentioned preferred states, respectively.

The specific method of the dilution step of diluting the treatment solution can be carried out based on the above-mentioned treatment solution preparation step. The stirring device and stirring method used in the dilution step can also be carried out using the known stirring devices listed in the above-mentioned treatment solution preparation step.

[Application] The processing liquid of the present invention can be used for various materials used in the manufacture of semiconductors. The following is a detailed description of the target object of the processing liquid of the present invention.

The above-mentioned treatment liquid can be used, for example, to remove insulating films, anti-etching agents, anti-reflective films, etching residues, and ashing residues on the substrate. The above-mentioned treatment liquid is preferably used in the cleaning step of the object (especially, semiconductor substrate) subjected to CMP treatment or polishing. As described above, when using the treatment liquid, it can be used as a diluted treatment liquid obtained by diluting the treatment liquid.

[Object] As the object of the treatment liquid, for example, an object having metal can be listed, and a semiconductor substrate having metal is preferred. Furthermore, when the semiconductor substrate has metal, for example, the metal can be present at any of the surface and back surface, side surface, and groove of the semiconductor substrate. Furthermore, when the semiconductor substrate has metal, it includes not only the case where the metal is present directly on the surface of the semiconductor substrate, but also the case where the metal is present on the semiconductor substrate through other layers.

As the metal, for example, at least one metal M selected from the group consisting of copper (Cu), cobalt (Co), ruthenium (Ru), aluminum (Al), tungsten (W), titanium (Ti), tantalum (Ta), chromium (Cr), uranium (Hf), nimium (Os), platinum (Pt), nickel (Ni), manganese (Mn), iron (Fe), zirconium (Zr), molybdenum (Mo), palladium (Pd), lumber (La), and iridium (Ir) can be listed, Cu, Co, Ru, Mo, or W is preferred, Cu, Co, or Ru is more preferred, and Cu is further preferred. That is, as the target object, the target object containing Cu is preferred. Moreover, as the target object, the target object containing W is also preferred.

The metal may be any substance containing metal (metal atoms), and examples thereof include a single substance of metal M and an alloy containing metal M.

The object to which the processing liquid is applied may include, for example, a semiconductor substrate, a metal wiring film, a barrier metal, and an insulating film.

Examples of wafers constituting semiconductor substrates include wafers made of silicon-based materials such as silicon (Si) wafers, silicon carbide (SiC) wafers, and resin-based wafers containing silicon (glass epoxy wafers), gallium phosphide (GaP) wafers, gallium arsenide (GaAs) wafers, and indium phosphide (InP) wafers. Examples of silicon wafers include n-type silicon wafers doped with pentavalent atoms (such as phosphorus (P), arsenic (As), and antimony (Sb)) and p-type silicon wafers doped with trivalent atoms (such as boron (B) and gallium (Ga)). Silicon used as silicon wafers include, for example, amorphous silicon, single crystal silicon, polycrystalline silicon, and polysilicon. Among them, wafers made of silicon-based materials such as silicon wafers, silicon carbide wafers, and resin-based wafers containing silicon (glass epoxy wafers) are preferred.

Examples of insulating films include silicon oxide films (e.g., silicon dioxide (SiO ₂ ) films and tetraethyl orthosilicate (Si(OC ₂ H ₅ ) ₄ ) films (TEOS films)), silicon nitride films (e.g., silicon nitride (Si ₃ N ₄ ) and silicon carbide nitride (SiNC)), and low dielectric constant (Low-k) films (e.g., carbon-doped silicon oxide (SiOC) films, BD (black diamond) films, and silicon carbide (SiC) films), with low dielectric constant (Low-k) films being preferred.

As metal wiring films, copper-containing films, cobalt-containing films, and ruthenium-containing films are preferred. As copper-containing films, for example, wiring films consisting only of metallic copper (copper wiring films) and wiring films made of alloys consisting of metallic copper and other metals (copper alloy wiring films) can be listed. As copper alloy wiring films, alloy wiring films consisting of one or more metals selected from Al, Ti, Cr, Mn, Ta, and W and copper can be listed. More specifically, there are copper-aluminum alloy wiring films (CuAl alloy wiring films), copper-titanium alloy wiring films (CuTi alloy wiring films), copper-chromium alloy wiring films (CuCr alloy wiring films), copper-manganese alloy wiring films (CuMn alloy wiring films), copper-titanium alloy wiring films (CuTa alloy wiring films), and copper-tungsten alloy wiring films (CuW alloy wiring films).

As the cobalt-containing film, for example, there can be listed a metal film consisting only of metallic cobalt (cobalt metal film) and a metal film made of an alloy consisting of metallic cobalt and other metals (cobalt alloy metal film). As the cobalt alloy metal film, there can be listed a metal film made of an alloy consisting of one or more metals selected from Ti, Cr, Fe, Ni, Mo, Pd, Ta and W and cobalt. More specifically, there are cobalt-titanium alloy metal films (CoTi alloy metal films), cobalt-chromium alloy metal films (CoCr alloy metal films), cobalt-iron alloy metal films (CoFe alloy metal films), cobalt-nickel alloy metal films (CoNi alloy metal films), cobalt-molybdenum alloy metal films (CoMo alloy metal films), cobalt-palladium alloy metal films (CoPd alloy metal films), cobalt-tungsten alloy metal films (CoTa alloy metal films), and cobalt-tungsten alloy metal films (CoW alloy metal films).

Examples of the ruthenium-containing film include a metal film consisting of only metallic ruthenium (ruthenium metal film) and a metal film made of an alloy consisting of metallic ruthenium and other metals (ruthenium alloy metal film).

As a method for forming the above-mentioned insulating film, copper-containing film, cobalt-containing film, and ruthenium-containing film on a wafer constituting a semiconductor substrate, there is no particular limitation as long as it is a method commonly performed in the field. As a method for forming an insulating film, for example, the following method can be cited: a silicon oxide film is formed by heat-treating a wafer constituting a semiconductor substrate in the presence of oxygen, and then silane and ammonia are introduced to form a silicon nitride film by chemical vapor deposition (CVD). As a method for forming a copper-containing film, a cobalt-containing film, and a ruthenium-containing film, for example, the following method can be cited: a circuit is formed on a wafer having the above-mentioned insulating film by a known method such as an anti-etching agent, and then a copper-containing film, a cobalt-containing film, and a ruthenium-containing film are formed by a method such as gold plating and CVD.

<Objects treated with CMP> As an object to be used for cleaning the treatment liquid, an object treated with CMP (especially a semiconductor substrate) is preferred, and an object containing Cu treated with CMP is more preferred. CMP treatment refers to a process that uses, for example, a polishing slurry containing polishing particles (abrasive grains) to flatten the surface of a semiconductor substrate having a metal wiring film, a barrier metal, and an insulating film through a combination of chemical action and mechanical polishing.

There may be a situation where residues such as abrasive grains (e.g., silicon dioxide and aluminum oxide) used in the CMP treatment, polished metal wiring films, and metal impurities from barrier metals remain on the surface of the object subjected to the CMP treatment. In addition, organic substances from the CMP treatment liquid used in the CMP treatment may also remain as residues. Such residues may, for example, cause short circuits between wirings and deteriorate the electrical properties of the semiconductor substrate, so the semiconductor substrate subjected to the CMP treatment is provided with a cleaning treatment for removing such residues from the surface. As a specific example of the object subjected to the CMP treatment, the substrate subjected to the CMP treatment described in Journal of Precision Engineering Vol.84, No.3, 2018 can be cited, but it is not limited to this.

<Polished object> The surface of the object can be polished after the CMP treatment. Polishing is a process that uses a polishing pad to reduce the residue on the surface of the object. Specifically, the surface of the object that has been subjected to the CMP treatment is brought into contact with the polishing pad, and the object and the polishing pad are made to slide relative to each other while supplying a polishing composition to the contacted portion. As a result, the residue on the surface of the object is removed by the frictional force of the polishing pad and the chemical action of the polishing composition.

As a polishing composition, a known polishing composition can be appropriately used according to the type of the object and the type and amount of the residue to be removed. There is no particular limitation on the components contained in the polishing composition, and examples thereof include water-soluble polymers such as polyvinyl alcohol, water as a dispersion medium, and acids such as nitric acid. Regarding the polishing device and polishing conditions used in the polishing treatment, they can be appropriately selected from known devices and conditions according to the type of the object and the type of the residue. As a polishing treatment, for example, the treatment described in paragraphs [0085] to [0088] of International Publication No. 2017/169539 can be cited, and the contents are incorporated into this specification.

In one embodiment of the polishing treatment, the above-mentioned treatment liquid is preferably used as a polishing composition to perform polishing treatment on the object. In other words, the treatment liquid is preferably used to polish the object having residue after CMP treatment.

[How to use] The treatment liquid can be used by a known method. The following is a detailed description of how to use the treatment liquid.

[Treatment step] As a method of using a treatment liquid, for example, a method of treating an object including a step of bringing the object into contact with the treatment liquid can be cited. Hereinafter, the step of bringing the object into contact with the treatment liquid is also referred to as a "contact step". There is no particular limitation on the method of bringing the object into contact with the treatment liquid, and for example, a method of immersing the object in the treatment liquid placed in a tank, a method of spraying the treatment liquid on the object, a method of causing the treatment liquid to flow on the object, and a combination thereof can be cited. The above method can be appropriately selected according to the purpose. In addition, the above method can appropriately adopt a style that is usually performed in the field. For example, there are wiping cleaning methods that remove residues by physically contacting a cleaning member such as a brush with the surface of the object while supplying the treatment liquid, and rotation (dropping) methods that drip the treatment liquid while rotating the object. In the immersion method, it is better to perform ultrasonic treatment on the object immersed in the treatment liquid in order to further reduce the impurities remaining on the surface of the object.

The contacting of the object with the treatment solution in the contacting step may be performed only once or twice or more. When the contacting is performed twice or more, the same method may be repeated or different methods may be combined.

The contacting step may be performed by a single-piece method or a batch method. The single-piece method is a method in which one object is usually processed, and the batch method is a method in which a plurality of objects are usually processed at the same time.

The temperature of the treatment liquid is not particularly limited as long as it is a temperature usually performed in the field. Generally, cleaning is performed at room temperature (about 25°C), but in order to improve the slag removal performance and suppress damage to the components, the temperature can be arbitrarily selected. For example, the temperature of the treatment liquid is preferably 10 to 60°C, and more preferably 15 to 50°C.

The contact time between the object and the treatment solution can be appropriately changed according to the type and content of each component contained in the treatment solution and the object and purpose of the treatment solution. In practice, 10 to 120 seconds is preferred, 20 to 90 seconds is more preferred, and 30 to 60 seconds is even more preferred.

The supply amount (supply rate) of the treatment solution is preferably 50 to 5000 mL/min, more preferably 500 to 2000 mL/min.

In the contacting step, a mechanical stirring method may be used to further enhance the processing ability of the processing liquid. As mechanical stirring methods, for example, there may be listed a method of circulating the processing liquid on the object, a method of flowing or spraying the processing liquid on the object, and a method of stirring the processing liquid with ultrasound or megafrequency.

Furthermore, after the contacting step, a step of bringing the object into contact with a rinsing liquid (hereinafter, also referred to as a "rinsing step") may be performed. By performing the rinsing step, the object obtained in the contacting step can be cleaned with the rinsing liquid to effectively remove residues. The rinsing step is preferably performed continuously after the object treatment step and the object is rinsed with the rinsing liquid. The rinsing step may be performed using the above-mentioned mechanical stirring method.

As the rinse liquid, for example, water (preferably DI water), methanol, ethanol, isopropyl alcohol (IPA), N-methylpyrrolidone, γ-butyrolactone, dimethyl sulfoxide, ethyl lactate, and propylene glycol monomethyl ether acetate can be listed. In addition, an aqueous rinse liquid having a pH exceeding 8.0 (diluted aqueous ammonium hydroxide, etc.) can be used.

As a method of bringing the rinse liquid into contact with the object, the method of bringing the above-mentioned treatment liquid into contact with the object can be similarly applied. The contact time between the object and the rinse liquid can be appropriately changed according to the type and content of each component contained in the treatment liquid and the object and purpose of use of the treatment liquid. In practice, 10 to 120 seconds is preferred, 20 to 90 seconds is more preferred, and 30 to 60 seconds is even more preferred.

Furthermore, after the above-mentioned rinsing step, a drying step of drying the object can be performed. As drying methods, for example, there can be listed a rotary drying method, a method of passing dry gas over the object, a method of heating the substrate by a heating mechanism such as a heating plate and an infrared lamp, a Marangoni drying method, a Notagoni drying method, an IPA (isopropyl alcohol) drying method, and any combination of these methods.

[Manufacturing method of semiconductor device] The above-mentioned processing method of the object can be preferably applied to the manufacturing method of semiconductor device. The above-mentioned processing method can be implemented in combination before or after other steps performed on the substrate. Other steps can be incorporated into the implementation of the above-mentioned processing method, and the above-mentioned processing method can also be incorporated into other steps for implementation. As other steps, for example, the formation step of structures such as metal wiring, gate structure, source structure, drain structure, insulating film, ferromagnetic layer and non-magnetic layer (for example, layer formation, etching, chemical mechanical polishing and modification, etc.), the formation step of anti-etching agent, exposure step and removal step, heat treatment step, cleaning step and inspection step can be listed.

The above processing method can be performed at any stage of the back-end process (BEOL: Back end of the line), middle process (MOL: Middle of the line) and front-end process (FEOL: Front end of the line), and it is preferably performed in the front-end process or middle process. [Example]

The present invention is further described in detail below based on the embodiments. The materials, usage amounts, proportions, processing contents and processing steps shown in the following embodiments can be appropriately changed as long as they do not deviate from the main purpose of the present invention. Therefore, the scope of the present invention should not be interpreted as limiting the embodiments shown below.

In the following examples, the pH of the treatment liquid was measured at 25°C using a pH meter (manufactured by HORIBA, Ltd., model "F-74") in accordance with JIS Z8802-1984. In addition, when preparing the treatment liquids of the examples and comparative examples, the treatment of the container, the preparation, filling, storage and analysis of the treatment liquid were all carried out in a clean room that meets ISO Class 2 or below.

[Raw materials of treatment solution] The treatment solution was produced using the compounds listed in the following table. Each component used to produce the treatment solution was classified as semiconductor grade or as a high purity grade based on the semiconductor grade.

[Reducing agents] ･Ascorbic acid ･Caffeic acid (polyphenolic compound) ･Alizarin (polyphenolic compound) ･Endorphin (polyphenolic compound) ･Urushiol (polyphenolic compound) ･Resorcinol (polyphenolic compound) ･Hydroquinone (polyphenolic compound) ･Rheum officinale (polyphenolic compound) ･Quercetin (polyphenolic compound) ･Catechin (polyphenolic compound) ･Hydrogen peroxide ･Hydrazine ･Gallic acid (polyphenolic compound) ･3-O-ethylglycerol ascorbic acid (ascorbic acid derivative) ･Sodium ascorbate (ascorbic acid salt) ･Catechin (polyphenolic compound) ･1,2,4-pyrogallol (polyphenolic compound) ･Methyl gallate (polyphenolic compound, gallic acid derivative) ･Ethyl gallate (polyphenol compound, gallic acid derivative) ･Propyl gallate (polyphenol compound, gallic acid derivative) ･Ethyl gallate (polyphenol compound, gallic acid derivative) ･Gallic acid (polyphenol compound, gallic acid derivative) ･Gallic acid (polyphenol compound)

[Specified compounds] ･Dehydroascorbic acid ･2,3-Diketogulonic acid ･4-Oxaloylcrotonic acid ･Compound X: 3,4,5-Trioxane-1-carboxylic acid

[Other compounds] ･TEAH: Tetraethylammonium hydroxide (specific quaternary ammonium compound) ･TBAH: Tetrabutylammonium hydroxide (specific quaternary ammonium compound) ･ETMAH: Ethyltrimethylammonium hydroxide (specific quaternary ammonium compound) ･Choline: 2-Hydroxyethyltrimethylammonium hydroxide (specific quaternary ammonium compound) ･1,2-Diaminopropane (amine compound) ･N-Methyl-1,3-diaminopropane (amine compound) ･Ethanolamine (amine compound) ･Propanolamine (amine compound) ･Citric acid (chelating agent) ･Formic acid (chelating agent) ･Oxalic acid (chelating agent) ･Tartaric acid (chelating agent) ･Lactic acid (chelating agent) ･HEDPO: 1-hydroxyethylidene-1,1’-diphosphonic acid (chelating agent) ･EDTPO: ethylenediaminetetrakis(methylenephosphonic acid) (chelating agent) ･Histidine (chelating agent) ･Triazole (preservative) ･Tetrazole (preservative) ･Pyrrole (preservative) ･Polyacrylic acid (Mw=2,000, polymer) ･Polyethylene glycol (Mw=500, surfactant)

Regarding the pH of the treatment liquid, sulfuric acid and/or potassium hydroxide were used as pH adjusters as necessary for adjustment. In the treatment liquid, the components indicated as components of the treatment liquid in the table and the remaining components (residues) excluding the pH adjuster were ultrapure water.

[Preparation of treatment liquid] The method for preparing the treatment liquid is described using Example 1 as an example. Ascorbic acid, dehydroascorbic acid, and TEAH were added to ultrapure water, respectively, so that the final treatment liquid obtained had the blending amount described in the following table. The obtained mixed liquid was stirred thoroughly to obtain the treatment liquid of Example 1.

According to the manufacturing method of Example 1, the processing liquids of each Example or each Comparative Example having the composition shown in the following table were manufactured.

[Evaluation of treatment solution] The obtained treatment solution was evaluated for its corrosion inhibition of Cu and removal of organic residues. The following is an explanation of the evaluation method.

[Evaluation of Cu corrosion inhibition] Using the treatment solution produced by the above method, the corrosion inhibition of Cu was evaluated. A 2.0 cm × 2.0 cm Cu wafer was placed in 150 mL of the treatment solution of each embodiment or each comparative example and immersion treated at room temperature (25°C) for 10 minutes. The film thickness of the wafer before and after the immersion treatment was measured using VR300DEC (resistivity meter, manufactured by Kokusai Electric Semiconductor Service Inc.), and the etching rate (ER-A) (Å/min) was calculated from the film thickness difference before and after the immersion treatment. Using DIW as the treatment solution, the etching rate (ER-B) (Å/min) was measured by the same method.

The ratio (ER-A/ER-B) of the etching rate (ER-A) obtained when the processing solution of the embodiment or the comparative example is used relative to the etching rate (ER-B) obtained when DIW is used as the processing solution is evaluated by the following evaluation criteria. The smaller the ER-A/ER-B, the better the corrosion inhibition of Cu. 7: ER-A/ER-B≦0.3 6: 0.3＜ER-A/ER-B≦0.5 5: 0.5＜ER-A/ER-B≦0.9 4: 0.9＜ER-A/ER-B≦1.1 3: 1.1＜ER-A/ER-B≦1.5 2: 1.5＜ER-A/ER-B≦2.0 1: 2.0＜ER-A/ER-B

[Evaluation of organic residue removal performance] Using the processing liquid produced by the above method, the organic residue removal performance when cleaning the semiconductor substrate subjected to chemical mechanical polishing was evaluated. Using FREX300S-II (polishing device, manufactured by EBARA CORPORATION), polishing liquid 1 was used as the polishing liquid, and a 12-inch diameter wafer having a TEOS film (Low-k film) on the surface was polished under the conditions of an in-plane average polishing pressure of 105hPa, a polishing liquid supply rate of 200mL/min, and a polishing time of 30 seconds. Next, polishing liquid 2 was used as the polishing liquid, and the wafer subjected to the above polishing treatment was polished under the conditions of an in-plane average polishing pressure of 70hPa, a polishing liquid supply rate of 200mL/min, and a polishing time of 60 seconds. Using the samples of the processing liquid of each embodiment or each comparative example adjusted to room temperature (23°C), the obtained wafer subjected to CMP treatment was wiped and cleaned for 60 seconds and then dried. In addition, the compositions of the above-mentioned polishing liquid 1 and polishing liquid 2 are as follows. Polishing liquid 1 (pH 7.0) ･Colloidal silica (PL3, manufactured by FUSO CHEMICAL CO., LTD.) 0.1 mass% ･Glycine                                        1.0 mass% ･3-Amino-1,2,4-triazole                                          0.2 mass% ･Benzotriazole (BTA)                                          30 mass ppm ･Hydrogen peroxide     ... ･Citric acid                                      1.0 mass% ･Alkyl alkoxide surfactant                              100 mass ppm ･BTA                                       0.2 mass% ･Hydrogen peroxide                                                   1.0 mass% ･pH adjuster (potassium hydroxide and nitric acid) ･Water                                                Residue

Afterwards, the polished surface of the obtained wafer was observed using S-4800 (Scanning Electron Microscope, SEM: Scanning Electron Microscope, manufactured by Hitachi High-Tech Corporation), and the target was determined by analyzing the constituent elements using an energy dispersive X-ray spectroscopy (EDX: Energy Dispersive X-ray spectroscopy) as needed. In this way, the number of defects was measured based on the organic residue (residue with organic matter as the main component) present in 2cm×2cm (unit area).

The organic residue removal performance of the processing liquid was evaluated using the following evaluation criteria. The smaller the amount of organic residue per unit area detected on the polishing surface of the wafer, the better the organic residue removal performance. 7: The number of organic residues per unit area is less than 2 6: The number of organic residues per unit area is 2 or more and less than 3 5: The number of organic residues per unit area is 3 or more and less than 5 4: The number of organic residues per unit area is 5 or more and less than 10 3: The number of organic residues per unit area is 10 or more and less than 20 2: The number of organic residues per unit area is 20 or more and less than 30 1: The number of organic residues per unit area is 30 or more

[Results] In the table, the column "Content (mass %)" indicates the content (mass %) of each component relative to the total mass of the treatment solution. In the table, "Quaternary ammonium compound" indicates a specific quaternary ammonium compound represented by formula (B). In the table, the value in the column "B/A" indicates the mass ratio of the content (B) of the specific compound to the content (A) of the reducing agent (content of the specific compound (B)/content of the reducing agent (A)). In the table, the value in the column "C/B" indicates the mass ratio of the content (C) of the specific quaternary ammonium compound to the content (B) of the specific compound (content of the specific quaternary ammonium compound (C)/content of the specific compound (B)). In the table, the value in the "A/D" column indicates the mass ratio of the content of the reducing agent (A) to the content of the chelating agent (D) (content of the reducing agent (A)/content of the chelating agent (D)). In the table, the value in the pH column indicates the pH of the treatment solution before and after dilution at 25°C measured by the above-mentioned pH meter. In the table, the "Cu corrosion resistance" column indicates the evaluation results of the corrosion inhibition of Cu. Table 2 is a continuation of Table 1, Table 4 is a continuation of Table 3, and Table 6 is a continuation of Table 5. For example, the treatment solution of Example 28 shown in Tables 1 and 2 is a treatment solution containing 0.06 mass% of ascorbic acid, 0.01 mass% of dehydroascorbic acid, 0.126 mass% of TEAH, 0.02 mass% of citric acid, and 0.106 mass% of 1,2-diaminopropane, and a pH of 11.0.

[Table 1] Treatment fluid Reducing agent (A) Content (mass%) Specific compound (B) Content (mass%) Quaternary Ammonium Compounds (C) Content (mass%) Chelating agent (D) Content (mass%) Embodiment 1 Ascorbic acid 0.06 Dehydroascorbic acid 0.01 TEAH 0.126 - - Embodiment 2 Ascorbic acid 0.03 Dehydroascorbic acid 0.01 TEAH 0.126 Citric Acid 0.02 Embodiment 3 Ascorbic acid 0.01 Dehydroascorbic acid 0.01 TEAH 0.126 Citric Acid 0.02 Embodiment 4 Ascorbic acid 0.06 Dehydroascorbic acid 2,3-diketogulonic acid 0.01 0.01 TEAH 0.126 Citric Acid 0.02 Embodiment 5 Ascorbic acid 0.01 Dehydroascorbic acid 2,3-diketogulonic acid 0.01 0.01 TEAH 0.126 Citric Acid 0.02 Embodiment 6 Ascorbic acid 0.06 2,3-Diketogulonic acid 0.01 TEAH 0.126 Citric Acid 0.02 Embodiment 7 Ascorbic acid 0.06 Dehydroascorbic acid 0.02 TEAH 0.126 Citric Acid 0.02 Embodiment 8 Ascorbic acid 0.06 Dehydroascorbic acid 0.05 TEAH 0.126 Citric Acid 0.02 Embodiment 9 Caffeic acid 0.06 Dehydroascorbic acid 0.01 TEAH 0.126 Citric Acid 0.02 Embodiment 10 Alizarin 0.06 Dehydroascorbic acid 0.01 TEAH 0.126 - - Embodiment 11 Endorphins 0.06 Dehydroascorbic acid 0.01 TEAH 0.126 Citric Acid 0.02 Embodiment 12 Urushiol 0.06 Dehydroascorbic acid 0.01 TEAH 0.126 Citric Acid 0.02 Embodiment 13 Resorcinol 0.06 Dehydroascorbic acid 0.01 TEAH 0.126 - - Embodiment 14 Hydroquinone 0.06 Dehydroascorbic acid 0.01 TEAH 0.126 Citric Acid 0.02 Embodiment 15 Rhein 0.06 Dehydroascorbic acid 0.01 TEAH 0.126 Citric Acid 0.02 Embodiment 16 Quercetin 0.06 Dehydroascorbic acid 0.01 TEAH 0.126 Citric Acid 0.02 Embodiment 17 Catechins 0.06 Dehydroascorbic acid 0.01 TEAH 0.126 Citric Acid 0.02 Embodiment 18 Hydrogen peroxide 0.06 Dehydroascorbic acid 0.01 TEAH 0.126 Citric Acid 0.02 Embodiment 19 Hydrazine 0.06 Dehydroascorbic acid 0.01 TEAH 0.126 Citric Acid 0.02 Embodiment 20 Ascorbic acid hydroquinone 0.03 0.03 Dehydroascorbic acid 0.01 TEAH 0.126 Citric Acid 0.02 Embodiment 21 Ascorbic acid 0.06 Dehydroascorbic acid 0.01 TEAH TBAH 0.126 0.126 - - Embodiment 22 Ascorbic acid 0.06 Dehydroascorbic acid 0.01 TBAH 0.126 - - Embodiment 23 Ascorbic acid 0.06 Dehydroascorbic acid 0.01 TEAH 0.126 Formic acid 0.02 Embodiment 24 Ascorbic acid 0.06 Dehydroascorbic acid 0.01 TEAH 0.126 oxalic acid 0.02 Embodiment 25 Ascorbic acid 0.06 Dehydroascorbic acid 0.01 TEAH 0.126 Citric Acid 0.5 Embodiment 26 Ascorbic acid 0.06 Dehydroascorbic acid 0.01 TEAH 0.126 Citric Acid 4.0 Embodiment 27 Ascorbic acid 0.06 Dehydroascorbic acid 0.01 TEAH 0.126 Citric Acid 2.5 Embodiment 28 Ascorbic acid 0.06 Dehydroascorbic acid 0.01 TEAH 0.126 Citric Acid 0.02 Embodiment 29 Ascorbic acid 0.06 Dehydroascorbic acid 0.01 TEAH 0.126 Citric Acid 0.02 Embodiment 30 Ascorbic acid 0.06 Dehydroascorbic acid 0.01 TEAH 0.126 Citric Acid 0.02 Embodiment 31 Ascorbic acid 0.06 Dehydroascorbic acid 0.01 TEAH 0.126 Citric Acid 0.02 Embodiment 32 Gallic acid 0.06 Compound X 0.01 TEAH 0.126 Citric Acid 0.02 Embodiment 33 Gallic acid 0.06 Compound X 0.01 TEAH 0.126 - - Embodiment 34 Gallic acid 0.06 Compound X 0.01 TEAH 0.126 Citric Acid 0.02 Embodiment 35 Ascorbic acid 6.0 Dehydroascorbic acid 1.0 TEAH 12.6 Citric Acid 2.0 Embodiment 36 Ascorbic acid 0.03 Dehydroascorbic acid 0.01 TEAH 0.126 Citric Acid 0.02 Embodiment 37 Ascorbic acid 0.03 Dehydroascorbic acid 0.01 TEAH 0.126 Citric Acid 0.02 Embodiment 38 Ascorbic acid 0.03 Dehydroascorbic acid 0.01 TEAH 0.126 Citric Acid 0.02 Embodiment 39 Gallic acid 0.06 4-Oxaloylcrotonic acid 0.01 TEAH 0.126 Citric Acid 0.02 Embodiment 40 Gallic acid 0.06 4-Oxaloylcrotonic acid 0.01 TEAH 0.126 Citric Acid 0.02 Embodiment 41 Gallic acid 0.06 4-Oxaloylcrotonic acid 0.01 TEAH 0.126 Citric Acid 0.02 Embodiment 42 Gallic acid 0.06 4-Oxaloylcrotonic acid 0.01 TEAH 0.126 Citric Acid 0.02 Embodiment 43 Gallic acid 0.06 4-Oxaloylcrotonic acid 0.01 TEAH 0.126 Citric Acid 0.02 Embodiment 44 Gallic acid 0.06 4-Oxaloylcrotonic acid 0.01 TEAH 0.126 Citric Acid 0.02

[Table 2] Treatment fluid Object Other additives Content (mass%) B/A C/B A/D pH Organic residue removal Cu corrosion resistance Embodiment 1 - - 0.17 12.6 - 11.0 6 6 Embodiment 2 - - 0.33 12.6 1.5 11.0 6 5 Embodiment 3 - - 1.0 12.6 0.5 11.0 3 4 Embodiment 4 - - 0.33 6.3 3.0 11.0 5 6 Embodiment 5 - - 2.0 6.3 0.5 11.0 3 5 Embodiment 6 - - 0.17 12.6 3.0 11.0 5 5 Embodiment 7 - - 0.33 6.3 3.0 11.0 6 6 Embodiment 8 - - 0.83 2.5 3.0 11.0 7 6 Embodiment 9 - - 0.17 12.6 3.0 11.0 5 4 Embodiment 10 - - 0.17 12.6 - 11.0 5 5 Embodiment 11 - - 0.17 12.6 3.0 11.0 5 4 Embodiment 12 - - 0.17 12.6 3.0 11.0 5 4 Embodiment 13 - - 0.17 12.6 - 11.0 5 5 Embodiment 14 - - 0.17 12.6 3.0 11.0 5 4 Embodiment 15 - - 0.17 12.6 3.0 11.0 5 4 Embodiment 16 - - 0.17 12.6 3.0 11.0 5 4 Embodiment 17 - - 0.17 12.6 3.0 11.0 5 4 Embodiment 18 - - 0.17 12.6 3.0 11.0 4 3 Embodiment 19 - - 0.17 12.6 3.0 11.0 5 3 Embodiment 20 - - 0.17 12.6 3.0 11.0 5 5 Embodiment 21 - - 0.17 25.2 - 11.0 5 6 Embodiment 22 - - 0.17 12.6 - 11.0 5 6 Embodiment 23 - - 0.17 12.6 3.0 11.0 6 6 Embodiment 24 - - 0.17 12.6 3.0 11.0 7 7 Embodiment 25 - - 0.17 12.6 0.1 11.0 6 5 Embodiment 26 - - 0.17 12.6 0.015 11.0 5 3 Embodiment 27 - - 0.17 12.6 0.024 11.0 5 4 Embodiment 28 1,2-Diaminopropane 0.106 0.17 12.6 3.0 11.0 7 7 Embodiment 29 N-Methyl-1,3-diaminopropane 0.106 0.17 12.6 3.0 11.0 6 6 Embodiment 30 Ethanolamine 0.106 0.17 12.6 3.0 11.0 6 6 Embodiment 31 Propanolamine 0.106 0.17 12.6 3.0 11.0 6 6 Embodiment 32 1,2-Diaminopropane 0.106 0.17 12.6 3.0 11.0 6 7 Embodiment 33 - - 0.17 12.6 - 11.0 4 6 Embodiment 34 1,2-Diaminopropane 0.106 0.17 12.6 3.0 11.0 6 7 Embodiment 35 1,2-Diaminopropane 10.6 0.17 12.6 3.0 11.0 7 7 Embodiment 36 Triazole 0.05 0.33 12.6 1.5 11.0 6 7 Embodiment 37 Tetrazole 0.05 0.33 12.6 1.5 11.0 6 7 Embodiment 38 Pyrrole 0.05 0.33 12.6 1.5 11.0 6 7 Embodiment 39 1,2-Diaminopropane 0.106 0.17 12.6 3.0 11.0 7 7 Embodiment 40 1,2-Diaminopropane 10.6 0.17 12.6 3.0 11.0 7 6 Embodiment 41 - - 0.17 12.6 3.0 11.0 6 7 Embodiment 42 1,2-Diaminopropane 0.106 0.17 12.6 3.0 11.0 7 7 Embodiment 43 1,2-Diaminopropane 10.6 0.17 12.6 3.0 11.0 7 6 Embodiment 44 - - 0.17 12.6 3.0 11.0 7 7

[table 3] Treatment fluid Reducing agent (A) Content (mass%) Specific compound (B) Content (mass%) Quaternary Ammonium Compounds (C) Content (mass%) Chelating agent (D) Content (mass%) Embodiment 45 Ascorbic acid 0.03 Dehydroascorbic acid 0.01 TEAH 0.126 Histidine Citrate 0.02 0.05 Embodiment 46 Gallic acid 0.06 4-Oxaloylcrotonic acid 0.01 TEAH 0.126 Histidine Citrate 0.02 0.05 Embodiment 47 Gallic acid 0.06 4-Oxaloylcrotonic acid 0.01 TEAH 0.126 Histidine Citrate 0.02 0.05 Embodiment 48 Ascorbic acid 0.06 4-Oxaloylcrotonic acid 0.01 TEAH 0.126 Histidine Citrate 0.02 0.05 Embodiment 49 3-O-Ethylglycerol Ascorbic Acid 0.03 Dehydroascorbic acid 0.01 TEAH 0.126 Citric Acid 0.02 Embodiment 50 Sodium ascorbate 0.03 Dehydroascorbic acid 0.01 TEAH 0.126 Citric Acid 0.02 Embodiment 51 Catechol 0.06 4-Oxaloylcrotonic acid 0.01 TEAH 0.126 Citric Acid 0.02 Embodiment 52 1,2,4-Benzenetriol 0.06 4-Oxaloylcrotonic acid 0.01 TEAH 0.126 Citric Acid 0.02 Embodiment 53 Methyl Gallate 0.06 4-Oxaloylcrotonic acid 0.01 TEAH 0.126 Citric Acid 0.02 Embodiment 54 Ethyl Gallate 0.06 4-Oxaloylcrotonic acid 0.01 TEAH 0.126 Citric Acid 0.02 Embodiment 55 Propyl Gallate 0.06 4-Oxaloylcrotonic acid 0.01 TEAH 0.126 Citric Acid 0.02 Embodiment 56 Octyl Gallate 0.06 4-Oxaloylcrotonic acid 0.01 TEAH 0.126 Citric Acid 0.02 Embodiment 57 Ascorbic acid 0.03 Dehydroascorbic acid 0.01 TEAH 0.126 tartaric acid 0.02 Embodiment 58 Ascorbic acid 0.03 Dehydroascorbic acid 0.01 TEAH 0.126 Lactic acid 0.02 Embodiment 59 Ascorbic acid 0.03 Dehydroascorbic acid 0.01 TEAH 0.126 HEDPO 0.02 Embodiment 60 Ascorbic acid 0.03 Dehydroascorbic acid 0.01 TEAH 0.126 EDTPO 0.02 Embodiment 61 Ascorbic acid 0.06 Dehydroascorbic acid 6.0 TEAH 0.126 Citric Acid 0.02 Embodiment 62 Ascorbic acid 0.06 Dehydroascorbic acid 5.0 TEAH 0.126 Citric Acid 0.02 Embodiment 63 Ascorbic acid 0.06 Dehydroascorbic acid 1.0 TEAH 0.126 Citric Acid 0.02 Embodiment 64 Ascorbic acid 0.06 Dehydroascorbic acid 0.5 TEAH 0.126 Citric Acid 0.02 Embodiment 65 Ascorbic acid 0.06 Dehydroascorbic acid 0.2 TEAH 0.126 Citric Acid 0.02 Embodiment 66 Ascorbic acid 0.03 Dehydroascorbic acid 0.01 TEAH 0.126 Citric Acid 0.02 Embodiment 67 Ascorbic acid 0.03 Dehydroascorbic acid 0.01 TEAH 0.126 Citric Acid 0.02 Embodiment 68 Ascorbic acid 0.03 Dehydroascorbic acid 0.01 TEAH 0.126 Citric Acid 0.02 Embodiment 69 Ascorbic acid 0.03 Dehydroascorbic acid 0.01 TEAH 0.126 Citric Acid 0.02 Embodiment 70 Ascorbic acid 0.03 Dehydroascorbic acid 0.01 TEAH 0.126 Citric Acid 0.02 Embodiment 71 Ascorbic acid 0.06 Dehydroascorbic acid 2,3-diketogulonic acid 0.01 0.01 TEAH 0.126 Citric Acid 0.02 Embodiment 72 Ascorbic acid 0.06 Dehydroascorbic acid 2,3-diketogulonic acid 0.01 0.01 TEAH 0.126 Citric Acid 0.02 Embodiment 73 Ascorbic acid 0.06 Dehydroascorbic acid 2,3-diketogulonic acid 0.01 0.01 TEAH 0.126 Citric Acid 0.02 Embodiment 74 Ascorbic acid 0.06 Dehydroascorbic acid 2,3-diketogulonic acid 0.01 0.01 TEAH 0.126 Citric Acid 0.02 Embodiment 75 Ascorbic acid 0.6 Dehydroascorbic acid 0.01 TEAH 0.126 Citric Acid 0.02 Embodiment 76 Ascorbic acid 6.0 Dehydroascorbic acid 0.01 TEAH 0.126 Citric Acid 0.1 Embodiment 77 Ascorbic acid 6.0 Dehydroascorbic acid 0.1 TEAH 0.126 Citric Acid 0.1 Embodiment 78 Ascorbic acid 6.0 Dehydroascorbic acid 1.0 TEAH 0.126 Citric Acid 0.1 Embodiment 79 Ascorbic acid 6.0 Dehydroascorbic acid 0.01 TEAH 1.30 Citric Acid 0.02 Embodiment 80 Ascorbic acid 6.0 Dehydroascorbic acid 1.0 TEAH 0.126 Citric Acid 0.5 Embodiment 81 Ascorbic acid 6.0 Dehydroascorbic acid 1.0 TEAH 1.30 Citric Acid 0.2 Embodiment 82 Ascorbic acid 6.0 Dehydroascorbic acid 1.0 TEAH 1.30 Citric Acid 0.2

[Table 4] Treatment fluid Object Other additives Content (mass%) B/A C/B A/D pH Organic residue removal Cu corrosion resistance Embodiment 45 - - 0.33 12.6 0.43 11.0 6 7 Embodiment 46 - - 0.17 12.6 0.86 11.0 6 7 Embodiment 47 - - 0.17 12.6 0.86 11.0 6 7 Embodiment 48 - - 0.17 12.6 0.86 11.0 6 6 Embodiment 49 - - 0.33 12.6 1.5 11.0 7 7 Embodiment 50 - - 0.33 12.6 1.5 11.0 7 7 Embodiment 51 - - 0.17 12.6 3.0 11.0 7 7 Embodiment 52 - - 0.17 12.6 3.0 11.0 7 7 Embodiment 53 - - 0.17 12.6 3.0 11.0 7 7 Embodiment 54 - - 0.17 12.6 3.0 11.0 7 7 Embodiment 55 - - 0.17 12.6 3.0 11.0 7 7 Embodiment 56 - - 0.17 12.6 3.0 11.0 7 7 Embodiment 57 - - 0.33 12.6 1.5 11.0 7 7 Embodiment 58 - - 0.33 12.6 1.5 11.0 6 6 Embodiment 59 - - 0.33 12.6 1.5 11.0 7 7 Embodiment 60 - - 0.33 12.6 1.5 11.0 7 7 Embodiment 61 1,2-Diaminopropane 0.106 100.0 0.02 3.0 11.0 7 5 Embodiment 62 1,2-Diaminopropane 0.106 83.3 0.03 3.0 11.0 7 5 Embodiment 63 1,2-Diaminopropane 0.106 16.7 0.1 3.0 11.0 7 6 Embodiment 64 1,2-Diaminopropane 0.106 8.3 0.3 3.0 11.0 7 6 Embodiment 65 1,2-Diaminopropane 0.106 3.3 0.6 3.0 11.0 7 7 Embodiment 66 - - 0.33 12.6 1.5 8.0 5 5 Embodiment 67 - - 0.33 12.6 1.5 9.0 5 5 Embodiment 68 - - 0.33 12.6 1.5 10.0 5 5 Embodiment 69 - - 0.33 12.6 1.5 12.0 6 6 Embodiment 70 - - 0.33 12.6 1.5 13.0 6 7 Embodiment 71 - - 0.33 6.3 3.0 8.0 6 6 Embodiment 72 - - 0.33 6.3 3.0 12.0 6 7 Embodiment 73 1,2-Diaminopropane 0.106 0.33 6.3 3.0 8.0 6 7 Embodiment 74 1,2-Diaminopropane 0.106 0.33 6.3 3.0 12.0 6 7 Embodiment 75 1,2-Diaminopropane 0.106 0.02 12.6 30.0 11.0 6 7 Embodiment 76 1,2-Diaminopropane 0.106 0.002 12.6 60.0 11.0 6 7 Embodiment 77 1,2-Diaminopropane 0.106 0.02 1.3 60.0 11.0 6 7 Embodiment 78 1,2-Diaminopropane 0.106 0.17 0.1 60.0 11.0 5 6 Embodiment 79 1,2-Diaminopropane 0.106 0.002 130.0 300.0 11.0 6 7 Embodiment 80 1,2-Diaminopropane 0.106 0.17 0.1 12.0 11.0 7 7 Embodiment 81 1,2-Diaminopropane 0.106 0.17 1.3 30.0 11.0 6 7 Embodiment 82 1,2-Diaminopropane 1.06 0.17 1.3 30.0 11.0 6 7

[table 5] Treatment fluid Reducing agent (A) Content (mass%) Specific compound (B) Content (mass%) Quaternary Ammonium Compounds (C) Content (mass%) Chelating agent (D) Content (mass%) Embodiment 83 Ascorbic acid 2.3 Dehydroascorbic acid 0.39 ETMAH 4.00 Citric Acid 2.0 Embodiment 84 Ascorbic acid 2.3 Dehydroascorbic acid 0.39 Choline 4.00 Citric Acid 2.0 Embodiment 85 Ascorbic acid 2.3 Dehydroascorbic acid 0.39 TEAH 4.00 Citric Acid 2.0 Embodiment 86 Ascorbic acid 2.3 Dehydroascorbic acid 0.39 ETMAH 4.00 Citric Acid 2.0 Embodiment 87 Ascorbic acid 2.3 Dehydroascorbic acid 0.39 Choline 4.00 Citric Acid 2.0 Embodiment 88 Ascorbic acid 2.3 Dehydroascorbic acid 0.39 TEAH 4.00 Citric Acid 2.0 Embodiment 89 Ascorbic acid 2.3 Dehydroascorbic acid 0.39 ETMAH 4.00 Citric Acid 2.0 Embodiment 90 Ascorbic acid 2.3 Dehydroascorbic acid 0.39 Choline 4.00 Citric Acid 2.0 Comparison Example 1 - - Dehydroascorbic acid 0.01 - - - - Comparison Example 2 Ascorbic acid 0.06 - - - - - -

[Table 6] Treatment fluid Object Other additives Content (mass%) B/A C/B A/D pH Organic residue removal Cu corrosion resistance Embodiment 83 1,2-Diaminopropane 0.106 0.17 10.3 1.2 8.0 6 3 Embodiment 84 1,2-Diaminopropane 0.106 0.17 10.3 1.2 8.0 6 3 Embodiment 85 Polyacrylic acid 0.160 0.17 10.3 1.2 6.0 7 3 Embodiment 86 Polyacrylic acid 0.160 0.17 10.3 1.2 6.0 7 3 Embodiment 87 Polyacrylic acid 0.160 0.17 10.3 1.2 6.0 7 3 Embodiment 88 Polyethylene glycol 0.160 0.17 10.3 1.2 6.0 7 3 Embodiment 89 Polyethylene glycol 0.160 0.17 10.3 1.2 6.0 7 3 Embodiment 90 Polyethylene glycol 0.160 0.17 10.3 1.2 6.0 7 3 Comparison Example 1 - - - - - 11.0 3 1 Comparison Example 2 - - - - - 11.0 1 3

From the above table, it is confirmed that the treatment solution of the present invention has excellent Cu corrosion inhibition (corrosion resistance) and excellent organic residue removal. From the results of Examples 1 to 6, it is confirmed that the effect of the present invention is more excellent when the content of the reducing agent is 0.02 mass % or more relative to the total mass of the treatment solution. From the results of Examples 6 to 8, it is confirmed that the effect of the present invention is more excellent when the content of the specific compound is 0.02 mass % or more relative to the total mass of the treatment solution. From the results of Examples 61 to 65, it was confirmed that when the content of the specific compound relative to the total mass of the treatment solution was 3.0 mass % or less, the corrosion resistance was more excellent, and when it was 0.3 mass % or less, the corrosion resistance effect was more excellent. From the results of Examples 61 to 65, it was confirmed that when the mass ratio (B/A) of the content of the specific compound (B) relative to the content of the reducing agent (A) was 50 or less, the corrosion resistance was more excellent, and when it was 5 or less, the corrosion resistance was more excellent. The results of Examples 61 to 65 confirmed that when the mass ratio (C/B) of the content of the specific quaternary ammonium compound (C) to the content of the specific compound (B) is 0.1 or more, the corrosion resistance is more excellent, and when it is 0.5 or more, the corrosion resistance is more excellent. The results of Examples 9 to 20 and 45 to 56 confirmed that when the reducing agent is at least one selected from the group including ascorbic acid and ascorbic acid derivatives or salts thereof and polyphenol compounds, the effect of the present invention is more excellent. The results of Examples 25 to 27 confirmed that when the content of the chelating agent is 0.01 mass % or more, the effect of the present invention is more excellent. From the results of Examples 25 to 27, it was confirmed that the effect of the present invention is more excellent when the mass ratio (A/D) of the content of the reducing agent (A) to the content of the chelating agent (D) is 0.02 or more, and the effect of the present invention is more excellent when it is 0.1 or more. From the results of Examples 1 and 28 to 32, it was confirmed that the effect of the present invention is more excellent when the treatment liquid contains an amine compound. From the results of Examples 39 to 40 and 42 to 43, it was confirmed that the corrosion resistance is more excellent when the content of the amine compound is 5.0 mass% or less relative to the total mass of the treatment liquid. From the results of Examples 2 and 36 to 38, it was confirmed that the effect of the present invention is more excellent when the treatment liquid contains a preservative. The results of Examples 66 to 70 show that the effect of the present invention is more excellent when the pH of the treatment solution is 10.5 to 13.0. The results of Examples 28 and 35 show that the effect of the present invention is excellent even when the concentration of the treatment solution is different.

[Evaluation of corrosion inhibition of W] The corrosion inhibition of W (tungsten) was evaluated using the treatment solutions of Examples 83 to 90 prepared by the above method and the treatment solutions of Comparative Examples 1 and 2. A 2.0 cm × 2.0 cm W wafer was placed in a container filled with the treatment solution of each Example or Comparative Example and subjected to immersion treatment for 30 minutes at room temperature (25°C). Thereafter, the film thickness of the obtained wafer was measured using a resistivity meter (VR250, manufactured by Kokusai Electric Semiconductor Service Inc.), and the etching rate (Å/minute) was calculated from the difference in film thickness before and after the above immersion treatment.

The corrosion inhibition of W in the treatment solution was evaluated according to the following evaluation criteria. The lower the etching rate, the better the corrosion inhibition. 7: less than 1.5Å/min 6: 1.5Å/min or more and less than 1.8Å/min 5: 1.8Å/min or more and less than 2.1Å/min 4: 2.1Å/min or more and less than 2.4Å/min 3: 2.4Å/min or more and less than 2.7Å/min 2: 2.7Å/min or more and less than 3.0Å/min 1: 3.0Å/min or more

The evaluation results of the corrosion inhibition of W are shown in Table 7. The compositions of the treatment solutions of the Examples and Comparative Examples are shown in Tables 5 and 6.

[Table 7] pH W Corrosion Inhibition Embodiment 83 8.0 4 Embodiment 84 8.0 4 Embodiment 85 6.0 7 Embodiment 86 6.0 7 Embodiment 87 6.0 7 Embodiment 88 6.0 7 Embodiment 89 6.0 7 Embodiment 90 6.0 7 Comparison Example 1 11.0 2 Comparison Example 2 11.0 2

As shown in Table 7, it is confirmed that the treatment liquid of the present invention also has excellent W corrosion inhibition. By comparing Examples 83 to 90, it is confirmed that when the pH of the treatment liquid is 5.0 to 7.0, the organic residue removal property and W corrosion inhibition are more excellent.

without.

Claims (20)

A treatment agent comprising: a reducing agent; and a specific compound selected from at least one of the group consisting of dehydroascorbic acid, 2,3-diketogulonic acid, 4-oxalylcrotonic acid and 3,4,5-trioxane-1-carboxylic acid. The treatment solution as described in claim 1, wherein the reducing agent contains at least one selected from the group consisting of ascorbic acid and ascorbic acid derivatives or their salts and polyphenol compounds. The treatment solution as described in claim 1, wherein the reducing agent contains at least one selected from the group consisting of ascorbic acid and ascorbic acid derivatives or salts thereof and gallic acid and gallic acid derivatives. The treatment liquid as described in claim 1, wherein the mass ratio of the content of the aforementioned specific compound to the content of the aforementioned reducing agent is 0.01 to 199. The treatment solution as described in claim 1, further comprising a quaternary ammonium compound represented by formula (B), In formula (B), R ¹ to R ⁴ each independently represents an alkyl group which may have a substituent or a linking group represented by -O-, a plurality of R ¹ to R ⁴ may be bonded to each other to form a ring, the total number of carbon atoms of the groups represented by R ¹ to R ⁴ is 5 or more, and ^X- represents an anion. The treatment solution as described in claim 5, wherein the mass ratio of the content of the aforementioned quaternary ammonium compound to the content of the aforementioned specific compound is 0.01 to 100.0. The treatment solution as described in claim 1 has a pH of 8.0 to 13.0. The treatment solution as described in claim 1 further contains a chelating agent. The treatment solution as described in claim 8, wherein the aforementioned chelating agent contains an organic acid. The treatment solution as described in claim 9, wherein the aforementioned organic acid contains at least one selected from the group consisting of polycarboxylic acid, hydroxycarboxylic acid and phosphonic acid. The treatment solution as described in claim 9, wherein the aforementioned organic acid contains at least one selected from the group consisting of citric acid, formic acid, oxalic acid, tartaric acid, lactic acid, 1-hydroxyethylidene-1,1'-diphosphonic acid and ethylenediaminetetrakis(methylenephosphonic acid). The treatment liquid as described in claim 8, wherein the mass ratio of the content of the reducing agent to the content of the chelating agent is 0.005 to 5.0. The treatment solution as described in claim 1 further contains an amine compound. The treatment solution as described in claim 13, wherein the amine compound contains a compound represented by formula (C1), In formula (C1), R ⁵ to R ⁸ each independently represents a hydrogen atom or an alkyl group which may have a substituent or a linking group represented by -O-, and a plurality of R ⁵ to R ⁸ may be bonded to each other to form a ring. In formula (C1), R ⁹ represents an alkylene group having 2 or more carbon atoms which may have a substituent or a linking group represented by -O- or -NR ^N -, and ^RN represents a hydrogen atom or an alkyl group. The treatment liquid as described in claim 14, wherein in the aforementioned formula (C1), the carbon number of the group represented by ^R9 is 2 to 4. The treatment liquid as described in claim 1 further contains a preservative. The treatment liquid as described in claim 1 further contains water, and the content of the water is 60% by mass or more relative to the total mass of the treatment liquid. A treatment liquid as described in any one of claim 1 to claim 17, which is used to clean an object containing Cu that has been subjected to chemical mechanical polishing. A method for treating an object, comprising the step of bringing the object containing Cu that has been subjected to chemical mechanical polishing into contact with a treatment solution as described in any one of claims 1 to 18. A method for manufacturing a semiconductor device, comprising the object cleaning method described in claim 19.