JP6646073B2 - Processing liquid - Google Patents

Description

  The present invention relates to a processing liquid mainly applied to processing of a semiconductor device substrate.

  2. Description of the Related Art In the manufacture of semiconductor integrated circuits, large-scale, high-density, and miniaturization are progressing. In the manufacture of integrated circuits, a lithography process using a positive or negative photoresist is employed. A photoresist film applied to a substrate (for example, a silicon substrate and a substrate on which a circuit structure is formed) is exposed through an exposure original such as a photomask. Thereafter, by developing the exposed photoresist film, a resist (resist pattern, resist film) having a shape corresponding to the original exposure plate is obtained. Etching is performed using the obtained resist as a mask.

When the metal layer and the insulating layer on the substrate are etched by dry etching means such as plasma using the obtained resist as a mask, residues derived from the resist, the metal layer, and the insulating layer adhere to the substrate. Usually, in order to remove the adhered residue, a cleaning step (and a rinsing step if necessary) is performed using a cleaning composition as a treatment liquid.
Further, the resist used as a mask at the time of etching is thereafter removed from the substrate by a dry method using ashing (ashing) (dry ashing) or a wet method using a stripping solution. Since a residue adheres to the substrate from which the resist has been removed by dry ashing, a cleaning step using a treatment liquid (cleaning composition) is usually performed to remove the residue.

On the other hand, the wet method using a stripping solution is a mode in which a resist used as a mask at the time of etching is stripped and removed using a treatment liquid (a stripping composition).
By the way, in the manufacture of a semiconductor device, after a permanent film (for example, a pattern film such as a color filter) is formed on a substrate, it is sometimes required to remove the permanent film. Specifically, when the formed permanent film has a defect in manufacturing or the like, it is conceivable to remove the permanent film from the entire substrate and reuse (recycle) the substrate. Here, examples of the permanent film include a finely processed color filter, a transparent insulating film, a resin lens, and the like, which are applied to the manufacture of a solid-state imaging device and an image display device.
Also when removing the permanent film, it has been studied to remove the permanent film by using a peeling composition as a treatment liquid, similarly to the resist used as a mask at the time of etching as described above.

  For example, Patent Literature 1 discloses a cleaning composition for removing a color resist as a liquid for removing a permanent film. More specifically, a cleaning composition comprising tetramethylammonium hydroxide (TMAH) is disclosed.

Korean Patent Publication No. 2014-0113114

The inventor of the present invention uses the removing solution described in Patent Document 1 to remove and remove an organic film (for example, various resists used as a mask at the time of etching and a permanent film) on a substrate, and dry etching residue. Alternatively, when the substrate on which the dry ashing residue adhered was washed, it was found that the removal solution described in Patent Document 1 did not satisfy the desired requirements for removability, and further improvement was required. became.
On the other hand, generally, when the organic film on the substrate is peeled off or when the dry etching residue or the dry ashing residue adhered to the substrate is washed, a metal such as an electrode or a wiring arranged on the substrate is used. Often the film is exposed. For this reason, the treatment liquid needs to have a corrosion preventing property against a metal film (particularly, an aluminum film) such as an electrode or a wiring formed on the substrate.

  Therefore, the present invention has a corrosion preventing property for a metal film disposed on a substrate and a removability for an organic film on the substrate, or a removal for a dry etching residue or a dry ashing residue attached to the substrate. An object of the present invention is to provide a processing solution having excellent properties.

The present inventor has conducted intensive studies to achieve the above object, and as a result, determined that water, a hydrophilic organic solvent, a quaternary ammonium salt and a predetermined amount (0.001 mass ppt to 1 mass ppm based on the total mass of the treatment liquid). The present inventors have found that a desired effect can be obtained by using a treatment solution containing the inorganic anion of (1) and the present invention, and have reached the present invention.
That is, it has been found that the above-described object can be achieved by the following configuration.

(1) A treatment liquid containing water, a hydrophilic organic solvent, a quaternary ammonium salt, and an inorganic anion,
The treatment liquid, wherein the content of the inorganic anion is 0.001 mass ppt to 1 mass ppm based on the total mass of the treatment liquid.
(2) The treatment liquid according to (1), wherein the inorganic anion is a sulfate ion, a chloride ion, or a nitrate ion.
(3) The treatment liquid according to (1) or (2), wherein the inorganic anion is a nitrate ion.
(4) For the total mass of the processing solution,
The content of the water is 1 to 30% by mass,
The content of the hydrophilic organic solvent is 40 to 98% by mass,
The processing solution according to any one of (1) to (3), wherein the content of the quaternary ammonium salt is 0.1 to 30% by mass.
(5) For the total mass of the processing solution,
The content of the water is 20 to 98% by mass,
The content of the hydrophilic organic solvent is 1 to 40% by mass,
The processing solution according to any one of (1) to (3), wherein the content of the quaternary ammonium salt is 0.1 to 30% by mass.
(6) The treatment liquid according to any one of (1) to (5), further comprising an amine compound.
(7) The treatment liquid according to (6), wherein the amine compound contains at least one selected from hydroxylamine and a hydroxylamine salt.
(8) The treatment liquid according to (7), wherein the content of at least one selected from the group consisting of hydroxylamine and hydroxylamine salt is 0.1 to 15% by mass based on the total mass of the treatment liquid.
(9) The treatment liquid according to any one of (1) to (8), further comprising an oxidizing agent.
(10) The treatment liquid according to any one of (1) to (9), further comprising a halide.

  ADVANTAGE OF THE INVENTION According to this invention, it has the corrosion prevention property with respect to the metal film arrange | positioned at the board | substrate, and the removability with respect to the organic film on a board | substrate, or the removal with respect to the dry etching residue or the dry ashing residue attached to the board. It is possible to provide a processing solution having excellent properties.

It is a schematic diagram of the board | substrate which has the hole produced in the Example column.

Hereinafter, the present invention will be described in detail.
The description of the components described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.

In the present invention, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit and an upper limit.
In the notation of a group (atom group) in the present specification, the notation of not indicating substituted or unsubstituted includes those having no substituent and those having a substituent as long as the effects of the present invention are not impaired. Is what you do. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). This is synonymous with each compound.

In this specification, “radiation” means, for example, the emission line spectrum of a mercury lamp, far ultraviolet rays represented by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, electron beams, and the like. Further, in this specification, light means actinic rays or radiation. Unless otherwise specified, the term “exposure” in the present specification means not only exposure with far ultraviolet rays such as a mercury lamp and an excimer laser, X-rays, and EUV light, but also particles such as electron beams and ion beams. Line drawing is also included in the exposure.
In this specification, “(meth) acrylate” represents both or either acrylate and methacrylate, and “(meth) acryl” represents both or any of acryl and methacryl.
In this specification, “monomer” and “monomer” have the same meaning. The monomer in the present specification is distinguished from an oligomer and a polymer, and unless otherwise specified, refers to a compound having a weight average molecular weight of 2,000 or less. In this specification, a polymerizable compound refers to a compound having a polymerizable functional group, and may be a monomer or a polymer. The polymerizable functional group refers to a group that participates in a polymerization reaction.
In this specification, “preparation” means not only providing specific materials by synthesizing or preparing them, but also procuring predetermined materials by purchasing or the like.

In the present invention, the dry etching residue is a by-product generated by performing dry etching (for example, plasma etching), for example, a resist-derived organic residue, a Si-containing residue, and a metal-containing residue. Refers to residues and the like.
In the present invention, the dry ashing residue is a by-product generated by performing dry ashing (for example, plasma ashing), and includes, for example, an organic residue, a Si-containing residue, and a resist-derived residue. Refers to metal-containing residues.
In the following description, the above-mentioned dry etching residue and dry ashing residue may be collectively referred to as “residues”.

(Treatment liquid)
The treatment liquid of the present invention contains water, a hydrophilic organic solvent, a quaternary ammonium salt, and an inorganic anion. The feature of the present invention is that the content of the inorganic anion in the treatment liquid having the above composition is set to 0.001 mass ppm to 1 mass ppm with respect to the total mass of the treatment liquid. In particular, the inorganic anion preferably uses an inorganic acid as an ion source.
The treatment liquid of the present invention, having the above-described structure, has a property of preventing corrosion of a metal film disposed on a substrate, a property of removing an organic film on a substrate, or a dry etching residue adhering to a substrate. Alternatively, it has excellent removability for dry ashing residues.
Details of the reason why the desired effect can be obtained by containing a predetermined amount of the inorganic anion are unknown, but the quaternary ammonium salt and the inorganic anion interact with each other in the treatment solution to be superior to the residue and the like. It is considered that the removability is exhibited. Further, it is presumed that the treatment liquid has a high removal rate, which can suppress damage to the metal film on the substrate (in other words, has a corrosion preventing property). In particular, it has been confirmed that a more remarkable effect is exhibited when a nitrate ion containing nitric acid as an ion source is contained as an inorganic anion.
The treatment liquid is, for example, to remove a permanent film formed on a substrate or to peel off and remove various resists used as a mask at the time of etching, or to wash and remove a dry etching residue or a dry ashing residue attached to a substrate. It is preferably used for.
Hereinafter, each component contained in the treatment liquid of the present invention will be described, and then a method for producing the treatment liquid of the present invention will be described.

<Water>
The treatment liquid of the present invention contains water as a solvent.
The content of water is not particularly limited, but may be 1 to 99.999% by mass based on the total mass of the treatment liquid. As will be described later, the treatment liquid of the present invention may be formulated into any of an aqueous treatment liquid and an organic solvent treatment liquid by adjusting the contents of the hydrophilic organic solvent and water.
As the water, ultrapure water used for semiconductor production is preferable, and it is more preferable to further purify it and use water in which inorganic anions and metal ions are reduced. The purification method is not particularly limited, but purification using a filtration membrane or an ion exchange membrane, or purification by distillation is preferable.

<Hydrophilic organic solvent>
The treatment liquid of the present invention contains a hydrophilic organic solvent. By containing the hydrophilic organic solvent, it is possible to promote the solubilization of the additional components, unnecessary organic substances and residues, and to further improve the corrosion prevention effect.
The hydrophilic organic solvent is preferably an organic solvent that can be uniformly mixed with water at any ratio.
The hydrophilic organic solvent is not particularly limited, but includes, for example, a water-soluble alcohol solvent, a water-soluble ketone solvent, a water-soluble ester solvent, a water-soluble ether solvent (for example, glycol diether), a sulfone solvent, and a sulfoxide. A solvent, a nitrile solvent, and an amide solvent can be mentioned, and any of these can be used to obtain the desired effect of the present invention.

  Examples of the water-soluble alcohol-based solvent include, for example, alkanediol (for example, containing alkylene glycol), alkoxy alcohol (for example, containing glycol monoether), saturated aliphatic monohydric alcohol, unsaturated non-aromatic monohydric alcohol, and And low molecular weight alcohols having a ring structure.

  As the alkanediol, for example, glycol, 2-methyl-1,3-propanediol, 1,3-propanediol, 2,2-dimethyl-1,3-diol, 1,4-butanediol, 1,3- Butanediol, 1,2-butanediol, 2,3-butanediol, pinacol, and alkylene glycol.

  Examples of the alkylene glycol include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol and tetraethylene glycol.

  Examples of the alkoxy alcohol include 3-methoxy-3-methyl-1-butanol, 3-methoxy-1-butanol, 1-methoxy-2-butanol, and glycol monoether.

  Examples of the glycol monoether include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono n-propyl ether, ethylene glycol monoisopropyl ether, ethylene glycol mono n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol. Monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether, 1-methoxy-2-propanol, 2-methoxy-1-propanol, 1-ethoxy-2-propanol, 2-ethoxy- 1-propanol, propylene glycol mono-n-propyl ether Dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, ethylene glycol monobenzyl ether, and diethylene glycol monobenzyl ether. .

  Examples of the saturated aliphatic monohydric alcohol include methanol, ethanol, n-propyl alcohol, isopropyl alcohol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, 2-pentanol, t-pentyl alcohol, and 1-hexanol.

  Examples of unsaturated non-aromatic monohydric alcohols include allyl alcohol, propargyl alcohol, 2-butenyl alcohol, 3-butenyl alcohol, and 4-penten-2-ol.

  Examples of the low molecular weight alcohol having a ring structure include tetrahydrofurfuryl alcohol, furfuryl alcohol, and 1,3-cyclopentanediol.

  Examples of the water-soluble ketone solvent include acetone, propanone, cyclobutanone, cyclopentanone, cyclohexanone, diacetone alcohol, 2-butanone, 5-hexanedione, 1,4-cyclohexanedione, 3-hydroxyacetophenone, and 1,3. -Cyclohexanedione, and cyclohexanone.

  Examples of the water-soluble ester solvent include ethyl acetate, ethylene glycol monoacetate, glycol monoesters such as diethylene glycol monoacetate, and propylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, And glycol monoether monoesters such as ethylene glycol monoethyl ether acetate.

  Examples of the sulfone-based solvent include sulfolane, 3-methylsulfolane, and 2,4-dimethylsulfolane.

  Examples of the sulfoxide-based solvent include dimethyl sulfoxide and the like. When a sulfoxide-based solvent is used, it is preferable to use one having a grade in which inorganic ions such as sulfate ions, chloride ions, or nitrate ions and metal ions described below are reduced, or to purify further.

  Examples of the nitrile-based solvent include acetonitrile.

  Examples of the amide solvents include N, N-dimethylformamide, 1-methyl-2-pyrrolidone, 2-pyrrolidinone, 1,3-dimethyl-2-imidazolidinone, 2-pyrrolidinone, ε-caprolactam, formamide, N-methyl Examples include formamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpropanamide, and hexamethylphosphoric triamide.

Among the hydrophilic organic solvents, water-soluble alcohol solvents, sulfone solvents, amide solvents, and sulfoxide solvents are preferred from the viewpoint of further improving the corrosion prevention effect, and water-soluble alcohol solvents, and sulfoxide solvents. Solvents are more preferred, and among these, ethylene glycol monobutyl ether, tri (propylene glycol) methyl ether, and diethylene glycol monoethyl ether are even more preferred. It is preferable to use inorganic ions such as sulfate ions, chloride ions, and nitrate ions, and those having a grade in which metal ions described below are reduced, or to use them after further purification.
The hydrophilic organic solvents may be used alone or in combination of two or more.
The content of the hydrophilic organic solvent is not particularly limited, but may be 1 to 99.999% by mass based on the total mass of the treatment liquid.

By adjusting the contents of water and a hydrophilic organic solvent contained in the treatment liquid of the present invention, the liquid properties can be adjusted to any of aqueous and organic solvent-based formulations.
(Aqueous treatment liquid)
When the aqueous treatment liquid is used, the content of water is preferably 20 to 98% by mass, more preferably 35 to 98% by mass, and more preferably 50 to 95% by mass based on the total mass of the treatment solution. More preferably, Further, the content of the hydrophilic organic solvent is preferably from 1 to 40% by mass, more preferably from 5 to 35% by mass, and more preferably from 10 to 30% by mass based on the total mass of the treatment liquid. Is more preferable.

(Organic solvent treatment liquid)
When using an organic solvent-based treatment liquid, the content of water is preferably 1 to 30% by mass, more preferably 2 to 25% by mass, and preferably 4 to 20% by mass, based on the total mass of the treatment solution. More preferably, it is set to be% by mass. Further, the content of the hydrophilic organic solvent is preferably from 40 to 98% by mass, more preferably from 45 to 98% by mass, and more preferably from 50 to 95% by mass, based on the total mass of the treatment liquid. Is more preferred.

<Quaternary ammonium salt>
Further, the treatment liquid of the present invention contains a quaternary ammonium salt. By adding a quaternary ammonium salt, the removability of organic films (various resists, permanent films) and residues on the substrate can be further improved. The quaternary ammonium salt also functions as a pH adjuster.
The quaternary ammonium salt is preferably a compound represented by the following general formula (1).

(In the formula (1), R ^{4A to} R ^4D each independently represent an alkyl group having 1 to 6 carbon atoms, a hydroxyalkyl group, a benzyl group, or an aryl group having 1 to 6 carbon atoms. X ⁻ represents a counter anion. Represents.)

Wherein ^(1), R 4A ^{to R 4D} each independently represent an alkyl group having 1 to 6 carbon atoms (e.g., methyl group, ethyl group, and a butyl group), a hydroxyalkyl group having 1 to 6 carbon atoms (e.g. , A hydroxymethyl group, a hydroxyethyl group, and a hydroxybutyl group), a benzyl group, and an aryl group (for example, a phenyl group, a naphthyl group, and a naphthalene group). Especially, an alkyl group, a hydroxyethyl group, or a benzyl group is preferable.

In the formula (1), X ⁻ represents a counter anion and is not particularly limited. For example, various acid anions such as carboxylate ion, phosphate ion, sulfate ion, phosphonate ion, and nitrate ion, and hydroxides And halide ions (eg, chloride ions, fluoride ions, and bromide ions).

As the compound represented by the formula (1), specifically, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, trimethylhydroxyethylammonium hydroxide, dimethyldi (hydroxyethyl) ammonium hydroxide, methyltrimethylammonium hydroxide (Hydroxyethyl) ammonium hydroxide, tetra (hydroxyethyl) ammonium hydroxide, benzyltrimethylammonium hydroxide, and choline.
Of these, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, dimethyldi (hydroxyethyl) ammonium hydroxide, benzyltrimethylammonium hydroxide, and choline are preferred.
The quaternary ammonium salts may be used alone or in combination of two or more.

  The content of the quaternary ammonium salt in the treatment liquid is not particularly limited, but is preferably 0.1 to 30% by mass, and is preferably 0.5 to 10% by mass based on the total mass of the treatment solution. Is more preferable, and it is still more preferable that it is 0.5-5 mass%.

<Inorganic anion>
Further, the treatment liquid of the present invention contains an inorganic anion. By including a predetermined amount of the inorganic anion in the treatment liquid, it is possible to further improve the removability of the organic film and the residue on the substrate without corroding a metal film such as an electrode or a wiring disposed on the substrate. it can.
Although it does not specifically limit as an inorganic anion, a nitrate ion, a chloride ion, or a sulfate ion is preferable, and a nitrate ion is more preferable. Further, the treatment liquid may contain two or more kinds of inorganic anions.
The inorganic anion is preferably one using an inorganic acid as an ion source. Examples of a method for adding an inorganic anion to the treatment liquid include a method of adding an inorganic acid such as nitric acid, hydrochloric acid, or sulfuric acid to the treatment liquid.
Examples of the inorganic acid include nitric acid, hydrochloric acid, sulfuric acid, and phosphoric acid.
The content of the inorganic anion is 0.001 mass ppt to 1 mass ppm, preferably 0.001 mass ppt to 0.75 mass ppm, and preferably 1 mass ppt to 0.75 mass ppm based on the total mass of the treatment liquid. Is more preferable, and 1 mass ppt to 0.5 mass ppm is still more preferable.
When two or more inorganic anions are contained in the treatment liquid, it is preferable that the treatment liquid contains at least nitrate ions, and the amount of nitrate ions is within the above range. Among them, the treatment liquid contains at least nitrate ions and sulfate ions, and more preferably, the respective amounts of nitrate ions and sulfate ions are within the above ranges, and the treatment liquid contains nitrate ions, chloride ions, In particular, it is particularly preferable that at least sulfate ions are contained, and the respective amounts of nitrate ions, chloride ions, and sulfate ions are within the above ranges.

When the treatment liquid contains at least one inorganic anion selected from nitrate ions, chloride ions, and sulfate ions, the treatment liquid further contains at least one inorganic anion selected from nitrate ions, chloride ions, and sulfate ions. Content ratio (mass ratio) between the content of the species ion species (the amount of each of the nitrate ions, chloride ions, and sulfate ions when two or more species are contained) and the content of the quaternary ammonium salt Is preferably adjusted to the following range.
The content of the quaternary ammonium salt is the content of at least one ionic species selected from nitrate ions, chloride ions, and sulfate ions (at least two of the nitrate ions, chloride ions, and sulfate ions are included). When included, the mass ratio is preferably 1 × 10 ² to 1 × 10 ¹⁴ , more preferably 1 × 10 ⁴ to 1 × 10 ^13, and more preferably 1 × 10 ^7. even more preferably to to 1 × ^{10 12,} it is particularly preferable to ^{1 × 10 9 ~1 × 10 12} .
According to recent studies, by adjusting the content ratio in this manner, the treatment liquid of the present invention can not only maintain the above-described effects of the present invention well even after aging, but also has excellent recyclability. Has been confirmed. In particular, the effect is remarkable with nitrate ions and sulfate ions.
At the time of recycling, if washing is repeated, trace amounts of inorganic anions and metal-derived ions are eluted into the processing solution. The effects of the present invention may change due to their accumulation, but it has been found that the recyclability is excellent when it is within the above range. It is presumed that nitrate ions, chloride ions, and sulfate ions are more likely to interact particularly with quaternary ammonium salts than other inorganic anions.

(Method of removing inorganic anions)
The content of the inorganic anion contained in the treatment liquid of the present invention can be adjusted by a known method. When it is necessary to reduce the content of inorganic anions contained in the treatment liquid, for example, after passing through a reverse osmosis membrane or the like to perform primary purification, a cation exchange resin, an anion exchange resin, or The solution can be reduced by passing the solution through a purification device made of a mixed bed type ion exchange resin to perform secondary purification.
Also, a method described in JP-A-2007-254168 can be used. Specifically, a method in which the treatment liquid subjected to the secondary purification is further passed through a purification apparatus comprising a specific mixed-bed type ion exchange resin in which the anion exchange resin is mixed at a low mixing ratio with the cation exchange resin. It is.

  The step of reducing the content of the inorganic anion as described above is not particularly limited as long as the inorganic anion finally contained in the treatment liquid can be reduced. Before adjusting the processing solution, a mode used for a compound used in the processing solution (for example, any solvent selected from water and a hydrophilic organic solvent), or after adjusting the processing solution and before contacting the substrate By the way, the process may be performed on the processing solution.

  From the viewpoint of stably producing a treatment liquid, it is preferable to perform the treatment on the compound used in the treatment liquid before adjusting the treatment liquid.

  In addition, the amount of inorganic anions contained in the treatment liquid or the water and the solvent used in the treatment liquid can be analyzed by ion chromatography. In addition, it is preferable that all analysis and measurement be performed in a clean room. Preferably, the clean room meets 14644-1 clean room standards. Preferably, any one of ISO class 1, ISO class 2, ISO class 3, and ISO class 4 is satisfied, preferably, ISO class 1 and ISO class 2 are satisfied, and ISO class 1 is particularly preferable.

<Optional components>
(Corrosion inhibitor)
The treatment liquid of the present invention preferably contains a corrosion inhibitor. The corrosion inhibitor has a function of eliminating over-etching of a metal (for example, Co or W) that becomes a wiring film.
Although it does not specifically limit as a corrosion inhibitor, For example, 1,2,4-triazole (TAZ), 5-aminotetrazole (ATA), 5-amino-1,3,4-thiadiazole-2-thiol, 3-amino -1H-1,2,4 triazole, 3,5-diamino-1,2,4-triazole, tolyltriazole, 3-amino-5-mercapto-1,2,4-triazole, 1-amino-1,2 , 4-Triazole, 1-amino-1,2,3-triazole, 1-amino-5-methyl-1,2,3-triazole, 3-mercapto-1,2,4-triazole, 3-isopropyl-1 , 2,4-triazole, naphthotriazole, 1H-tetrazole-5-acetic acid, 2-mercaptobenzothiazole (2-MBT), 1-phenyl-2-tetrazoli -5-thione, 2-mercaptobenzimidazole (2-MBI), 4-methyl-2-phenylimidazole, 2-mercaptothiazoline, 2,4-diamino-6-methyl-1,3,5-triazine, thiazole, Imidazole, benzimidazole, triazine, methyltetrazole, bismuthiol I, 1,3-dimethyl-2-imidazolidinone, 1,5-pentamethylenetetrazole, 1-phenyl-5-mercaptotetrazole, diaminomethyltriazine, imidazolinethione, 4 -Methyl-4H-1,2,4-triazol-3-thiol, 5-amino-1,3,4-thiadiazole-2-thiol, benzothiazole, tritolyl phosphate, indazole, adenine, cytosine, guanine, thymine, Phosphate inhibitors, ami , Pyrazoles, propane thiols, silanes, secondary amines, benzohydroxamic acids, heterocyclic nitrogen inhibitors, citric acid, ascorbic acid, thiourea, 1,1,3,3-tetramethylurea, urea , Urea derivatives, uric acid, potassium ethyl xanthate, glycine, dodecylphosphonic acid, iminodiacetic acid, acid, boric acid, malonic acid, succinic acid, nitrilotriacetic acid, 2,3,5-trimethylpyrazine, 2-ethyl- 3,5-dimethylpyrazine, quinoxaline, acetylpyrrole, pyridazine, histadine, pyrazine, glutathione (reduced), cysteine, cystine, thiophene, mercaptopyridine N-oxide, thiamine HCl, tetraethylthiuram disulfide, 2,5- Dimercapto-1,3-thiadiazole ascorbic acid Ascorbic acid, catechol, t- butyl catechol, phenol, pyrogallol.

  Further, it is also preferable to include a substituted or unsubstituted benzotriazole as a corrosion inhibitor. The substituted benzotriazole is preferably, for example, a benzotriazole substituted with an alkyl group, an aryl group, a halogen group, an amino group, a nitro group, an alkoxy group, or a hydroxyl group. The substituted bebenzotriazole may be condensed with one or more aryl (eg, phenyl) or heteroaryl groups.

Substituted or unsubstituted benzotriazoles include, in addition to those described above, benzotriazole (BTA), 5-aminotetrazole, 1-hydroxybenzotriazole, 5-phenylthiol-benzotriazole, 5-chlorobenzotriazole, 4-chlorobenzotriazole Triazole, 5-bromobenzotriazole, 4-bromobenzotriazole, 5-fluorobenzotriazole, 4-fluorobenzotriazole, naphthotriazole, tolyltriazole, 5-phenyl-benzotriazole, 5-nitrobenzotriazole, 4-nitrobenzotriazole , 3-amino-5-mercapto-1,2,4-triazole, 2- (5-amino-pentyl) -benzotriazole, 1-amino-benzotriazole, 5-methyl-1H-benzo Liazole, benzotriazole-5-carboxylic acid, 4-methylbenzotriazole, 4-ethylbenzotriazole, 5-ethylbenzotriazole, 4-propylbenzotriazole, 5-propylbenzotriazole, 4-isopropylbenzotriazole, 5-isopropylbenzo Triazole, 4-n-butylbenzotriazole, 5-n-butylbenzotriazole, 4-isobutylbenzotriazole, 5-isobutylbenzotriazole, 4-pentylbenzotriazole, 5-pentylbenzotriazole, 4-hexylbenzotriazole, 5- Hexylbenzotriazole, 5-methoxybenzotriazole, 5-hydroxybenzotriazole, dihydroxypropylbenzotriazole, 1- [N, N-bis (2 Ethylhexyl) aminomethyl] -benzotriazole, 5-t-butylbenzotriazole, 5- (1 ′, 1′-dimethylpropyl) -benzotriazole, 5- (1 ′, 1 ′, 3′-trimethylbutyl) benzotriazole , 5-n-octylbenzotriazole, and 5- (1 ', 1', 3 ', 3'-tetramethylbutyl) benzotriazole.
The corrosion inhibitors may be used alone or in combination of two or more.

  The corrosion inhibitor is preferably selected from compounds represented by the following formulas (A) to (C), and substituted or unsubstituted tetrazole, from the viewpoint of further improving the corrosion inhibitory property. .

In the formula (A), R ^{1A to} R ^5A each independently represent a hydrogen atom, a substituent or an unsubstituted hydrocarbon group, a hydroxyl group, a carboxy group, or a substituted or unsubstituted amino group. However, the structure contains at least one group selected from a hydroxyl group, a carboxy group and a substituted or unsubstituted amino group.
In the formula (B), R ^{1B to} R ^4B each independently represent a hydrogen atom, a substituent, or an unsubstituted hydrocarbon group.
In the above formula ^{(C), R 1C, R} 2C and ^{R N} are each independently represent a hydrogen atom, a substituent or unsubstituted hydrocarbon group. Further, R ^1C and R ^2C may combine to form a ring.

In the formula (A), examples of the hydrocarbon represented by R ^{1A to} R ^5A include an alkyl group (preferably having 1 to 12, preferably 1 to 6, and particularly preferably 1 to 3 carbon atoms), an alkenyl group ( The number of carbon atoms is preferably 2 to 12, more preferably 2 to 6, an alkynyl group (the number of carbon atoms is preferably 2 to 12, and more preferably 2 to 6), and an aryl group (the number of carbon atoms is 6 to 22). Preferably, it is 6-14, more preferably 6-10, and an aralkyl group (carbon number is preferably 7-23, more preferably 7-15, and particularly preferably 7-11).
Examples of the substituent include a hydroxyl group, a carboxy group, or a substituted or unsubstituted amino group (the substituent is preferably an alkyl group having 1 to 6 carbon atoms, and an alkyl group having 1 to 3 carbon atoms). Is more preferable).
In the formula (A), in the structure, a hydroxyl group, a carboxy group and a substituted or unsubstituted amino group (as a substituent, an alkyl group having 1 to 6 carbon atoms is preferable, and an alkyl group having 1 to 3 carbon atoms is preferable. Groups are more preferable).

In the formula (A), examples of the substituent or unsubstituted hydrocarbon group represented by R ^{1A to} R ^5A include an unsubstituted hydrocarbon group having 1 to 6 carbon atoms, and a hydroxyl group, a carboxy group, or an amino group. And a C1-C6 hydrocarbon group substituted with a group.
Examples of the compound represented by the formula (A) include 1-thioglycerol, L-cysteine, thiomalic acid, and the like.

In formula (B), the hydrocarbon groups and substituents represented by R ^{1B to} R ^4B have the same meanings as the hydrocarbons and substituents represented by R ^{1A to} R ^{5A in} formula (A) described above. Examples of the substituent or unsubstituted hydrocarbon group represented by R ^{1B to} R ^4B include a hydrocarbon group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group, and a t-butyl group. Can be
Examples of the compound represented by the formula (B) include catechol and t-butyl catechol.

In formula ^(C), R ^1C, hydrocarbon groups and substituents represented by ^{R 2C} and ^{R N,} respectively and hydrocarbon and substituents represented by ^R 1A ^{to R 5A} of formula (A) described above synonymous is there. R ^1C, as a substituted or unsubstituted hydrocarbon group represented by R ^2C and R ^N are, for example, include a hydrocarbon group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group and a butyl group, Can be
Further, R ^1C and R ^2C may combine to form a ring, for example, a benzene ring. When R ^1C and R ^2C combine to form a ring, they may further have a substituent (for example, a hydrocarbon group having 1 to 5 carbon atoms).
Examples of the compound represented by the formula (C) include 1H-1,2,3-triazole, benzotriazole, 5-methyl-1H-benzotriazole, and the like.

  Examples of the substituted or unsubstituted tetrazole include, for example, an unsubstituted tetrazole, and a hydroxyl group, a carboxyl group, or a substituted or unsubstituted amino group as the substituent (an alkyl group having 1 to 6 carbon atoms as the substituent). Preferably, an alkyl group having 1 to 3 carbon atoms is more preferable).

  Other corrosion inhibitors other than the above include phosphoric acid, boric acid, organic acids (for example, phthalic acid, ascorbic acid, adipic acid, malic acid, oxalic acid, and salicylic acid), and silicon compounds. Among them, a silicon compound can be suitably used as a corrosion inhibitor, and tetraethoxysilane, tetramethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, phenyltrimethoxysilane, or diphenyl Dimethoxysilane is preferred. Among them, methyltrimethoxysilane is more preferable.

When a corrosion inhibitor is contained, its content is preferably 0.01 to 5% by mass, more preferably 0.05 to 5% by mass, and preferably 0 to 5% by mass, based on the total mass of the treatment liquid. More preferably, the content is from 1 to 3% by mass.
The corrosion inhibitors may be used alone or in combination of two or more. When two or more kinds are used in combination, the total content may be within the above range.

(Amine compound)
The treatment liquid of the present invention preferably contains an amine compound.
The amine compound is not particularly limited, and includes hydroxylamine, hydroxylamine salt, alkanolamine, and the like.
Among them, from the viewpoint of promoting the decomposition and solubilization of the organic film and the residue on the substrate and further preventing the corrosion of the object to be treated, it is preferably at least one selected from hydroxylamine and hydroxylamine salt.

Here, "hydroxylamine" relating to hydroxylamine and hydroxylamine salt refers to hydroxylamines in a broad sense including substituted or unsubstituted alkylhydroxylamine, etc. be able to.
The hydroxylamine is not particularly limited, but preferred embodiments include unsubstituted hydroxylamine and hydroxylamine derivatives.
Examples of the hydroxylamine derivative include, but are not limited to, O-methylhydroxylamine, O-ethylhydroxylamine, N-methylhydroxylamine, N, N-dimethylhydroxylamine, N, O-dimethylhydroxylamine, N-ethyl Hydroxylamine, N, N-diethylhydroxylamine, N, O-diethylhydroxylamine, O, N, N-trimethylhydroxylamine, N, N-dicarboxyethylhydroxylamine, N, N-disulfoethylhydroxylamine, etc. Is mentioned.
The hydroxylamine salt is preferably the above-mentioned inorganic or organic acid salt of hydroxylamine, and is a salt of an inorganic acid formed by bonding a nonmetal such as Cl, S, N, and P with hydrogen. More preferably, the salt is any one of hydrochloric acid, sulfuric acid and nitric acid.
The hydroxylamine salt used to form the treatment liquid of the present invention includes hydroxylammonium nitrate (also referred to as HAN), hydroxylammonium sulfate (also referred to as HAS), and hydroxylamine hydrochloride (also referred to as HAC). Preferred), hydroxylammonium phosphate, hydroxylammonium hydrochloride, N, N-diethylhydroxylammonium sulfate, N, N-diethylhydroxylammonium nitrate, or mixtures thereof.
Further, an organic acid salt of hydroxylamine can also be used, and examples thereof include hydroxylammonium citrate, hydroxylammonium oxalate, and hydroxylammonium fluoride.
The treatment liquid of the present invention may be in a form containing both hydroxylamine and a salt thereof. The above compounds may be used alone or in combination of two or more.
Among these, hydroxylamine or hydroxylammonium sulfate is preferable, and hydroxylammonium sulfate is more preferable, from the viewpoint that the desired effect of the present invention is remarkably obtained.

  When at least one selected from hydroxylamine and hydroxylamine salt is contained, the content thereof is 0.1 to 15 with respect to the total mass of the treatment liquid from the viewpoint of further improving the effect of the present invention. It is preferably within the range of 0.5% by mass, more preferably within the range of 0.5% to 10% by mass.

Further, it is preferable to contain alkanolamine as an amine compound from the viewpoint of promoting the solubilization of the additive component, the organic film on the substrate and the residue, and preventing corrosion.
The alkanolamine may be any of primary, secondary and tertiary amines, preferably a monoamine, diamine or triamine, more preferably a monoamine. The alkanol group of the amine preferably has 1 to 5 carbon atoms.
In the treatment liquid of the present invention, a compound represented by the following formula (2) is preferable.
Formula (2): R ¹ R ² —N—CH ₂ CH ₂ —O—R ³
(In Formula (2), R ¹ and R ² each independently represent a hydrogen atom, a methyl group, an ethyl group, or a hydroxyethyl group, and R ³ each independently represent a hydrogen atom or a hydroxyethyl group. Wherein, in the formula, at least one alkanol group is included)
Specific examples of the alkanolamine include monoethanolamine, diethanolamine, triethanolamine, tert-butyldiethanolamine, isopropanolamine, 2-amino-1-propanol, 3-amino-1-propanol, isobutanolamine, Examples include amino-2-ethoxy-propanol, and 2-amino-2-ethoxy-ethanol, also known as diglycolamine. The alkanolamines may be used alone or in combination of two or more.

  When alkanolamine is contained, its content is preferably from 0.1 to 60% by mass, more preferably from 0.5 to 50% by mass, and preferably from 0.5 to 50% by mass, based on the total mass of the treatment liquid. More preferably, the content is 5 to 20% by mass.

(Oxidant)
The treatment liquid of the present invention may contain an oxidizing agent. Here, the oxidizing agent may be any compound having an oxidizing action. Above all, hydrogen peroxide, ammonium persulfate, chloric acid, chlorous acid, hypochlorous acid, perchloric acid, permanganic acid are more excellent in both the removability of residues and the corrosiveness to insulating films. And at least one compound selected from the group consisting of iodic acid, hypoiodic acid, hypoiodic acid, periodic acid, and orthoperiodic acid. In the present invention, hydrogen peroxide or orthoperiodic acid is particularly preferred. The oxidizing agent may be used alone or in combination of two or more.

  When the oxidizing agent is contained, its content is preferably 0.01 to 10% by mass, more preferably 0.01 to 5% by mass, based on the total mass of the treatment liquid.

(Halide)
The treatment liquid of the present invention may contain a halide. Halides promote the decomposition and solubilization of the residue.
The halide is a compound containing one or more halogen elements, and examples of the halogen element include one or more selected from the group consisting of fluorine, chlorine, bromine, and iodine. Among them, fluoride or chloride is preferable from the viewpoint of promoting the decomposition and solubilization of the residue, and fluoride is particularly preferable from the viewpoint of further improving its effect.

Examples of the fluoride include, but are not limited to, hydrofluoric acid (HF), fluorosilicic acid (H ₂ SiF ₆ ), fluoroboric acid, ammonium fluorosilicate ((NH ₄ ) ₂ SiF ₆ ), and hexafluorophosphoric acid Tetramethylammonium, ammonium fluoride, ammonium fluoride salt, ammonium bifluoride salt, quaternary ammonium tetrafluoroborate represented by the formula NR ₄ BF ₄ , tetrafluoroborate represented by PR ₄ BF ₄ quaternary phosphonium, and tetrafluoroboric acid tetrabutylammonium (TBA-BF ₄₎ can be mentioned. Any of these can be used to obtain the desired effect of the present invention.
In the above-mentioned quaternary ammonium tetrafluoroborate represented by the above formula NR ₄ BF ₄ and quaternary phosphonium tetrafluoroborate represented by PR ₄ BF ₄ , R is the same or different. May be. R represents hydrogen, a linear, branched, or cyclic C1-C6 alkyl group (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group); And a C10 aryl group (for example, a benzyl group).
Examples of the quaternary ammonium tetrafluoroborate represented by the formula NR ₄ BF ₄ and the quaternary phosphonium tetrafluoroborate represented by PR ₄ BF ₄ include, for example, tetramethylammonium tetrafluoroborate and tetrafluoroborate Ammonium tetraethylammonium, tetrapropylammonium tetrafluoroborate, and tetrabutylammonium tetrafluoroborate.
The fluorides may be used alone or in combination of two or more.
Among the above, ammonium fluoride or fluorosilicic acid is preferable in that the desired effects of the present invention are remarkably obtained.

  When a fluoride is contained, its content is preferably 0.01 to 30% by mass, more preferably 0.1 to 15% by mass, and more preferably 0.1 to 15% by mass, based on the total mass of the treatment liquid. More preferably, it is 1 to 5% by mass.

(Chelating agent)
The treatment liquid may further contain a chelating agent. The chelating agent chelates the oxidized metal contained in the residue. Therefore, the recyclability of the treatment liquid is improved by adding the chelating agent.
The chelating agent is not particularly limited, but is preferably a polyaminopolycarboxylic acid.
A polyaminopolycarboxylic acid is a compound having a plurality of amino groups and a plurality of carboxylic acid groups. Polyaminopolycarboxylic acids include, for example, mono- or polyalkylenepolyamine polycarboxylic acids, polyaminoalkane polycarboxylic acids, polyaminoalkanol polycarboxylic acids, and hydroxyalkyl ether polyamine polycarboxylic acids.

  Examples of the polyaminopolycarboxylic acid include butylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid (DTPA), ethylenediaminetetrapropionic acid, triethylenetetraminehexaacetic acid, 1,3-diamino-2-hydroxypropane-N, N, N ′, N'-tetraacetic acid, propylenediaminetetraacetic acid, ethylenediaminetetraacetic acid (EDTA), trans-1,2-diaminocyclohexanetetraacetic acid, ethylenediaminediacetic acid, ethylenediaminedipropionic acid, 1,6-hexamethylene-diamine-N, N , N ', N'-tetraacetic acid, N, N-bis (2-hydroxybenzyl) ethylenediamine-N, N-diacetic acid, diaminopropanetetraacetic acid, 1,4,7,10-tetraazacyclododecane-tetraacetic acid , Diaminopropanoltetraacetic acid, and (hydroxyethyl ) Ethylenediamine triacetic acid. Among them, diethylenetriaminepentaacetic acid (DTPA), ethylenediaminetetraacetic acid (EDTA), or trans-1,2-diaminocyclohexanetetraacetic acid is preferable. These compounds can be used alone or in combination of two or more.

  When a chelating agent is contained, the content is preferably 0.01 to 5% by mass, more preferably 0.01 to 3% by mass, based on the total mass of the treatment liquid.

(PH adjuster)
Although the pH of the treatment liquid of the present invention is not particularly limited, when it contains hydroxylamine and a hydroxylamine salt as optional components, it is preferably at least pKa of the conjugate acid of hydroxylamine and the hydroxylamine salt. When the conjugate acid of hydroxylamine and the hydroxylamine salt has a pKa or more, the removability of the residue is dramatically improved. In other words, when the ratio of hydroxylamine and hydroxylamine salt in the treatment liquid in a molecular state is large, the residue is more excellent in removing the residue. For example, the pKa of the conjugate acid of hydroxylamine is about 6.

  The lower limit of the pH of the treatment liquid of the present invention is preferably pH 7.0, more preferably pH 7.5, and particularly preferably pH 8.0. As an upper limit, pH14 is preferable and pH13.4 is more preferable.

Known pH adjusters can be used, but generally do not contain metal ions. For example, ammonium hydroxide, monoamines, imines (for example, 1,8-diazabicyclo [5.4] .0] undecane-7-ene, and 1,5-diazabicyclo [4.3.0] non-5-ene), 1,4-diazabicyclo [2.2.2] octane, and guanidine salts (eg, carbonate Guanidine) and the like, and any of these can be used to obtain the effects of the present invention. Among them, ammonium hydroxide or imines (eg, 1,8-diazabicyclo [5.4.0] undecane-7-ene and 1,5-diazabicyclo [4.3.0] non-5-ene) Is preferable from the viewpoint of remarkably obtaining the effects of the present invention.
The pH adjusters may be used alone or in combination of two or more.

  When a pH adjuster is contained, the content of the pH adjuster in the treatment liquid is not particularly limited as long as the treatment liquid can achieve a desired pH, but is generally 0.1 to 0.1% based on the total mass of the treatment liquid. It is preferably 5% by mass, more preferably 0.1 to 2% by mass.

(Other additives)
The treatment liquid of the present invention may contain other additives as long as the effects of the present invention are exhibited. Examples of other additives include a surfactant, an antifoaming agent, a rust preventive, and a preservative described below.

<Kit and concentrate>
The processing liquid of the present invention may be a kit in which the raw material is divided into a plurality. In particular, it is preferable to use a kit when the treatment solution contains, as optional components, hydroxylamine and a hydroxylamine salt, which are amine compounds, or when the treatment solution contains an oxidizing agent and a quaternary ammonium salt.
Although not particularly limited, a specific method of using the treatment liquid as a kit includes, for example, a liquid composition containing at least one hydroxylamine compound selected from hydroxylamine and a hydroxylamine salt in water as the first liquid. An embodiment is provided in which a liquid composition containing other components is prepared as the second liquid. As an example of its use, a preferred embodiment is to mix both solutions to prepare a treatment solution, and then to apply the above treatment in a timely manner. Any of the hydrophilic organic solvent, the inorganic anion, and the quaternary ammonium salt may be contained. By doing so, it is possible to prevent the liquid performance from deteriorating due to the decomposition of the hydroxylamine compound or other components, and it is possible to exhibit the desired action effectively. The content of each component in the first liquid and the second liquid can be appropriately set as the content after mixing based on the content described above.
As another example, there is an embodiment in which a liquid composition containing a quaternary ammonium salt is prepared as a first liquid, and a liquid composition containing an oxidizing agent is prepared as a second liquid. A preferred embodiment is to mix the two solutions to prepare a treatment solution, and then to apply the above treatment in a timely manner. Other components such as a hydrophilic organic solvent and an inorganic anion may be contained in either. By doing so, it is possible to prevent the liquid performance from deteriorating due to the decomposition of the oxidizing agent or other components, and it is possible to exhibit the desired function effectively. The content of each component in the first liquid and the second liquid can be appropriately set as the content after mixing based on the content described above.
Further, the treatment liquid may be prepared as a concentrated liquid. In this case, it can be diluted with water at the time of use.

<Container>
The treatment liquid of the present invention can be filled in an arbitrary container, stored, transported, and used as long as corrosiveness or the like (regardless of whether or not it is a kit) is not a problem. As the container, a container having a high degree of cleanness and a small amount of elution of impurities is preferably used for semiconductor applications. Usable containers include, but are not limited to, the “Clean Bottle” series manufactured by Aicello Chemical Co., Ltd., and the “Pure Bottle” manufactured by Kodama Resin Industry Co., Ltd. The inner wall of this container is made of a resin different from one or more resins selected from the group consisting of polyethylene resin, polypropylene resin, and polyethylene-polypropylene resin, or a metal that has been subjected to rust prevention and metal elution prevention treatment. Preferably, it is formed.
As the above different resin, a fluorine-based resin (perfluoro resin) can be preferably used. As described above, by using a container whose inner wall is made of a fluorine-based resin, the inner wall is made of polyethylene resin, polypropylene resin, or elution of oligomers of ethylene and propylene as compared with the case where a container made of a polyethylene-polypropylene resin is used. The occurrence of defects can be suppressed.
As a specific example of such a container whose inner wall is made of a fluororesin, for example, a FluoroPure PFA composite drum manufactured by Entegris and the like can be mentioned. Also, pages 4 to 4 of JP-A-3-502677, page 3 of WO 2004/016526, pages 9 and 16 of WO 99/46309, etc. Containers can also be used.

<Filtering>
The treatment liquid of the present invention is preferably filtered with a filter for the purpose of removing foreign substances or reducing defects.
The material of the filter is not particularly limited as long as it is conventionally used for filtration or the like. For example, a filter made of a fluororesin such as PTFE (polytetrafluoroethylene), a polyamide-based resin such as nylon, and a polyolefin resin (including high-density and ultra-high molecular weight) such as polyethylene and polypropylene (PP) can be used. . Among these materials, polypropylene (including high-density polypropylene) or nylon is preferable.
The pore size of the filter is suitably about 0.001 to 1.0 μm, preferably about 0.02 to 0.5 μm, and more preferably about 0.01 to 0.1 μm. By setting the content in this range, it is possible to reliably remove fine foreign substances such as impurities or agglomerates contained in the treatment liquid while suppressing filtration clogging.
When using filters, different filters may be combined. At that time, the filtering by each filter may be performed only once or may be performed two or more times. The two or more times of filtering means, for example, the case where the liquid is circulated and the same filter is used for two or more times of filtering.

Filtering can be performed by combining different filters as described above. When filtering is performed two or more times by combining different filters, it is preferable that the diameters of the holes after the second filtering are the same as or larger than the diameters of the holes after the first filtering. Further, first filters having different hole diameters within the above-described range may be combined. The pore diameter here can refer to the nominal value of the filter manufacturer. Commercially available filters can be selected from various filters provided by, for example, Nippon Pall Co., Advantech Toyo Co., Ltd., Nippon Integris Co., Ltd. (former Nippon Microlith Co., Ltd.), Kitz Microfilter Co., Ltd., and the like.
As the second filter, a filter formed of the same material or the like as the first filter described above can be used. The pore size of the second filter is suitably about 0.01 to 1.0 μm, and preferably about 0.1 to 0.5 μm. By setting the content in this range, when the component particles are contained in the liquid, the foreign matter mixed in the liquid can be removed while the component particles remain.
For example, only a part of the components of the treatment liquid to be finally prepared is mixed in advance to prepare a mixed liquid, and the mixed liquid is subjected to filtering by the first filter, and then filtered by the first filter. The remaining components for constituting the treatment liquid may be added to the mixed liquid after the filtering, and the second filtering may be performed on the mixed liquid.

<Metal concentration>
The treatment liquid of the present invention has an ion concentration of a metal (a metal element of Na, K, Ca, Cu, Mg, Mn, Li, Al, Cr, Ni, Fe, Co, and Zn) contained as an impurity in the liquid. Is preferably 5 ppm or less (preferably 1 ppm or less). Particularly, in the production of the most advanced semiconductor devices, since it is assumed that a processing solution with higher purity is required, the metal concentration may be lower than the ppm order, that is, ppb order or less. More preferably, it is more preferably on the order of ppt (all the above concentrations are based on mass), and it is particularly preferable that the concentration is substantially not contained.

As a method for reducing the metal concentration, for example, a distillation and / or ion exchange resin is used in at least one of a stage of a raw material used in producing a treatment solution and a stage after preparing the treatment solution. To perform sufficient filtration.
As another method of reducing the metal concentration, the elution of impurities as described in the section on the container that contains the processing solution for the “container” that contains the raw materials used in the production of the processing solution Use of a small number of containers can be mentioned. In addition, a method of lining the inner wall of the pipe with a fluororesin so as to prevent metal components from being eluted from the “pipe” at the time of preparing the treatment liquid may also be used.

<Impurities and coarse particles>
The treatment liquid of the present invention preferably has a small amount of impurities such as metals in the liquid in view of its intended use. In particular, the Na, K, and Ca ion concentrations in the liquid are more preferably in the range of 5 ppm or less (by mass).
Further, it is preferable that the processing liquid does not substantially contain coarse particles.
Note that the coarse particles contained in the treatment liquid are particles such as dust, dust, organic solids, and inorganic solids contained as impurities in the raw material, and dust and dust brought as contaminants during preparation of the treatment liquid. , Organic solids, inorganic solids, and the like, and those that are not dissolved in the treatment liquid but exist as particles. The amount of coarse particles present in the treatment liquid can be measured in the liquid phase using a commercially available measuring device in a light scattering type liquid-in-liquid particle measurement method using a laser as a light source.

〔Processing method〕
The use of the processing liquid and the object to be processed using the processing liquid of the present invention are not particularly limited. It can be preferably used for cleaning and removing the dry etching residue or dry ashing residue adhered thereon.
That is, the processing liquid of the present invention can be suitably applied to a stripping liquid, a cleaning liquid, a rinsing liquid, and the like.

<Substrate>
The substrate in the object to be processed is not particularly limited, and examples include a silicon substrate (Si substrate), a silicon oxide substrate (SiO substrate), and a silicon nitride substrate (SiN substrate). Further, the substrate may include not only the wafer but also the entire substrate structure on which a circuit structure is provided. In particular, the treatment liquid of the present invention is preferably applied to a substrate having a circuit structure because the treatment liquid of the present invention suppresses corrosiveness to a metal material (for example, an electrode material) such as an electrode or a wiring disposed on the substrate. it can.
Although the wafer size of the substrate is not particularly limited, a substrate having a diameter of 8 inches, 12 inches, or 14 inches can be suitably used (1 inch = 25.4 mm).
Hereinafter, embodiments in which the treatment liquid of the present invention is applied to each of the above uses will be described.

[Permanent film removal method, resist removal method]
(Permanent film removal method)
The method for removing a permanent film using the processing liquid of the present invention may include a step of applying the processing liquid to the substrate provided with the permanent film. As a result, the processing liquid described above permeates into the inside of the permanent film and the interface between the permanent film and the substrate, and the permanent film can be peeled and removed.

The method for applying the treatment liquid in the method for removing the permanent film is not particularly limited. There is a method in which the treatment liquid is ejected from the ejection port of the ejection mechanism or jetted (sprayed) from the ejection port of the ejection mechanism, and the processing liquid is brought into contact with the permanent film or the substrate.
Specifically, the processing liquid introduced into the introduction port of the apparatus reaches the discharge port via a flow path connected to the introduction port, is discharged from the discharge port, and is processed in a processing container (for example, a processing container). Adheres to the substrate placed in the tank. The flow path may have a path for reusing the processing liquid. The substrate may be placed on a rotary table having a rotary drive unit, and may be rotated together with the rotary table when or after the processing liquid is applied.

It is preferable to use a single-wafer apparatus for applying the treatment liquid of the present invention. Specifically, the single wafer processing apparatus has a processing tank. In the processing tank, processing such as transport and rotation of the substrate, supply of the processing liquid, and the like are performed. Thereby, it is preferable that the substrate is brought into contact with the above-mentioned processing liquid in the processing tank, and the processing liquid is applied to the substrate (discharge, ejection, falling, dropping, etc.).
Advantages of using the above-described single-wafer apparatus include a good reproducibility because a fresh processing liquid is always supplied, and a high uniform in-plane processing property.
The single-wafer apparatus preferably includes a nozzle in the treatment tank. As a method of applying the processing liquid to the substrate, there is a method of discharging the processing liquid while swinging the nozzle in the surface direction of the substrate, and applying the processing liquid to the substrate. Use of this method is preferable in that the deterioration of the processing liquid can be prevented.

The processing temperature in the method for removing a permanent film is preferably 40 ° C. or higher, more preferably 50 ° C. or higher, even more preferably 60 ° C. or higher. The upper limit is preferably 100 ° C or lower, more preferably 90 ° C or lower.
The processing temperature is measured under the following conditions in the single-wafer apparatus. A radiation thermometer IT-550F (trade name) manufactured by HORIBA, Ltd. is fixed at a height of 30 cm above the wafer in the single wafer processing apparatus. A thermometer is pointed on the wafer surface 2 cm outside the center of the wafer, and the temperature is measured while flowing the processing liquid. The temperature is digitally output from the radiation thermometer and recorded continuously by a personal computer. Among these, the value obtained by averaging the temperatures for 10 seconds at which the temperature is stabilized is defined as the temperature on the wafer. When the storage temperature or the batch processing is used, the temperature in the tank can be maintained and set for a predetermined time (for example, one minute) until the temperature is stabilized. In the case of management by the circulation system, the temperature may be maintained and set until the temperature in the circulation flow path is stabilized for a predetermined time (for example, one minute).

The supply rate of the processing liquid when using a single-wafer apparatus is not particularly limited, but is preferably 0.05 to 5 L / min, and more preferably 0.1 to 3 L / min. The use of the above range is preferable in that the uniformity in the plane of the processing target can be more favorably secured and stable performance can be secured during continuous processing.
When the substrate is rotated, it is preferable to rotate the substrate at 50 to 1000 rpm from the same viewpoint as above, though it depends on the size and the like.
The moving speed at which the discharge port (nozzle) is moved is not particularly limited, but is preferably 0.1 cm / s or more, and more preferably 1 cm / s or more. The upper limit is preferably 30 cm / s or less, more preferably 15 cm / s or less. The movement trajectory line may be a straight line or a curve (for example, an arc shape). In any case, the movement speed can be calculated from the actual distance of the trajectory line and the time spent for the movement. The time required for processing one substrate is preferably in the range of 10 to 1200 seconds.

As a method of applying the treatment liquid in the above-described method of removing the permanent film, a method using a single-wafer apparatus has been exemplified. However, the present invention is not limited to this.
As a specific example of such an immersion method, there is a method in which a substrate provided with a permanent film is immersed in a processing liquid in a processing tank, and the substrate is brought into contact with the processing liquid in the processing tank. The temperature of the processing liquid when the substrate is immersed is as shown in the processing temperature in the above-described method of removing the permanent film. In addition, other conditions (for example, time for immersing the substrate) can be appropriately set, and are not particularly limited.

  Examples of the permanent film include a finely processed color filter, a transparent insulating film, a resin lens, and the like, which are applied to the manufacture of a solid-state imaging device and an image display device. These materials are not particularly limited, and known materials can be used.

The above-described method for removing a permanent film can be applied after manufacturing a semiconductor substrate product. That is, for example, when there is a defect or the like in the permanent film already formed on the semiconductor substrate product, the permanent film can be removed from the semiconductor substrate product and the substrate can be reused.
Here, the term “semiconductor substrate product” is a general term for a product including a semiconductor element obtained through a process such as a lithography process using the above substrate.
Unlike a resist that is removed after an etching step in the manufacture of a semiconductor substrate product, such a permanent film remains undissolved by development and is not expected to be removed after processing. It is expected to be difficult. However, the use of the treatment liquid of the present invention makes it possible to remove the permanent film satisfactorily.

  In addition, the treatment liquid of the present invention can be suitably used for removing a color filter described in, for example, WO2015 / 115538 and JP-A-2015-31800.

(Resist removal method)
Furthermore, the treatment liquid of the present invention can be applied not only to the removal of a permanent film formed on a substrate, but also to the removal and removal of various resists used as masks during etching in the manufacture of semiconductor substrate products. . That is, it can be used as a stripping and removing solution for removing a resist dissolved by a process such as development and the residue. The removal and removal of the various resists can be carried out in the same manner as for the permanent film. The material of the photoresist is not particularly limited, and a known material can be used.

When the treatment liquid of the present invention is applied to the peeling of a permanent film and an organic film such as a resist, the composition is not particularly limited,
water and,
A hydrophilic organic solvent,
A quaternary ammonium salt;
0.001 mass ppt to 1 mass ppm of inorganic anions with respect to the total mass of the treatment liquid,
Furthermore, it is preferable that at least one of the following aspects selected from (1) to (3) is used.

(1) The treatment liquid further contains at least one selected from a corrosion inhibitor and an amine compound.
(2) The hydrophilic organic solvent includes an aprotic polar solvent or a sulfone-based solvent.
(3) The treatment liquid further contains a surfactant.

  When the treatment liquid of the present invention is applied to peeling of a permanent film and an organic film such as a resist, the treatment liquid may be an aqueous treatment liquid or an organic solvent treatment liquid. When the permanent film is a film of an organic compound, it is preferable to use an organic solvent-based treatment liquid.

As the corrosion inhibitor, amine compound, and sulfone-based solvent, those described above can be used.
Examples of the aprotic polar organic solvent include dimethyl sulfoxide (hereinafter abbreviated as DMSO), sulfolane, dimethyl sulfone, N, N-dimethylformamide (DMF), N, N-dimethylacetamide, N, N-diethylacetamide, N-methyl -2-pyrrolidone (hereinafter abbreviated as NMP), N-vinyl-2-pyrrolidone, ε-caprolactam, 1,3-dimethyl-2-imidazolidinone, tetramethylurea, hexamethylphosphoric triamide, γ-butyrolactone, δ Valerolactone, ε-caprolactone, acetonitrile, pyridine, dimethoxyethane, diglyme, triglyme, ethylene carbonate, propylene carbonate and the like. Among these, DMSO and NMP are preferable in terms of peelability and permeability, and DMSO is more preferable. When the treatment liquid contains dimethyl sulfoxide, the removability of the resist formed in contact with the hydrophobic resist and the hydrophobic material becomes more excellent, and the damage to the electrode can be further suppressed. These aprotic polar organic solvents may be used alone or in combination of two or more.

As the surfactant, nonionic, anionic, cationic surfactants and amphoteric surfactants can be used. The content of the surfactant is preferably 0.0001 to 5% by mass, and more preferably 0.0001 to 1% by mass. These surfactants may be used alone or in combination.
As nonionic surfactants, for example, polyalkylene oxide alkyl phenyl ether surfactants, polyalkylene oxide alkyl ether surfactants, block polymer surfactants composed of polyethylene oxide and polypropylene oxide, polyoxyalkylene distyrene Phenyl ether-based surfactants, polyalkylene tribenzyl phenyl ether-based surfactants, and acetylene polyalkylene oxide-based surfactants.
Examples of anionic surfactants include alkyl sulfates, alkyl sulfonic acids, alkyl benzene sulfonic acids, alkyl naphthalene sulfonic acids, alkyl diphenyl ether sulfonic acids, polyoxyethylene alkyl ether carboxylic acids, polyoxyethylene alkyl ether acetic acids, and polyoxyethylene alkyl ethers. And propionic acid and their salts.
Examples of the cationic surfactant include a quaternary ammonium salt-based surfactant and an alkylpyridium-based surfactant.
Examples of the amphoteric surfactant include a betaine surfactant, an amino acid surfactant, an imidazoline surfactant, and an amine oxide surfactant.

(Process target with permanent film or resist film)
Hereinafter, a permanent film and a resist film, which are preferable as a processing target of the above-described processing liquid of the present invention, and a substrate on which each of the above films is disposed will be described in detail.

(substrate)
In the removal of the permanent film and the removal of the resist using the processing liquid of the present invention, the above-described substrate can be used as the substrate on which the resist is disposed.

(Resist)
In removing and removing the resist using the treatment liquid of the present invention, the resist film to be treated is not particularly limited, and examples thereof include a positive type, a negative type, and a positive / negative type photoresist.
Specific examples of the positive resist include (meth) acrylate resin, vinyl cinnamate, cyclized polyisobutylene, azo-novolak resin, and diazoketone-novolak resin, as well as novolak resin and polyhydroxystyrene. At least one of the resins is exemplified.
Specific examples of the negative resist include an azide-cyclized polyisoprene type, an azide-phenol resin type, and a chloromethyl polystyrene type. Further, specific examples of the positive / negative resist include poly (p-butoxycarbonyloxystyrene).
Other examples of resists for patterning are disclosed in Japanese Patent Nos. 5,222,804, 5,244,740, 5,244,933, 5,286,236, 5,210,755, 5,277,128, 5,303,604, 5,216,892, 5,531,139, 5,553,078, and 5,155,803. Can be referred to and incorporated herein by reference.

(Permanent film (for example, color filter))
In the method for removing a permanent film using the processing solution of the present invention, the permanent film to be processed is not particularly limited, and examples thereof include a resist for a color filter (hereinafter, also referred to as a “color resist”). Hereinafter, the color resist to which the processing solution of the present invention can be preferably applied will be described in detail.

  Here, the color filter includes components such as coloring materials that are not included in a normal resist, and it is expected that it will be difficult to remove them. However, although the details of this reason have not been clarified, the treatment liquid of the present invention exerts its effect in removing the color filter. Therefore, the treatment liquid of the present invention is particularly suitable for removing a color filter among permanent films.

Specifically, RGB 5000 series / 6000 series (trade name) and CMY 3000 series (trade name) manufactured by FUJIFILM Corporation can be suitably used as the color resist. In addition, Japanese Patent No. 5274680, Japanese Patent No. 5283747, Japanese Patent No. 05334624, Japanese Patent No. 05339781, Japanese Patent No. 05340102, Japanese Patent No. 053444843, Japanese Patent No. Reference can be made to those disclosed in Japanese Patent Nos. 5448352 and 5448416, which are incorporated herein by reference.
Hereinafter, a forming material and a forming method of the color filter will be described in detail with reference to an example.

  Each pixel of the color filter can be formed by curing the following colored curable resin composition. Examples of the colored curable resin composition include those containing an alkali-soluble resin, a polymerizable compound, a polymerization initiator, and a colorant.

-Alkali-soluble resin As the alkali-soluble resin, those having at least one group that promotes alkali solubility in the molecule are preferable. From the viewpoint of heat resistance, a polyhydroxystyrene resin, a polysiloxane resin, an acrylic resin, an acrylamide resin, or an acrylic / acrylamide copolymer resin is preferable. From the viewpoint of developing property control, an acrylic resin, an acrylamide resin, or an acryl / acrylamide copolymer resin is preferable. Examples of the group that promotes alkali solubility (hereinafter also referred to as an acidic group) include a carboxy group, a phosphoric acid group, a sulfonic acid group, and a phenolic hydroxyl group. Those which are soluble in a solvent and can be developed with a weak alkaline aqueous solution are preferred, and (meth) acrylic acid is particularly preferred. These acidic groups may be used alone or in combination of two or more.
As the alkali-soluble resin, a polymer having a carboxy group in a main chain or a side chain is preferable. Specifically, such as methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, and novolak resin In addition to alkali-soluble phenolic resins and the like, examples thereof include acidic cellulose derivatives having a carboxylic acid in a side chain, and polymers obtained by adding an acid anhydride to a polymer having a hydroxyl group. In particular, a copolymer of (meth) acrylic acid and another monomer copolymerizable therewith is suitable. Other monomers copolymerizable with (meth) acrylic acid include alkyl (meth) acrylate, aryl (meth) acrylate, and vinyl compounds. Examples of the alkyl (meth) acrylate and the aryl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, and (iso) pentyl. (Meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) A) acrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, and the like. Examples of the vinyl compound include styrene, α-methylstyrene, vinyltoluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, tetrahydrofurfuryl methacrylate, polystyrene macromonomer, polymethyl methacrylate macromonomer and the like. Examples of the N-substituted maleimide monomer described in JP-A-10-300922 include N-phenylmaleimide and N-cyclohexylmaleimide.
The alkali-soluble resin also preferably has a polymerizable group. Examples of the polymerizable group include an ethylenically unsaturated bond group. Specifically, a (meth) acryloyl group or a vinyl group is preferable, and a (meth) acryloyl group is more preferable. The acrylic polymer is preferably a vinyl polymer having a repeating unit derived from at least one of (meth) acrylic acid, (meth) acrylic acid ester, and (meth) acrylamide.

  The synthesis of the polymerizable alkali-soluble resin can be performed based on the synthesis method described in paragraphs 0027 to 0057 of JP-A-2003-262958. Of these, the synthesis method 1 in the publication is preferred. As the exemplified compounds, the compounds described in paragraphs 0058 to 0061 of JP-A-2003-262958 can be referred to, and are incorporated herein. Specific examples of the compound include the following compound (resin P-1) (weight average molecular weight: 14000).

  The alkali-soluble resin is also preferably a polymer represented by the following formula.

L ^X1 represents a single bond or a linking group. Examples of the linking group include the linking group L described above. Among them, a single bond is preferred.
R ^{X1, R Y1} is a hydrogen atom, a methyl group, an ethyl group, a propyl group, or a cyano group, a hydrogen atom or a methyl group is preferable.
^RA is an acidic group. Preferred examples are as defined above.
R ^Y2 represents a substituent, among which an alkyl group (preferably having 1 to 12 carbon atoms, more preferably having 1 to 6 carbon atoms, and particularly preferably having 1 to 3 carbon atoms), and an aryl group (having 6 to 22 carbon atoms). Preferably, it has 6-14 carbon atoms, more preferably 6-10 carbon atoms, and an aralkyl group (7-23 carbon atoms are preferable, 7-15 carbon atoms are more preferable, and 7-11 carbon atoms are particularly preferable). Is preferred. These groups may further have a substituent, and examples of the further substituent include a hydroxyl group and a carboxy group.
nx and ny are mole fractions, and nx + ny may be less than 1 (meaning that it may have another repeating unit), and is preferably 1. The lower limit of nx is preferably 0.05 or more, more preferably 0.1 or more, and even more preferably 0.2 or more. As a maximum, 0.7 or less is preferred, 0.6 or less is more preferred, and 0.5 or less is still more preferred. The lower limit of ny is preferably 0.3 or more, more preferably 0.4 or more, and still more preferably 0.6 or more. The upper limit is preferably 0.9 or less, more preferably 0.8 or less.

  The alkali-soluble resin is preferably soluble in an aqueous solution of tetramethylammonium hydroxide (TMAH) having a concentration of 0.1% by mass or more at 23 ° C. Furthermore, it is preferable that it is soluble in 1% by mass or more of TMAH aqueous solution, and it is further preferable that it is soluble in 2% by mass or more of TMAH aqueous solution.

The acid value of the alkali-soluble resin is preferably 30 to 200 mgKOH / g, and more preferably 70 to 120 mgKOH / g. With such a range, the development residue in the unexposed portion can be effectively reduced.
The weight average molecular weight (Mw) of the alkali-soluble resin is preferably from 2,000 to 50,000, particularly preferably from 7000 to 20,000.
The content of the alkali-soluble resin is preferably from 10 to 50% by mass, more preferably from 15 to 40% by mass, and particularly preferably from 20 to 35% by mass, based on the total solid content of the colored curable resin composition. It is.
The alkali-soluble resin may be used alone or in combination of two or more.

-Polymerizable compound The polymerizable compound may be any compound having a polymerizable group in the molecule, and among them, a monomer having an ethylenically unsaturated double bond (hereinafter, sometimes referred to as "specific monomer") is preferable. . The specific monomer is preferably a polyfunctional monomer.
The specific monomer may be used alone or in combination of two or more.
The specific monomer is preferably a (meth) acrylate monomer. As these specific compounds, the compounds described in paragraphs 0095 to 0108 of JP-A-2009-288705 can be suitably used in the present embodiment. The specific monomer is preferably one represented by the following formulas (MO-1) to (MO-6).

  In the formula, n is each 0 to 14, and m is each 1 to 8. A plurality of R, T and Z present in one molecule may be the same or different. When T is an oxyalkylene group, the terminal on the carbon atom side is bonded to R. At least one of R is a polymerizable group.

n is preferably from 0 to 5, and more preferably from 1 to 3.
m is preferably 1 to 5, and more preferably 1 to 3.
As specific examples of the polymerizable compound represented by the above formulas (MO-1) to (MO-6), compounds described in paragraphs 0248 to 0251 of JP-A-2007-269779 are described in the present embodiment. Can also be suitably used.

Among them, as the polymerizable compound, dipentaerythritol triacrylate (KAYARAD D-330 as a commercial product; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (KAYARAD D-320 as a commercial product, Nippon Kayaku Co., Ltd.) Company), dipentaerythritol penta (meth) acrylate (commercially available KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (commercially available KAYARAD DPHA; Nippon Kayaku stock) In addition to the structure in which these (meth) acryloyl groups are via an ethylene glycol or propylene glycol residue, diglycerin EO (ethylene oxide) -modified (meth) acrylate (M-460 as a commercial product; Toa Gosei ) Is preferable. These oligomer types can also be used.
The molecular weight of the polymerizable compound is not particularly limited, but is preferably 300 or more and 1500 or less, and more preferably 400 or more and 700 or less.
The content of the polymerizable compound is preferably in the range of 1 to 50% by mass, more preferably in the range of 3 to 40% by mass, and more preferably 5 to 30% by mass with respect to the total solid content in the composition. % Is more preferable. Within this range, the curability is good and preferable without excessively lowering the refractive index and the transparency. As the polymerizable compound, one kind may be used alone, or two or more kinds may be used in combination.

-Polymerization initiator The polymerization initiator may be a thermal polymerization initiator or a photopolymerization initiator, but a photopolymerization initiator is preferred. For example, organic halide compounds, oxydiazole compounds, carbonyl compounds, ketal compounds, benzoin compounds, acridine compounds, organic peroxide compounds, azo compounds, coumarin compounds, azide compounds, metallocene compounds, hexaarylbiimidazole compounds, organic boric acids Compound, disulfonic acid compound, oxime compound, onium salt compound, hydroxyacetophenone compound, aminoacetophenone compound, acylphosphine oxide compound, trihalomethyltriazine compound, benzyldimethyl ketal compound, α-hydroxyketone compound, α-aminoketone compound, acylphosphine compound , Phosphine oxide compound, metallocene compound, triallylimidazole dimer, onium compound, benzothiazole compound, benzo Examples include a phenone compound, a cyclopentadiene-benzene-iron complex compound, a halomethyloxadiazole compound, a 3-aryl-substituted coumarin compound, an α-aminoalkylphenone compound, and a benzoate compound.
As specific examples thereof, the description after paragraph [0135] of JP-A-2010-106268 ([0163] of the corresponding US Patent Application Publication No. 2011/0124824) can be referred to, and the contents thereof are described in the specification of the present application. Will be incorporated into the book.

  Among the above, it is preferable to use an oxime compound as the polymerization initiator. Among them, commercially available products such as IRGACURE OXE01 (the following formula) and IRGACURE OXE02 (the following formula) (all manufactured by BASF) can be suitably used.

The polymerization initiator is preferably in the range of 0.1 to 20% by mass, more preferably in the range of 0.5 to 10% by mass, and particularly preferably in the range of 1 to 8% by mass, based on the solid content of the colored curable resin composition. Range.
Two or more polymerization initiators may be used in combination as needed.

-Colorant The colorant is not particularly limited, and various dyes and pigments can be used. For example, chromatic colorants (chromatic colorants) such as red, magenta, yellow, blue, cyan, and green which form color pixels of a color filter, and black commonly used for forming a black matrix Any of the system-based coloring agents (black coloring agents) can be used. In the present embodiment, the colorant is preferably at least one selected from red, magenta, yellow, blue, cyan, and green.
Examples of the inorganic pigment include metal compounds represented by metal oxides, metal complex salts, and the like.Specifically, iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, Metal oxides such as silver, and composite oxides of the above metals can be given. Titanium nitride, silver tin compounds, silver compounds, and the like can also be used.
As organic pigments, perylene pigments, perinone pigments, quinacridone pigments, quinacridonequinone pigments, anthraquinone pigments, anthantrone pigments, benzimidazolone pigments, disazo pigments, azo pigments, indanthrone pigments, phthalocyanine pigments, triarylcarbonium pigments, dioxazines Pigment, aminoanthraquinone pigment, diketopyrrolopyrrole pigment, indigo pigment, thioindigo pigment, isoindoline pigment, isoindolinone pigment, pyranthrone pigment, and isobiolanthrone pigment.
Examples of dyes include triarylmethane, pyrazoleazo, anilinoazo, triphenylmethane, anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazoleazo, pyridoneazo, cyanine, and phenothiazine dyes. And azomethine, pyrrolopyrazole azomethine, xathene, phthalocyanine, benzopyran, indigo, and pyromethene dyes. Further, a multimer of these dyes may be used.

When the colorant is in the form of particles, the average primary particle diameter is preferably 5 nm or more, particularly preferably 30 nm or more. The upper limit is preferably 1 μm or less, more preferably 500 nm or less, and particularly preferably 100 nm or less.
The particle diameter is measured using a dynamic light scattering particle size distribution analyzer (Nikkiso Nanotrack (Nanotrac) Wave-EX150 [trade name], Horiba Seisakusho LB-500 [trade name]). Do it. The procedure is as follows. The sample dispersion is taken in a 20 ml sample bottle, and diluted with an insoluble solvent (eg, water) so that the solid component concentration becomes 0.2% by mass. Data acquisition was performed 50 times at a temperature of 25 ° C. using a 2 ml measurement quartz cell, and the “number average” obtained was defined as an average particle diameter. For other detailed conditions and the like, the description of JISZ8828: 2013 “Particle size analysis-dynamic light scattering method” can be referred to as necessary.

  The content of the coloring agent is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 30% by mass or more in the solid content of the colored curable resin composition. The upper limit is not particularly limited, but is preferably 80% by mass or less, more preferably 60% by mass or less. According to the treatment liquid of the present invention, even if the colorant is contained in such a large amount, the color resist can be sufficiently removed.

-Dispersant The colored curable resin composition may contain a dispersant. Examples of the dispersant include polymer dispersants (for example, polyamidoamine and salts thereof, polycarboxylic acids and salts thereof, high-molecular-weight unsaturated acid esters, modified polyurethanes, modified polyesters, modified poly (meth) acrylates, (meth) acrylic-based Copolymer, and naphthalenesulfonic acid formalin condensate), polyoxyethylene alkyl phosphate, polyoxyethylene alkylamine, alkanolamine, and pigment dispersant.
The polymer dispersant can be further classified into a linear polymer, a terminal-modified polymer, a graft polymer, and a block polymer based on its structure.
Specific examples of the pigment dispersant include “Disperbyk-101 (polyamideamine phosphate), 107 (carboxylate), 110 (copolymer containing an acid group), 130 (polyamide), 161 and 162 manufactured by BYK Chemie. , 163, 164, 165, 166, 170 (high molecular weight copolymer), "BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid), BYK2001", "EFKA4047, 4050, 4010, 4165 (EFKA)" Polyurethane), EFKA4330, 4340 (block copolymer), 4400, 4402 (modified polyacrylate), 5010 (polyesteramide), 5765 (high molecular weight polycarboxylate), 6220 (fatty acid polyester), 6745 (phthalocyanine derivative) , 6750 (azo Pigment derivative) "," Ajispar PB821, PB822 "manufactured by Ajinomoto Fantechno," Floren TG-710 (urethane oligomer) "manufactured by Kyoeisha Chemical Co., Ltd.," Polyflow No. 50E, No. 300 (acrylic copolymer) ", "Dispalon KS-860, 873SN, 874, # 2150 (aliphatic polycarboxylic acid), # 7004 (polyetherester), DA-703-50, DA-705, DA-725" manufactured by Kusumoto Kasei, Kaosha “Demol RN, N (naphthalenesulfonic acid formalin polycondensate), MS, C, SN-B (aromatic sulfonic acid formalin polycondensate)”, “Homogenol L-18 (polymer polycarboxylic acid)”, Emulgen 920, 930, 935, 985 (polyoxyethylene nonylphenyl ether) "," Acetami 86 (stearylamine acetate) ", manufactured by Lubrizol Corporation" Solsperse 5000 (phthalocyanine derivative), 22000 (azo pigment derivative), 13240 (polyesteramine), 3000, 17000, 27000 (polymer having a functional part at the terminal), 24000, 28000, 32000, 38500 (graft type polymer) "and" Nikkor T106 (polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate) "manufactured by Nikko Chemical Co., Ltd.

The concentration of the dispersant is preferably from 1 to 100 parts by mass, more preferably from 3 to 100 parts by mass, even more preferably from 5 to 80 parts by mass, per 1 part by mass of the colorant. Moreover, it is preferable that it is 5-30 mass% with respect to the total solid content of a coloring curable resin composition.
The dispersants may be used alone or in combination of two or more.

-Surfactant From the viewpoint of further improving coatability, various surfactants may be added to the colored curable resin composition. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used.
When the surfactant is contained, the content thereof is preferably in the range of 1 to 40% by mass, more preferably 5 to 20% by mass, based on the total mass of the solid content of the colored curable resin composition.

  The colored curable resin composition may contain other components as appropriate. Examples of other components include an organic solvent, an ultraviolet absorber, an adhesion improver, a sensitizing dye, a co-sensitizer, a diluent, a plasticizer, and a sensitizer.

-Formation of color filter The preparation of the colored curable resin composition and the formation of the cured film thereof may be performed according to a general method. In the following, the example of forming a color filter using the colored curable resin composition Will be described in more detail.
As a support for forming a color filter, for example, an imaging element (light receiving element) such as a CCD (Charge Coupled Device) and a CMOS (Complementary Metal-Oxide Semiconductor) is provided on a substrate (for example, a silicon substrate). The above-described substrate such as a substrate for a solid-state imaging device can be used.
The colored pattern may be formed on the imaging element forming surface side (front surface) of the solid-state imaging device substrate, or may be formed on the imaging element non-forming surface side (back surface).
A light-shielding film may be provided between each image sensor in the substrate for a solid-state image sensor and on the back surface of the substrate for a solid-state image sensor. Further, an undercoat layer may be partially provided on the support for improving adhesion to an upper layer, preventing diffusion of a substance, or flattening the substrate surface. By forming a color filter on both the portion where the undercoat layer is provided and the portion where the undercoat layer is not provided, the color filter on the hydrophilic layer and the color filter on the hydrophobic layer coexist on one substrate. Can be done.
Here, an overcoat layer described below can be used as the undercoat layer.
As a method of applying the colored curable resin composition onto the support, various coating methods such as slit coating, ink jet method, spin coating, casting coating, roll coating, and screen printing can be applied.

  Drying (prebaking) of the colored curable resin composition layer applied on the support can be performed at a temperature of 50 ° C to 140 ° C for 10 seconds to 300 seconds using a hot plate, an oven, or the like.

In the exposing step, the colored curable resin composition layer formed in the colored curable resin composition layer forming step is subjected to pattern exposure through a mask having a predetermined mask pattern using, for example, an exposure apparatus such as a stepper. As the radiation (light) that can be used at the time of exposure, ultraviolet rays such as g-line and i-line are particularly preferable (i-line is particularly preferable). Irradiation dose (exposure dose) is preferably 30~1500mJ / cm ^2, more preferably 50~1000mJ / cm ^2, more preferably 80~500mJ / cm ^2.

Then, by performing development such as an alkali development treatment, the colored curable resin composition in the non-light-irradiated portion in the exposure step elutes in the aqueous alkali solution, leaving only the photocured portion. As the developing solution, an organic alkali developing solution which does not easily cause damage to the underlying imaging element and circuit is desirable. The development temperature is usually from 20C to 30C, and the development time is, for example, from 20 seconds to 90 seconds. In order to remove the residue more, it may be performed for 120 seconds to 180 seconds in recent years. Further, in order to further improve the residue removal property, the step of shaking off the developer every 60 seconds and supplying a new developer may be repeated several times.
As a method and a material of a color filter that can be preferably applied in the present invention, JP-A-2014-199272, JP-A-2013-064999, JP-A-2013-064998, JP-A-2013-064993, and JP-A-2013-054081. JP-A-2013-040240, JP-A-2012-136669, JP-A-2012-012498, JP-A-2011-252046, JP-A-2011-252045, JP-A-2011-252044, JP-A-2011-162781, JP-A-2011-144299, JP-A-2011-144298, JP-A-2011-127044, JP-A-2011-127043, JP-A-2011-084726, JP-A-2010-2444028, JP-A-2010-159409, Open 2010-1559 3, JP-A-2010-085979, JP-A-2010-084135, JP-A-2009-244320, JP-A-2006-058821, and JP-A-2004-117856, and the like. Quote in the book.

  Next, it is preferable to perform heat treatment (post bake) after drying. At this time, it is preferable to form a multicolored pattern, and a cured film can be manufactured by sequentially repeating the above steps for each color. Thereby, a color filter is obtained. Post baking is a heat treatment after development to complete the curing. The heating temperature is preferably 250 ° C. or lower, more preferably 240 ° C. or lower, further preferably 230 ° C. or lower, and particularly preferably 220 ° C. or lower. Although there is no particular lower limit, it is preferable to perform a thermosetting treatment at 50 ° C. or more, more preferably 100 ° C. or more, in consideration of efficient and effective treatment. Instead of the post-baking by heating, the pixels of the color filter may be cured by UV (ultraviolet) irradiation.

The thickness of the cured film (color filter) is preferably 0.05 μm or more, more preferably 0.1 μm or more, and particularly preferably 0.5 μm or more. As a maximum, 10 micrometers or less are preferred, 5 micrometers or less are more preferred, 4 micrometers or less are still more preferred, and 3 micrometers or less are still more preferred.
The size (pattern width) of the colored pattern (colored pixel) is preferably 5 μm or less, more preferably 4 μm or less, and particularly preferably 3 μm or less. As a lower limit, 0.1 μm or more is practical.
Such a film thickness and size are generally used as a color filter. According to the treatment liquid of the present invention, a sufficient removal effect can be obtained even for the above-described color filter.

-Overcoat layer In the case where the above color filter is used as a permanent film, a step of forming an overcoat layer on a substrate (support) may be provided before the step of forming the colored curable resin composition layer. .
For the formation of the overcoat layer, for example, International Publication No. 2010/010899, Japanese Patent No. 4269480, Japanese Patent Application Laid-Open No. 2005-227525, Japanese Patent Application Laid-Open No. 2000-250217, Japanese Patent Application Laid-Open No. 9-221602, and It can be carried out using an epoxy-based radiation-sensitive resin composition (composition for forming an overcoat) based on JP-A-2001-343748.
Hereinafter, specific examples of the step of forming the overcoat layer will be described.

First, an epoxy-based radiation-sensitive resin composition is applied to the surface of the substrate, and prebaked to remove the solvent, thereby forming a film.
As a method for applying the composition solution, for example, an appropriate method such as a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, a bar coating method, and an inkjet method can be adopted. However, spin coating or slit die coating is particularly preferred.
The prebaking conditions vary depending on the type of each component, the mixing ratio, and the like, but are usually at 80 to 120 ° C for about 1 to 15 minutes.
It is preferable to use a silicon nitride substrate as the substrate.

Next, the prebaked film is exposed to light through a mask having a predetermined pattern to be polymerized, and then developed with a developer to remove unnecessary portions to form a pattern.
As radiation used for exposure, radiation such as visible light, ultraviolet light, far ultraviolet light, charged particle beam, and X-ray can be appropriately selected and used, and radiation having a wavelength in the range of 190 to 450 nm. Is preferred.
As the developing method, for example, any of a liquid puddle method, an immersion method, a shower method, and the like may be used. The development time is usually about 30 to 180 seconds at room temperature.
Examples of the developer include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and ammonia; primary amines such as ethylamine and n-propylamine; diethylamine; And tertiary amines such as trimethylamine, methyldiethylamine, ethyldimethylamine and triethylamine; tertiary alkanolamines such as dimethylethanolamine, methyldiethanolamine and triethanolamine Pyrrole, piperidine, N-methylpiperidine, N-methylpyrrolidine, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [4.3.0] -5-nonene and the like; Alicyclic tertiary amines; It is possible to use an aqueous solution (alkaline aqueous solution) of an alkaline compound such as aromatic tertiary amines such as gin, collidine, lutidine, and quinoline; and quaternary ammonium compounds such as tetramethylammonium hydroxide and tetraethylammonium hydroxide. it can.
In addition, an appropriate amount of a water-soluble organic solvent such as methanol and ethanol, and / or a surfactant may be added to the alkaline aqueous solution.
After the development, an unnecessary portion is removed, for example, by washing with running water for 30 to 90 seconds, for example, and then dried by blowing compressed air or compressed nitrogen to form a predetermined pattern.

  Thereafter, this pattern is heated by a heating device such as a hot plate and an oven at a predetermined temperature, for example, 150 to 250 ° C., for a predetermined time, for example, for 3 to 10 minutes on the hot plate, and for 30 to 90 minutes in the oven, for example. (Hereinafter, referred to as “post bake”), an overcoat layer can be obtained.

(How to regenerate the substrate)
As described above, the treatment liquid of the present invention is applied at the time of or after the manufacture of a semiconductor substrate product.
During or after the manufacture of a semiconductor substrate product, a portion (resist or permanent film) of the semiconductor substrate product that needs repair may be found. In this case, the substrate can be regenerated by removing the portion that needs to be repaired.
In other words, the method for regenerating a substrate according to the present invention comprises removing the permanent film or the resist film provided on the substrate with the treatment liquid of the present invention during or after the manufacture of the semiconductor substrate product, thereby removing the semiconductor substrate product from the semiconductor substrate product. The method includes a step of obtaining a substrate from which the permanent film or the resist film has been removed.

[Removal of residues]
Further, the treatment liquid of the present invention can be applied to cleaning and removal of a dry etching residue or a dry ashing residue attached to a substrate.
The cleaning and removing method using the processing liquid of the present invention includes a cleaning step of cleaning at least one of a dry etching residue and a dry ashing residue attached to a substrate with the processing liquid.

When the treatment liquid of the present invention is applied to cleaning and removal of residues, the composition is not particularly limited,
water and,
A hydrophilic organic solvent,
A quaternary ammonium salt;
0.001 mass ppt to 1 mass ppm of inorganic anions with respect to the total mass of the treatment liquid,
Furthermore, it is preferable that at least one of the following aspects selected from (1) to (3) is used.

(1) The treatment liquid further contains an amine compound.
(2) The treatment liquid further contains a corrosion inhibitor.
(3) The treatment liquid contains a water-soluble alcohol-based solvent as the hydrophilic organic solvent.

  When the treatment liquid of the present invention is applied to cleaning and removal of a residue, the treatment liquid may be an aqueous treatment liquid or an organic solvent treatment liquid. When the residue contains an organic substance, an organic solvent-based treatment liquid is preferably used.

  As the amine compound, the corrosion inhibitor, and the water-soluble alcohol-based solvent, those described above can be used.

The substrate to be cleaned in the cleaning step is not particularly limited as long as a dry etching residue and a dry ashing residue adhere thereto, and a known substrate such as a substrate including the above-described circuit structure can be processed. . The substrate to which the dry etching residue and the dry ashing residue adhere are specifically defined as a hole (for via), a pad pattern, a wiring, or the like provided through a dry etching process to form a metal film on the surface or inside. Is exposed.
The treatment liquid of the present invention can remove residues without corroding a metal film disposed on a substrate.

  The method of contacting the processing liquid with the substrate is not particularly limited, for example, a method of immersing the substrate in a processing liquid put in a tank, a method of spraying the processing liquid on the substrate, a method of flowing the processing liquid on the substrate, or Any combination thereof may be mentioned. From the viewpoint of residue removal, a method in which the substrate is immersed in the treatment liquid is preferable.

  The temperature of the treatment liquid is preferably 90 ° C. or lower, more preferably 25 to 80 ° C., further preferably 30 to 75 ° C., and particularly preferably 40 to 65 ° C.

The cleaning time can be adjusted according to the cleaning method used and the temperature of the processing solution.
In the case of cleaning by the immersion batch method (a batch method in which a plurality of objects to be cleaned are immersed and processed in a processing tank), the cleaning time is, for example, within 60 minutes, and preferably 1 to 60 minutes. , More preferably from 3 to 20 minutes, even more preferably from 4 to 15 minutes.

  In the case of single-wafer cleaning, the cleaning time is, for example, 10 seconds to 5 minutes, preferably 15 seconds to 4 minutes, more preferably 15 seconds to 3 minutes, and more preferably 20 seconds to 5 minutes. More preferably, it is 2 minutes.

Further, in order to further enhance the cleaning ability of the processing liquid, a mechanical stirring method may be performed.
Examples of the mechanical stirring method include a method of circulating the processing liquid on the substrate, a method of flowing or spraying the processing liquid on the substrate, and stirring by ultrasonic waves or megasonics.

In the case of single-wafer cleaning, the above-described single-wafer cleaning apparatus can be used. At that time, the supply rate of the processing liquid is preferably 0.05 to 5 L / min, more preferably 0.1 to 3 L / min. By setting the above numerical range, the effect of the present invention is more excellent. Further, stable performance can be ensured during continuous processing while ensuring better in-plane uniformity of the processing target.
When the chemical solution supply rate is 0.05 to 5 L / min, the content of the inorganic anion in the treatment liquid is desirably 1 mass ppt or more. When the chemical liquid supply speed increases, the frequency of the amount of the substance that comes into contact with the substrate also increases, and the liquid itself is easily charged. When the liquid is charged, the uniformity of the surface to be treated cannot be ensured (for example, the residue remains unevenly in the surface), which may result in a reduction in corrosion prevention. By including an inorganic anion of 1 mass ppt or more in the treatment liquid, charging of the liquid can be suppressed.

Further, after the cleaning step, the method may further include a step of rinsing the substrate with a solvent to clean the substrate.
The rinsing step is performed continuously from the cleaning step, and is preferably a rinsing step with a rinsing solvent for 5 seconds to 5 minutes. In the rinsing step, the mechanical stirring method described above may be performed.

Examples of the rinsing solvent include deionized (DI) water, methanol, ethanol, isopropyl alcohol, N-methylpyrrolidinone, γ-butyrolactone, dimethyl sulfoxide, ethyl lactate, and propylene glycol monomethyl ether acetate. However, the present invention is not limited to this. Alternatively, an aqueous rinsing solution having a pH> 8 (such as diluted aqueous ammonium hydroxide) may be used.
As the rinsing solvent, an aqueous solution of ammonium hydroxide, DI water, methanol, ethanol, or isopropyl alcohol is preferred, an aqueous solution of ammonium hydroxide, DI water, or isopropyl alcohol is more preferred, and an aqueous solution of ammonium hydroxide or DI water is even more preferred.
As a method of bringing the rinsing solvent into contact with the substrate, the above-described method of bringing the treatment liquid into contact with the substrate can be similarly applied.
The temperature of the rinsing solvent in the rinsing step is preferably 16 to 27 ° C.

After the rinsing step, a drying step of drying the substrate may be provided.
The drying method is not particularly limited. Examples of the drying method include spin drying, a method of flowing a dry gas over a substrate with a mask, a method of heating a substrate by a heating means such as a hot plate or an infrared lamp, Marangoni drying, Rotagoni drying, and IPA (isopropyl alcohol). ) Drying, or any combination thereof.
The drying time depends on the particular method used, but is generally preferably between 30 seconds and several minutes.

  Further, the treatment liquid of the present invention can also be applied as a rinsing liquid in the rinsing step described above. In this case, the treatment liquid may be an aqueous treatment liquid or an organic solvent-based treatment liquid, but is preferably an aqueous treatment liquid from the viewpoint that residues are less likely to remain in subsequent steps.

Further, the processing liquid of the present invention can be applied as a silicon etching liquid for a polycrystalline silicon film or an amorphous silicon film. Although not particularly limited, for example, by removing a part or all of a polycrystalline silicon film or an amorphous silicon film, the film can be used as an etchant for forming a capacitor structure having an uneven shape to be a capacitor.
Further, it can also be used for a silicon etching solution described in U.S. Patent Application Publication No. 2007/0175862, JP-A-2014-220300, and JP-A-2013-008900.

When the treatment liquid of the present invention is applied to an etching liquid, its composition is not particularly limited,
water and,
A hydrophilic organic solvent,
A quaternary ammonium salt;
0.001 mass ppt to 1 mass ppm of inorganic anions with respect to the total mass of the treatment liquid,
Further, it is preferable that at least one of the following embodiments is selected from the following (1) and (2).
(1) The treatment liquid further contains an amine compound.
(2) The hydrophilic organic solvent includes a water-soluble alcohol-based solvent.

Further, as another embodiment of the etching solution,
water and,
A hydrophilic organic solvent,
A quaternary ammonium salt;
0.001 mass ppt to 1 mass ppm of inorganic anions with respect to the total mass of the treatment liquid,
Further, an embodiment containing an oxidizing agent is preferable.
Further, in addition to the above, it is preferable that at least one type of any one selected from the following (1) to (3) is used.
(1) The treatment liquid further contains a corrosion inhibitor.
(2) The treatment liquid further contains an amine compound.
(3) The treatment liquid further contains a chelating agent.
Also, although not particularly limited, for example, as (3), as a chelating agent, a phosphonic acid-based chelating agent having a hydroxyl group and a phosphonic acid-based chelating agent having a hydroxyl group described in JP-A-2012-080128 Two or more anionic species having no oxidizing power other than the above may be used in combination.

When the treatment liquid of the present invention is applied to an etching liquid, the treatment liquid may be an aqueous treatment liquid or an organic solvent treatment liquid. When used for etching a polycrystalline silicon film or an amorphous silicon film, an aqueous treatment liquid is more advantageous in terms of etching rate.
As the amine compound and the water-soluble alcohol-based solvent, those described above can be used.

Note that, as described above, the semiconductor wafer for etching the polycrystalline silicon film or the amorphous silicon film is not particularly limited. can give.
Further, in the treatment liquid of the present invention, a metal electrode layer of Al, Cu, W, etc., an insulating film of Co, HfO, HfSiO, WO, AlO _x , SiO ₂ , SiOC, SiON, SiOCN, TiN, SiN, TiAlC, etc. Since damage and elution of the layer can also be suitably suppressed, it is also preferably applied to a semiconductor substrate containing these. In this specification, when the composition of a metal compound is represented by a combination of its elements, it means that the composition of the metal compound widely covers any composition. For example, SiOC (SiON) means that Si, O and C (N) coexist, and does not mean that the ratio of the amounts is 1: 1: 1. This is common in the present specification, and the same applies to another metal compound.

Hereinafter, the present invention will be described in more detail with reference to Examples. Materials, used amounts, ratios, processing contents, processing procedures, and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the following examples.
In the examples, “%” and “parts” shown as prescriptions and amounts are based on mass unless otherwise specified. Similarly, “ppm”, “ppt”, “ppq”, etc. are also based on mass. In the following table, “1 ppq” means “0.001 ppt”, and “less than 1 ppq” means “less than 0.001 ppt”.

  Further, the water and the hydrophilic organic solvent used in each of the treatment liquids of the examples and the comparative examples were purified by the method described in JP-A-2007-254168, and both contained an inorganic anion in the liquid. After confirming that the amount was less than 0.001 mass ppt, it was used for adjusting the treatment liquid.

  The amount of inorganic anions contained in the solution was analyzed by ion chromatography (DX-500, manufactured by Nippon Dionex KK). All the analytical measurements were performed in a clean room of a level satisfying ISO class 2 or less. In order to improve the measurement accuracy, the measurement of the treatment liquid having a content of the inorganic anion of 0.001 mass ppt (corresponding to 1 mass ppq in the table described later) is performed by concentrating the solution to 1/100 in terms of volume. Was calculated, and the content of the inorganic anion was calculated by converting to the concentration of the treatment liquid before concentration.

[Removal method 1: Peeling test of permanent film]
As described below, a test for peeling the color filter, which is a permanent film, from the substrate was performed.
<Preparation of treatment liquid>
Each processing solution (A1 to A115) of Examples and Comparative Examples shown in Tables 1 and 2 was prepared.
In each treatment solution, the concentrations (% by mass, mass ppq (1 mass ppq is equivalent to 0.001 mass ppt), mass ppt, mass ppm) of the various components used are as described in the table. The balance (% by mass) is water.
The components described in Tables 1 and 2 are as follows.
TMAH: Tetramethylammonium hydroxide (manufactured by SACHEM)
TEAH: Tetraethylammonium hydroxide (manufactured by SACHEM)
TBAH: Tetrabutylammonium hydroxide (manufactured by SACHEM)
AH212: dimethylbis (2-hydroxyethyl) ammonium hydroxide (Yokkaichi Gosei Co., Ltd.)
DMSO: dimethyl sulfoxide (manufactured by Wako Pure Chemical Industries, Ltd.)
Diethylene glycol monoethyl ether (Wako Pure Chemical Industries, Ltd.)
Propylene glycol (Wako Pure Chemical Industries)
Sulfolane (alias: tetrahydrothiophene 1,1-dioxide) (manufactured by Wako Pure Chemical Industries, Ltd.)
Hydroxylamine (BASF)
Alkanolamine (using diglycolamine) (Tokyo Kasei Co., Ltd.)
Surfynol MD-20 (manufactured by Nissin Chemical Co., Ltd.)
HF (Kanto Chemical)
H ₂ O ₂ (Kanto Chemical Co., Ltd.)

  In addition, the inorganic anions in each treatment solution were introduced by adding nitric acid, hydrochloric acid, and sulfuric acid as the ion sources so as to have the concentrations shown in the table.

<Preparation of Green Pigment Dispersion (Pigment Dispersion 1)>
C.I. I. Pigment Green 36 and C.I. I. 12.6 parts of a 100/55 (mass ratio) mixture with CI Pigment Yellow 139; A mixed solution consisting of 2.7 parts of a benzyl methacrylate / methacrylic acid copolymer (acid value 134 mgKOH / g, Mw = 30,000) as a resin and 78.3 parts of propylene glycol monomethyl ether acetate as a solvent was mixed with a bead mill. After mixing for a time, a Green pigment dispersion was prepared.

<Preparation of Red Pigment Dispersion (Pigment Dispersion 2)>
C.I. I. Pigment Red 254 (12.1 parts), BYK2001 (Disperbyk: manufactured by BYK (BYK), solid content concentration 45.1% by mass) 10.4 parts as a dispersing agent, and benzyl methacrylate / methacrylic acid copolymer ( A mixture of 3.8 parts of an acid value of 134 mg KOH / g, Mw = 30,000) and 73.7 parts of propylene glycol monomethyl ether acetate as a solvent were mixed by a bead mill for 15 hours to prepare a red pigment dispersion. did.

<Preparation of Blue Pigment Dispersion (Pigment Dispersion 3)>
C.I. I. Pigment Blue 15: 6 and C.I. I. Pigment Violet 23 and a 100/25 (mass ratio) mixture, BYK2001 (Disperbyk: manufactured by BYK Co., BYK), 4.7 parts of a solids concentration of 45.1% by mass as a dispersant, and a dispersion resin as a dispersant A mixed solution consisting of 3.5 parts of a benzyl methacrylate / methacrylic acid copolymer (acid value 134 mgKOH / g, Mw = 30,000) and 77.8 parts of propylene glycol monomethyl ether acetate as a solvent is mixed by a bead mill for 15 hours. Thus, a Blue pigment dispersion was prepared.

<Preparation of colored curable resin composition>
Using any of the above pigment dispersions 1 to 3, mixing and stirring were performed so as to obtain the following composition A to prepare a colored curable resin composition.
(Composition A)
Pigment dispersion (any of the above pigment dispersions 1 to 82) 82.35 parts Alkali-soluble resin 2.05 parts Polymerization initiator 1.2 parts DPHA (polymerizable compound) 1.4 parts M-305 (polymerizable compound) ) 1.4 parts p-methoxyphenol 0.001 parts PEGMEA 7.4 parts F-1 4.2 parts

The components contained in the composition A are as follows.
Polymerization initiator: IRGACURE OXE01 (trade name) manufactured by BASF
DPHA: Nippon Kayaku KARAYAD DPHA [trade name]
Dipentaerythritol hexaacrylate M-305: Triacrylate and Toagosei Co., Ltd.
Mixture of pentaerythritol tetraacrylate [brand name]
F-1: The mixture represented by the following formula was applied as a 0.2% solution of PEGMEA.
PGMEA: propylene glycol monomethyl ether acetate Alkali-soluble resin: (benzyl methacrylate / methacrylic acid / -2-hydroxyethyl methacrylate (= 60/22/18 [molar ratio]), weight average molecular weight: 15,000, (Number average molecular weight: 8,000)
In addition, it is measured as a polystyrene conversion value by a GPC (gel permeation chromatography) method.
The GPC method uses HLC-8020GPC (manufactured by Tosoh Corporation), and uses TSKgel SuperHZM-H, TSKgel SuperHZ4000 and TSKgel SuperHZ2000 (manufactured by Tosoh Corporation, 4.6 mm ID × 15 cm) as columns and THF (tetrahydrofuran) as an eluent. ).

  F-1: The following mixture (Mw = 14000)

<Production of silicon wafer with color filters>
The colored curable resin compositions of the respective colors prepared as described above were applied on an 8-inch silicon wafer sprayed with hexamethyldisilazane in advance to form a photocurable coating film. A heat treatment (pre-bake) was performed for 180 seconds using a hot plate at 100 ° C. so that the dry film thickness of the coating film was 1.0 μm. Next, using a stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.), the coating film was irradiated with i-line at a wavelength of 365 nm through a 1.0 μm square Bayer pattern mask at 50 to 1000 mJ / cm ² . (changing the exposure dose by 50mJ / cm ^2). Thereafter, the silicon wafer on which the irradiated coating film was disposed was placed on a horizontal rotary table of a spin shower developing machine (DW-30; manufactured by Chemitronics Co., Ltd.). Paddle development was performed at 23 ° C. for 180 seconds using a 40% dilution of CD-2000 (manufactured by Fuji Film Electronics Materials Co., Ltd.) to form a colored pattern on the silicon wafer.
The silicon wafer on which the coloring pattern was formed was fixed to the horizontal rotary table by a vacuum chuck method. Thereafter, while the silicon wafer was rotated at a rotation speed of 50 rpm by a rotating device, pure water was supplied from above the rotation center to the silicon wafer in a shower form from a jet nozzle to perform a rinsing process, and then spray-dried. Next, the obtained silicon wafer was heated on a hot plate at 200 ° C. for 5 minutes to obtain a silicon wafer provided with a color filter.

<Preparation of Al blanket wafer>
An aluminum (Al) layer was formed on another silicon wafer by a CVD (chemical vapor deposition) method to obtain an Al blanket wafer. The thickness of Al was about 0.5 μm.

<Implementation of color filter peeling test and Al corrosion prevention test>
Using each of the treatment solutions shown in Tables 1 and 2, a color filter peeling test and an Al corrosion prevention test were carried out according to the following procedures.
The silicon wafer and the Al blanket wafer on which the color filters were arranged were cut into 1 × 2 cm to obtain two test wafers (a test wafer with a color filter and a test wafer with Al). The stirrer and the treatment liquid were placed in a beaker, and the mixture was heated to 70 ° C. while stirring the treatment liquid at a rotation speed of 250 rpm. Thereafter, the test wafer was immersed for 5 minutes. Thereafter, the test wafer was taken out of the processing liquid, and ion-exchanged water (DIW) was jetted from the two-fluid nozzle onto the test wafer, and rinsed for 30 seconds.

<Evaluation of color filter peelability (removability)>
The test wafer with the color filter, which had been subjected to the above-mentioned <Performance of color filter peeling test and Al corrosion prevention test>, was observed with an optical microscope (magnification: 50 times) to observe the peelability of the color filter. The releasability (CF releasability) of the color filters was classified and evaluated as follows.
"A": A state in which no residue was confirmed by an optical microscope and 98% or more was removed. "B": A residue was confirmed by an optical microscope and a state in which more than 50% and less than 98% were removed. "C": An optical microscope. The residue can be confirmed by 50% and more than 50% remains

<Evaluation of Al corrosion prevention>
The evaluation of the corrosion inhibition of Al is performed by calculating the amount of film loss (%) calculated from the thickness of the Al layer before and after the processing of the above <Color filter peeling test and Al corrosion inhibition test> of the test wafer with Al. It went based on. The film thickness was calculated from the current value of the Al layer using a four-terminal type ammeter (trade name: VR200, manufactured by Kokusai Electric Alpha Co., Ltd.).
Film loss (%) = (XY) / X
X = initial film thickness (nm) before processing of test wafer with Al
Y = Thickness (nm) of the test wafer with Al after processing after the above processing
The evaluation criteria are as follows.

<Al corrosion protection>
"A": The amount of film loss is 5% or less.
"B": The amount of film loss is more than 5% and 10% or less.
“C”: The amount of film loss is more than 10% and 50% or less.
"D": The amount of film loss exceeds 50%.

(Table 1)

  For Examples A37, A38, and A39, treatment liquids were prepared and evaluated in the same manner except that hydroxylamine was changed to hydroxylamine sulfate (manufactured by Aldrich, 99.999% trace metals bases). The same results as those of Examples A37, A38 and A39 were obtained.

(Table 2)

In Tables 1 and 2, although the removability was ranked A, those with a relatively large amount of residue are indicated as A ^* .
In Tables 1 and 2, when Examples A2, A3, and A4 are compared with Examples A107, A108, and A109, respectively, Example A107 has a removability of “A”, but is compared with Example A2. And the amount of residue was large. In Example A108, although the removability was “A”, the amount of the residue was larger than that in Example A3. In Example A109, although the removability was “A”, the amount of the residue was larger than that in Example A4. That is, it was confirmed that the effect of the present invention was more excellent when water was 1% by mass or more in the organic solvent-based treatment liquid.

  In Tables 1 and 2, in Examples A112, A113, and A114, although the removability was “A”, a little more residues were confirmed. In contrast, it was confirmed that when the content of DMSO in each of the treatment liquids of Examples A112, A113, and A114 was 1% by mass or more, the residue could be reduced. That is, it was confirmed that, when the aqueous treatment liquid was used, when the content of the hydrophilic organic solvent was 1% by mass or more, the effect of the present invention was more excellent.

  From the results in Tables 1 and 2, it was confirmed that the treatment liquid of the present invention has excellent corrosion resistance to the metal film and excellent peelability of the color filter.

  On the other hand, the treatment liquid of the comparative example did not exhibit the desired effect because the content of the inorganic anion with respect to the total mass of the treatment liquid was not in the predetermined range.

[Removal method 2: Residue cleaning test]
A test for cleaning and removing the dry etching residue and the dry ashing residue from the substrate was performed as follows.
<Preparation of treatment liquid>
Each processing solution (B1 to B115) of Examples and Comparative Examples shown in Tables 3 and 4 was prepared. In each treatment solution, the concentrations (% by mass, mass ppq (1 mass ppq is equivalent to 0.001 mass ppt), mass ppt, mass ppm) of the various components used are as described in the table. The balance (% by mass) is water.
The components described in Tables 3 and 4 are the same as those in Tables 1 and 2 described above.

<Preparation of laminated substrate>

According to the following procedure, on a Si substrate, a laminated substrate (a pre-process laminated substrate) including, in this order, a wiring film composed of an Al alloy film and a titanium nitride film, a silicon oxide film, and a resist film having a predetermined opening. ) Formed.

Using the obtained laminated substrate, using this resist film as a mask, dry etching using plasma is performed, and the silicon oxide film and the titanium nitride film are etched until the surface of the Al alloy film is exposed, and holes are formed. Formed. Next, the resist film used as a mask was removed by ashing using plasma.
According to the above-described procedure, the hole 6 having the wiring film 4 composed of the Al alloy film 2 and the titanium nitride film 3 and the silicon oxide film 5 on the Si substrate 1 in this order and exposing the Al alloy film 2 at a predetermined position. Was manufactured as a sample (pattern wafer) to be processed (see FIG. 1).

<Observation of residue by scanning electron microscope>

When the cross section of the laminated substrate 10 is confirmed by a scanning electron microscope (SEM), the dry etching residue and the dry etching residue are formed on the wall surface and the bottom surface of the hole 6 (the bottom surface is the exposed surface of the Al alloy film 2). Dry ashing residue (residue 11) was observed.
The dry etching residue and the dry ashing residue are derived from not only the altered resist film, silicon oxide film, and titanium nitride film but also the Al alloy film exposed at the bottom of the hole 6.

<Cleaning and evaluation>
Next, the prepared pattern wafer section (approximately 2.0 cm × 2.0 cm) was immersed in each cleaning composition heated to 70 ° C. for 15 minutes, and then the pattern wafer section was taken out. min washing was performed with _{N 2} dry.
The surface of the section of the pattern wafer after the immersion test was observed by SEM, and the removability of dry etching residue and ashing residue, and the corrosion prevention of Al of the wiring exposed at the bottom of the hole 6 were evaluated according to the following evaluation criteria. An evaluation was performed.
The evaluation criteria are shown below.

<Removability of residue (removability)>
"A": The residue was completely removed, or less than 25% of the residue remained.
"B": Dissolution of the residue was not completed, and 25% or more and 50% or less of the residue remained.
"C": More than 50% of the residue remained.

<Al corrosion protection>
"A": The amount of film loss is 5% or less.
"B": The amount of film loss is more than 5% and 10% or less.
“C”: The amount of film loss is more than 10% and 50% or less.
"D": The amount of film loss exceeds 50%.
The evaluation of the corrosion inhibitory property of Al was performed in the same manner as the evaluation in the above [Permanent film peeling test].
The results are shown in Tables 3 and 4, respectively.

(Table 3)

  For Examples B37, B38, and B39, a treatment solution was prepared and evaluated in the same manner except that hydroxylamine was changed to hydroxylamine sulfate. The results were the same as those of Examples B37, B38, and B39. was gotten.

(Table 4)

In Tables 3 and 4, although the removability was ranked A, those with a relatively large amount of residue were indicated as A ^* .
In Tables 3 and 4, when Examples B2, B3, and B4 are compared with Examples B112, B113, and B114, respectively, Example B112 has a removability of “A” but is compared with Example B2. And the amount of residue was large. In Example B113, although the removability was “A”, the amount of the residue was larger than that in Example B3. In Example B114, although the removability was “A”, the amount of the residue was larger than that in Example B4. It was confirmed that the effect of the present invention was more excellent when the amount of the hydrophilic organic solvent was 1% by mass or more in the aqueous treatment liquid.

  In Tables 3 and 4, in Examples B107, B108, and B109, although the removability was “A”, a little more residue was confirmed. In contrast, it was confirmed that when the content of DMSO in each of the treatment solutions of Examples B107, B108, and B109 was reduced to make the content of water 1% by mass or more, the residue could be reduced. That is, it was confirmed that when the organic solvent-based treatment liquid was used, when the content of water was 1% by mass or more, the effect of the present invention was more excellent.

  From the results in Tables 3 and 4, it can be seen that the treatment liquid of the present invention has excellent anti-corrosion properties for metal films and excellent cleaning and removal properties for dry etching residues and dry ashing residues. confirmed.

  On the other hand, the treatment liquid of the comparative example did not exhibit the desired effect because the content of the inorganic anion with respect to the total mass of the treatment liquid was not in the predetermined range.

[Removal method 3: Residue cleaning test]
A test for cleaning and removing the dry etching residue from the substrate was performed as follows.
In the following evaluation, a model substrate after dry etching of polysilicon (poly-Si) and a model substrate having SiP and SiGe were prepared, and each of them was evaluated to remove residue and prevent corrosion. The sex was evaluated. In addition to the above-described model substrate, a model substrate is prepared after a dry etching process of a SiN film that can be used as a gap film of polysilicon (poly-Si). Residue removal properties of the film (resist residue) were similarly evaluated.

<Preparation of treatment liquid>
Each processing solution (C1 to C42) of the example and the comparative example shown in Table 5 was prepared. In each treatment solution, the concentrations (% by mass, mass ppq (1 mass ppq is equivalent to 0.001 mass ppt), mass ppt, mass ppm) of the various components used are as described in the table. The balance (% by mass) is water.
The components described in Table 5 are the same as the components in Table 1 described above.

<Removability of polysilicon residue>
Test wafer: A 500 nm thick Poly-Si wafer formed on single crystal <100> silicon was prepared. For this, a dry etching process was performed. Next, the Poly-Si wafer was subjected to a cleaning treatment under the following conditions using a single-wafer apparatus (POLOS (trade name) manufactured by SPS-Europe BV), and an evaluation test was performed.
・ Chemical solution temperature: 60 ° C
Discharge amount: 1 L / min.
・ Wafer rotation speed 500rpm
In the evaluation tests of <Removability of polysilicon residue> and <Removability of resist residue> described below, the amount of the residue was quantified by observing the obtained substrate with an optical microscope (50 times magnification).

<Evaluation of removability of polysilicon residue>
"A": The residue was completely removed, or less than 25% of the residue remained.
"B": Dissolution of the residue was not completed, and 25% or more and 50% or less of the residue remained.
"C": More than 50% of the residue remained.

<Removability of resist residue>
After a SiN film was formed on Poly-Si by CVD (chemical vapor deposition), a photoresist film was formed, and the photoresist was patterned by UV (ultraviolet) exposure and development to form a resist film. Thereafter, the SiN film was dry-etched with a fluorine-based gas, and the obtained substrate was evaluated.
The obtained substrate was immersed in each of the treatment solutions shown in Table 5 adjusted to 60 ° C., and treated for 30 seconds. Thereafter, the substrate was taken out of each processing solution, the substrate was washed with water, and further dried by air blowing.

<Evaluation of resist residue removal>
"A": A state in which no residue was confirmed by an optical microscope and 100% was removed. "B": A residue was confirmed in an optical microscope and a state in which more than 50% and less than 100% were removed. "C": A state by an optical microscope. Residue can be confirmed and 50% or more remains

<Electrode corrosion prevention>
A model substrate formed by CVD and having SiP and SiGe as electrodes was evaluated.
The obtained substrate was immersed in each of the treatment solutions shown in Table 5 adjusted to 60 ° C., and treated for 30 seconds. Thereafter, the substrate was taken out of each processing solution, the substrate was washed with water, and further dried by air blowing. In the following evaluation criteria, the "film loss" was determined by the same method as in the above <Evaluation of corrosion prevention of Al>.

<Evaluation of corrosion prevention properties for SiP>
"A": The amount of film loss is 5% or less.
“B”: The amount of film loss is more than 5% and 20% or less.
"C": The amount of film loss exceeds 20%.

<Evaluation of corrosion prevention property for SiGe>
"A": The amount of film loss is 5% or less.
“B”: The amount of film loss is more than 5% and 20% or less.
"C": The amount of film loss exceeds 20%.

(Table 5)

  From the results in Table 5, it can be seen that according to the treatment liquid of the present invention, while the residue of polysilicon (Poly-Si) and the residue of resist are excellent in removing the residue, other electrode films (SiP and SiGe) on the substrate are obtained. ) Was also confirmed to be excellent in corrosion prevention.

[Removal method 4: Residue cleaning test]
Regarding the above-described removal method 3, examples and comparative examples using a single-wafer apparatus will be described. The processing was performed using a single-wafer apparatus while changing the supply speed of the processing liquid. The processing targets are various model substrates used in the above-described removal method 3. The evaluation method and the evaluation criteria used in the removal method 4 are the same as those in the removal method 3.
The results are shown in Table 6.

(Table 6)

  If it exceeds 5 L / min, the removal of the residue from Poly-Si is reduced in the processing liquid having a nitrate ion content of less than 0.001 mass ppt (corresponding to "less than 1 mass ppq" in the table), It was confirmed that when the nitrate ion content in the solution exceeded 1 ppm by mass, the corrosion inhibition of SiP and SiGe was reduced.

  Therefore, it is clear from the above results that the chemical solution supply rate is preferably 0.05 to 5 L / min.

  On the other hand, when the content of the inorganic anion was 1 mass ppq to 1 mass ppm, "A" was evaluated at any flow rate. However, in Example A2 in which the inorganic anion is 1 mass ppq (corresponding to 0.001 mass ppt), when the chemical supply rate exceeds 5.5 L / min, the chemical supply rate is 0.05 L / min and Compared with the case of 3 L / min, the residue removal property for Poly-Si and the corrosion prevention property for SiP and SiGe were slightly inferior.

REFERENCE SIGNS LIST 1 Si substrate 2 Al alloy film 3 titanium nitride film 4 wiring film 5 silicon oxide film 6 hole 10 laminated substrate 11 residue

Claims (13)

Water, a hydrophilic organic solvent, a quaternary ammonium salt, nitric acid, sulfuric acid, and a treatment liquid containing an inorganic acid selected from the group consisting of hydrochloric acid ,
The treatment solution contains a nitrate ion using the nitric acid as an ion source, a sulfate ion using the sulfuric acid as an ion source, and an inorganic anion selected from the group consisting of chloride ions using the hydrochloric acid as an ion source. ,
The treatment liquid, wherein the content of the inorganic anion is 0.001 mass ppt to 1 mass ppm based on the total mass of the treatment liquid. The processing liquid according to claim 1, wherein the processing liquid contains nitrate ions using the nitric acid as an ion source .   A treatment liquid containing water, a hydrophilic organic solvent, a quaternary ammonium salt, and an inorganic anion,
  The inorganic anion is a sulfate ion,
  The treatment liquid, wherein the content of the inorganic anion is 0.001 mass ppt to 1 mass ppm based on the total mass of the treatment liquid. For the total mass of the processing solution,
The content of the water is 1 to 30% by mass,
The content of the hydrophilic organic solvent is 40 to 98% by mass,
The treatment liquid according to any one of claims 1 to 3, wherein the content of the quaternary ammonium salt is 0.1 to 30% by mass. For the total mass of the processing solution,
The content of the water is 20 to 98% by mass,
The content of the hydrophilic organic solvent is 1 to 40% by mass,
The treatment liquid according to any one of claims 1 to 3, wherein the content of the quaternary ammonium salt is 0.1 to 30% by mass.   A treatment liquid containing water, a hydrophilic organic solvent, a quaternary ammonium salt, and an inorganic anion,
  The content of the hydrophilic organic solvent is 50 to 95% by mass based on the total mass of the treatment liquid,
  The treatment liquid, wherein the content of the inorganic anion is 0.001 mass ppt to 1 mass ppm based on the total mass of the treatment liquid.   A treatment liquid containing water, a hydrophilic organic solvent, a quaternary ammonium salt, and an inorganic anion,
  For the total mass of the processing solution,
  The content of the water is 1 to 30% by mass,
  The content of the hydrophilic organic solvent is 50 to 98% by mass,
  The content of the quaternary ammonium salt is 0.1 to 30% by mass,
  The treatment liquid, wherein the content of the inorganic anion is 0.001 mass ppt to 1 mass ppm.   Water, a hydrophilic organic solvent, a quaternary ammonium salt, nitric acid, sulfuric acid, and a treatment liquid containing an inorganic acid selected from the group consisting of hydrochloric acid,
  The treatment liquid contains a nitrate ion using the nitric acid as an ion source, a sulfate ion using the sulfuric acid as an ion source, and an inorganic anion selected from the group consisting of chloride ions using the hydrochloric acid as an ion source. ,
  The content of the inorganic anion is 0.001 mass ppt to 1 mass ppm with respect to the total mass of the processing solution,
  The mass ratio represented by the content of the quaternary ammonium salt / the content of the inorganic anion is 1 × 10 ² ~ 1 × 10 ¹⁴ A processing solution. The processing solution according to any one of claims 1 to 8 , further comprising an amine compound. The treatment liquid according to claim 9 , wherein the amine compound contains at least one selected from hydroxylamine and a hydroxylamine salt. The treatment liquid according to claim 10 , wherein the content of at least one selected from the group consisting of hydroxylamine and hydroxylamine salt is 0.1 to 15% by mass based on the total mass of the treatment liquid. The processing solution according to any one of claims 1 to 11 , further comprising an oxidizing agent. Further comprises a halide, the processing liquid according to any one of claims 1 to 12.