JPWO2017119350A1 - PROCESS LIQUID, METHOD FOR CLEANING SUBSTRATE, AND METHOD FOR MANUFACTURING SEMICONDUCTOR DEVICE - Google Patents

Abstract

An object of the present invention is a processing solution for semiconductor devices, which is excellent in residue removal performance, excellent in corrosion prevention performance to a cleaning object, and further suppresses adhesion of foreign matter to the cleaning object, the above processing A method of cleaning a substrate using a liquid, and a method of manufacturing a semiconductor device. The treatment liquid of the present invention comprises at least one hydroxylamine compound selected from hydroxylamine and hydroxylamine salt, a nitrogen-containing compound having a specific structure, and at least one solvent selected from an organic solvent and water. And the number of objects to be counted of a size of 0.05 μm or more, counted by a light scattering type liquid particle counter, in the above-mentioned processing solution is 1 to 2,000 per 1 mL. Is one.

Description

The present invention relates to a processing solution and a method of cleaning a substrate. In particular, in the manufacture of semiconductor devices, a processing solution that can be suitably used for cleaning and removing dry etching residues and the like present on a substrate provided with a metal hard mask, and cleaning of a substrate using the processing solution On the way.
Furthermore, the present invention also relates to a method of manufacturing a semiconductor device using the processing solution.

Semiconductor devices such as CCDs (Charge-Coupled Devices) and memories are manufactured by forming fine electronic circuit patterns on a substrate using photolithography technology. Specifically, in a semiconductor device, a photoresist film is formed on a laminated film including a metal film (for example, Co, Cu) serving as a wiring material (e.g., Co, Cu) formed on a substrate, an etching stop film, and an interlayer insulating film And a photolithography process and a dry etching process (for example, plasma etching process).
In addition, a dry ashing process (for example, a plasma ashing process) for peeling the resist film is performed as needed.

On the other hand, in recent years, in order to realize further miniaturization, a metal material based resist film (so-called metal hard mask) such as TiN and AlOx has been studied as a resist film.
In the case of using a metal hard mask as a resist film, a dry etching process (for example, plasma etching process) is usually performed using the metal hard mask as a mask to form holes based on the pattern shape of the metal hard mask to form wiring A step of exposing a metal film surface to be a film is performed.

In the substrate that has undergone the dry etching process, residual substances such as dry etching residual substances adhere to the metal film and / or the interlayer insulating film, and processing for cleaning and removing these with a processing solution is generally performed. .
For example, Patent Documents 1 and 2 disclose a treatment liquid containing hydroxylamine, a solvent, and an amine compound or an organic ammonium compound, and a method of cleaning a substrate using the same.

Japanese Patent Application Laid-Open No. 11-194505 JP, 2012-142588, A

In general, a processing solution used for cleaning a substrate for a semiconductor device is required to be clean. If impurities are mixed in the processing solution, foreign matter may adhere to the substrate after the treatment, or the foreign matter may cause pattern defects, leading to a decrease in the yield (non-defective rate) of the processing object. It is for. For this reason, at the time of preparation of the processing solution or before its use, removal and purification of impurities such as a trace amount of organic contaminants, metal contaminants and fats and oils contained in the solution are performed by filtration with a filter or the like.
On the other hand, as a characteristic required for the processing solution, for example, while being excellent in residue removal performance for removing dry etching residues etc., a wiring metal (metal, metal nitride, alloy, which is a processing object), for example, wiring The corrosion inhibition performance (corrosion prevention performance) with respect to Co, Cu) used as a metal and / or an interlayer insulating film can be mentioned.

  The present inventors prepared the treatment solutions described in Patent Documents 1 and 2 respectively, and particularly applied to an embodiment using a metal hard mask to study suppression of foreign matter adhesion to the object to be treated, It has been found that the purity of the above-mentioned treatment liquid after purification is correlated with the residue removal performance and the corrosion prevention performance of the treatment liquid.

Therefore, the present invention provides a treatment liquid for semiconductor devices, which is excellent in residual substance removal performance, excellent in corrosion prevention performance with respect to a treatment object, and in which adhesion of foreign matter to the treatment object is suppressed. To be an issue.
Another object of the present invention is to provide a method of cleaning a substrate using the above-mentioned processing solution, and a method of manufacturing a semiconductor device.

As a result of intensive studies to achieve the above problems, the present inventors have found that they contain at least one nitrogen-containing compound selected from hydroxylamine compounds, amine compounds and organic ammonium compounds, and a solvent, and in a solution. According to the processing solution in which the number of objects to be counted measured by the dynamic light scattering method is within a predetermined range, it has been found that the above problems can be solved, and the present invention has been completed.
That is, it discovered that the said objective could be achieved by the following structures.

[1] at least one hydroxylamine compound selected from hydroxylamine and hydroxylamine salt,
At least one nitrogen-containing compound selected from a compound represented by the general formula (1) described later and a compound represented by the general formula (2) described later;
At least one solvent selected from an organic solvent and water;
Processing solution for semiconductor devices including
The treatment liquid, wherein the number of objects to be counted with a size of 0.05 μm or more counted by the light scattering type liquid-in-liquid counter in the treatment liquid is 1 to 2,000 per 1 mL.
[2] The treatment liquid according to [1], wherein the organic solvent contains at least one selected from N-methyl-pyrrolidone, dimethyl sulfoxide, and propylene glycol.
[3] With respect to the total mass of the above processing solution,
The water content is 20 to 98% by mass,
The processing liquid as described in [1] or [2] whose content of the said organic solvent is 0-30 mass%.
[4] With respect to the total mass of the above processing solution,
The water content is 1 to 30% by mass,
The processing liquid as described in [1] or [2] whose content of the said organic solvent is 20-98 mass%.
[5] The treatment liquid according to any one of [1] to [4], further containing a corrosion inhibitor.
[6] The treatment liquid according to any one of [1] to [5], further containing a chelating agent.
[7] The above-mentioned corrosion inhibitor is a compound represented by general formula (A) to general formula (C) described later, substituted or unsubstituted tetrazole, maleic anhydride, phthalic anhydride, fructose, ammonium thiosulfate, tetramethyl Guanidine, gallic acid ester, 2-mercapto-5-methylbenzimidazole, 2-mercaptothiazoline, 3- (2-aminophenylthio) -2-hydroxypropyl mercaptan, and 3- (2-hydroxyethylthio) -2 -The process liquid as described in [5] which is at least any one sort chosen from hydroxypropyl mercaptan.
[8] The treatment liquid according to any one of [1] to [7], further comprising 1 mass ppt to 10 mass ppm of Fe ions based on the total mass of the treatment liquid.
[9] The treatment liquid according to any one of [1] to [8], further comprising 1 mass ppt to 10 mass ppm of Co ions with respect to the total mass of the treatment liquid.
[10] In the above general formula (1), each of R ¹ , R ² and R ³ independently has a hydrogen atom or a substituent represented by the general formula (3) described later. The process liquid in any one of [1]-[9] which is a good linear, branched or cyclic alkyl group.
[11] In the above general formula (2), R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently selected from an alkyl group having 1 to 6 carbon atoms and a hydroxyalkyl group having 1 to 6 carbon atoms The processing liquid according to any one of [1] to [10], which is a monovalent organic group and X ⁻ is a hydroxide ion.
[12] A treatment liquid preparation process A for preparing the treatment liquid according to any one of [1] to [11],
A cleaning process for cleaning a substrate provided with a metal hard mask containing at least one of Cu, Co, W, AlOx, AlN, AlOxNy, WOx, Ti, TiN, ZrOx, HfOx and TaOx using the above processing solution And B. a method of cleaning a substrate.
In addition, it is a number represented by x = 1-3, y = 1-2.
[13] A treatment liquid preparation process A for preparing the treatment liquid according to any one of [1] to [11],
A cleaning process for cleaning a substrate provided with a metal hard mask containing at least one of Cu, Co, W, AlOx, AlN, AlOxNy, WOx, Ti, TiN, ZrOx, HfOx and TaOx using the above processing solution B,
A drainage recovery step C for recovering the drainage of the treatment liquid used in the cleaning step B;
Metal hard containing at least one selected from Cu, Co, W, AlOx, AlN, AlOxNy, WOx, Ti, TiN, ZrOx, HfOx, and TaOx newly prepared using the drainage of the recovered treatment liquid A cleaning step D for cleaning a substrate provided with a mask;
And a drainage recovery step E for recovering the drainage of the treatment liquid used in the cleaning step D,
The substrate cleaning method according to [12], wherein the cleaning process D and the drainage recovery process E are repeatedly performed to recycle the drainage of the processing liquid.
[14] Prior to the treatment liquid preparation step A, does it have a metal ion removal step F for removing at least one ion species selected from Fe ions and Co ions from at least one of the hydroxylamine compound and the solvent? Or
It has a metal ion removal step G for removing at least one kind of ion species selected from Fe ions and Co ions in the treatment liquid after the treatment liquid preparation step A and before performing the washing step B. The method for cleaning a substrate according to [12] or [13].
[15] Before the treatment liquid preparation step A, do you have the charge elimination step I for diselectrifying the solvent, or
The substrate according to any one of [12] to [14], which has a charge removal step J for discharging the treatment liquid after the treatment liquid preparation step A and before performing the washing step B. How to wash
[16] At least one of Cu, Co, W, AlOx, AlN, AlOxNy, WOx, Ti, TiN, ZrOx, HfOx and TaOx is treated with the treatment liquid according to any one of [1] to [11]. A method of manufacturing a semiconductor device, comprising the step of cleaning a substrate provided with a metal hard mask.
In addition, it is a number represented by x = 1-3, y = 1-2.

According to the present invention, there is provided a processing solution for a semiconductor device, which is excellent in residue removal performance, excellent in corrosion prevention performance on a processing target, and further suppresses adhesion of foreign matter to the processing target. be able to.
Further, according to the present invention, it is possible to provide a method of cleaning a substrate using the above-mentioned processing solution, and a method of manufacturing a semiconductor device.

It is a cross-sectional schematic diagram which shows an example of the laminated body applicable to the washing | cleaning method of the board | substrate of this invention.

Hereinafter, the present invention will be described in detail.
Although the description of the configuration requirements described below may be made based on the representative embodiments of the present invention, the present invention is not limited to such embodiments.
In addition, in this specification, the numerical range represented using "-" means the range which includes the numerical value described before and after "-" as a lower limit and an upper limit.

In the notation of groups (atom groups) in the present specification, notations not describing substitution and non-substitution include those having no substituent as well as those having a substituent, as long as the effects of the present invention are not impaired. It is 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). The same is true for each compound.
Further, "radiation" in the present specification means, for example, a bright 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. Also, as used herein, light means actinic rays or radiation. Unless otherwise specified, the “exposure” in the present specification is not only exposure by far ultraviolet rays represented by a mercury lamp or excimer laser, X-rays, EUV light, etc., but also drawing by particle beams such as electron beams or ion beams Also included in the exposure.
Moreover, in the present specification, “(meth) acrylate” represents both or either of acrylate and methacrylate, and “(meth) acrylic” represents both or either of acrylic and methacryl.
Moreover, in this specification, "monomer" and "monomer" are synonymous. A monomer as used herein 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 the present specification, the 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 involved in the polymerization reaction.
In addition, the term "preparation" as used herein means including procuring a predetermined material by purchasing or the like, in addition to providing a specific material by synthesis or preparation.

In the present invention, the dry etching residue is a by-product generated by performing dry etching (for example, plasma etching), and for example, an organic residue derived from a photoresist, a Si-containing residue, and a metal. Containing residue etc. In the following description, the above-mentioned dry etching residue may be simply referred to as “residue”.
In the present invention, the dry ashing residue is a by-product generated by performing dry ashing (for example, plasma ashing), and for example, organic residue derived from photoresist, Si-containing residue, and , Metal-containing residue etc.
In the present invention, "1 Å" is synonymous with "0.1 nanometer (nm)".

Treatment solution
The treatment liquid of the present invention comprises at least one hydroxylamine compound selected from hydroxylamine and hydroxylamine salt,
At least one nitrogen-containing compound selected from a compound represented by the general formula (1) described later and a compound represented by the general formula (2) described later;
At least one solvent selected from an organic solvent and water;
Processing solution for semiconductor devices including
In the above-mentioned processing solution, the number of objects to be counted with a size of 0.05 μm or more, which is counted by a light scattering type liquid-in-liquid counter, is 1 to 2,000 per 1 mL.

The treatment liquid of the present invention having the above-mentioned constitution is excellent in the residue removing performance when used for semiconductor device applications, and excellent in the corrosion prevention performance to the object to be treated. Further, in the object to be treated treated with the treatment liquid, there are few pattern defects which are caused by the adhesion of foreign matter and foreign matter. That is, it can be said that the treatment liquid of the present invention is suppressed in the influence of the decrease in the yield of the object to be treated.
This is not clear in detail, but is presumed as follows.
In removal and purification of impurities in the treatment liquid, filtration and purification of filters and the like are performed to remove and remove impurities such as trace amounts of organic contaminants, metal contaminants, and fats and oils contained in the solution. The treatment liquid of the present invention is characterized in that although the removal and purification are performed in excess during preparation, the impurities are not completely removed, but a trace amount is left in the liquid.

  Here, the above-mentioned impurities that may be contained in the treatment liquid are counted by the light scattering type liquid-in-liquid counter. The present inventors, on the basis of the number of objects to be counted with a size of 0.05 μm or more counted by a light scattering type liquid particle counter, the residue removal performance, the corrosion prevention performance for the processing object, and the processing object Each effect of suppression of foreign matter adhesion to an object was examined, and it was found that the number of the objects to be counted is 1 to 2,000 per 1 mL, whereby the above respective effects can be established at an excellent level.

The objects to be counted which are counted by the light scattering type liquid-in-liquid counter include bubbles (for example, bubbles containing dissolved oxygen) in addition to the above-mentioned impurities (for example, organic solid and inorganic solid). Be
Among these components contained in the solution, the treatment solution of the present invention is presumed to exhibit a desired effect particularly due to the presence of bubbles containing an organic solid and dissolved oxygen.
A semiconductor substrate in which a metal film surface to be a wiring film is exposed to the etched opening by dry etching using the processing solution of the present invention, for example, using a metal hard mask as a mask In the case where the etching residue adheres), the dissolution of the residue proceeds with the hydroxylamine compound contained as a metal reducing agent. At this time, the dissolved oxygen and the organic solid also approach the residue respectively, and the dissolved oxygen functions as an oxidizing agent, and the organic solid functions as a ligand, thereby promoting dissolution of the residue (particularly, metal residue). it is conceivable that. On the other hand, dissolved oxygen and organic solids (in particular, dissolved oxygen) not only have a dissolution promoting action on the residue but also a dissolution promoting action on the metal film formed on the substrate. However, it is inferred that the dissolved residue (in particular, metal residue component) is present at a high concentration on the surface of the metal film to function as a film, thereby causing the metal film to be dissolved oxygen and organic solids. It is considered that the corrosion action and the corrosion action by the above hydroxylamine compound are suppressed.
On the other hand, when the number of objects to be counted is 0 per 1 mL (that is, when the solution does not contain organic solids and bubbles), the residue removal performance and the corrosion prevention performance are insufficient. I know that. If the number of objects to be counted is 0 per 1 mL, it is presumed that the dissolution of the residue in the solution is not accelerated and the above-mentioned effect of suppressing the corrosion by the hydroxylamine compound is not expressed.
On the other hand, when the number of objects to be counted exceeds 2000 per 1 mL (that is, when the solution contains a large amount of organic solid matter and bubbles), the treatment solution is excellent in the residue removal performance, but corrosion prevention It has been confirmed that the performance decreases. It is considered that this is because the solution contains a large amount of dissolved oxygen and organic solids, and therefore corrosion of the metal film is likely to occur. Furthermore, since the adhesion probability to the metal film surface of organic solid content increases, it is confirmed that foreign substances remain on the substrate after the cleaning processing, and the number of defects on the substrate to be processed is large.
The components contained in the treatment liquid and the components that may be contained will be described below.

<Hydroxylamine compound>
The treatment liquid of the present invention contains at least one hydroxylamine compound selected from hydroxylamine and hydroxylamine salt. The hydroxylamine compound promotes the decomposition and solubilization of the residue and prevents the corrosion of the object to be treated.

Here, “hydroxylamine” relating to hydroxylamine and hydroxylamine salt in the treatment liquid of the present invention refers to hydroxylamines in a broad sense including substituted or unsubstituted alkylhydroxylamine and the like, and any of them may be used. Can also obtain the effects of the present invention.
The hydroxylamine is not particularly limited, but preferred embodiments include unsubstituted hydroxylamine and hydroxylamine derivatives.
The hydroxylamine derivative is not particularly limited. For example, 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, and N, N-disulfoethylhydroxylamine Etc.
The salt of hydroxylamine is preferably an inorganic acid salt or an organic acid salt of hydroxylamine as described above, and is a salt of an inorganic acid formed by combining a nonmetal such as Cl, S, N, and P with hydrogen. It is more preferable that it be a salt of any of hydrochloric acid, sulfuric acid and nitric acid.
The salts of hydroxylamine used in the treatment solution include hydroxyl ammonium nitrate (also referred to as HAN), hydroxyl ammonium sulfate (also referred to as HAS), hydroxyl ammonium hydrochloride (also referred to as HAC), hydroxyl ammonium phosphorus Acid salts, N, N-diethylhydroxylammonium sulfate, N, N-diethylhydroxylammonium nitrate, or mixtures thereof are preferred.
Also, an organic acid salt of hydroxylamine can be used, and hydroxyl ammonium citrate, hydroxyl ammonium oxalate, hydroxyl ammonium fluoride and the like can be exemplified.
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 singly or in appropriate combination of two or more.
Among the above, hydroxylamine, N, N-diethylhydroxylamine, or hydroxyl ammonium sulfate is preferable from the viewpoint that the effects of the present invention can be significantly obtained.

  The content of the hydroxylamine compound in the treatment liquid is preferably in the range of 0.01 to 30% by mass, and more preferably in the range of 10 to 20% by mass, with respect to the total mass of the treatment liquid. preferable. By setting the above range, the effects of the present invention can be remarkably obtained.

<Nitrogen-containing compounds>
The treatment liquid of the present invention contains at least one nitrogen-containing compound selected from a compound represented by the following general formula (1) and a compound represented by the following general formula (2). These nitrogen-containing compounds exert the function of removing the residue in the liquid. Moreover, the compound represented by General formula (2) functions also as a pH adjuster.

The content of the nitrogen-containing compound of at least one selected from the compound represented by the following general formula (1) and the compound represented by the following general formula (2) in the treatment liquid of the present invention is It is preferable that it is 1-80 mass% with respect to the total mass.
When the compound represented by the following general formula (1) is contained as a nitrogen-containing compound in the treatment liquid, its content is more preferably 20 to 70% by mass with respect to the total mass of the treatment liquid, More preferably, it is 50 to 70% by mass.
When the compound represented by the following general formula (2) is contained as a nitrogen-containing compound in the treatment liquid, the content is more preferably 5 to 20% by mass with respect to the total mass of the treatment liquid, More preferably, it is 5 to 10% by mass.
The above nitrogen-containing compounds may be used alone or in combination of two or more types in the treatment liquid.

(Compound represented by the general formula (1))

In the general formula (1), R ¹ , R ² and R ³ each independently represent a hydrogen atom, or a linear, branched or cyclic alkyl group, an alkenyl group, an alkynyl group, an acyl group, a linear or branched group And a monovalent organic group selected from an alkoxy group, an amidyl group (—CNHNH ₂ ), an alkoxyalkyl group, an alkylsulfonyl group, a carboxy group, and a sulfonic acid group, and salts thereof. The monovalent organic group may further have a substituent. In the formula, at least one of R ¹ , R ² and R ³ is preferably a group other than a hydrogen atom (in other words, in the formula, all of R ¹ , R ² and R ³ are hydrogen atoms) Is not preferred).

The linear, branched or cyclic alkyl group preferably has 1 to 10 carbon atoms, and more preferably 1 to 6 carbon atoms. As what has a linear and branched or cyclic alkyl group in at least any ^one of R < ¹ >, R < ² > and R < ³ > in General formula (1), a diglycol amine etc. are mentioned, for example.
As an alkenyl group, C1-C10 is preferable and C1-C6 is more preferable. In the general formula ^(1), as having at least one alkenyl group of R 1, ^{R 2,} and ^{R 3,} for example, diallylamine and the like.
As an alkynyl group, C1-C10 is preferable and C1-C6 is more preferable. In the general formula ^(1), as having at least one alkynyl group of R 1, ^{R 2,} and ^{R 3,} for example, 2-methyl-3-butyn-2-amine.
As an acyl group, C1-C10 is preferable and C1-C6 is more preferable. As what has an acyl group in at least any ^one of R < ¹ >, R < ² > and R < ³ > in General formula (1), N- hydroxymethyl acetamide etc. are mentioned, for example.
As a linear or branched alkoxy group, C1-C10 is preferable and C1-C6 is more preferable. As what has a linear or branched alkoxy group in at least one of R ¹ , R ² and R ^{3 in} the general formula (1), for example, 2- (aminooxy) tetrahydro-2H-pyran and the like can be mentioned. Be
As an alkoxy alkyl group, C1-C10 is preferable and C1-C6 is more preferable. In the general formula ^(1), as having the R 1, ^{R 2,} and alkoxyalkyl groups in at least one of ^{R 3,} for example, 1-methoxy-2-diethylamino - ethane, and the like.
As an alkyl sulfonyl group, C1-C10 is preferable and C1-C6 is more preferable. As what has an alkylsulfonyl group in at least any ^one of R < ¹ >, R < ² > and R < ³ > in General formula (1), methane sulfonamide etc. are mentioned, for example.
The carboxy group and the sulfonic acid group may each have a salt structure (eg, Na salt, K salt, etc.).

  The monovalent organic group may further have a substituent. Examples of the substituent include a hydroxy group, a carboxy group (or a salt thereof), a sulfonic acid group (or a salt thereof), an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, and a combination thereof. The alkyl group, the alkenyl group and the alkynyl group may contain a hetero atom as a substituent.

As an amine compound represented by General formula (1), an alkylamine, an alkanolamine, etc. are mentioned other than the compound mentioned above, for example.
As the alkylamine, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, sec-butylamine, isobutylamine, t-butylamine, pentylamine, 2-aminopentane, 3-aminopentane, 1-amino- 2-methylbutane, 2-amino-2-methylbutane, 3-amino-2-methylbutane, 4-amino-2-methylbutane, hexylamine, 5-amino-2-methylpentane, heptylamine, octylamine, nonylamine, decylamine, Primary alkyl amines such as undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, heptadecylamine, and octadecylamine, dimethylamine, diethylamine, dipylamine Pylamine, diisopropylamine, dibutylamine, diisobutylamine, di-sec-butylamine, di-t-butylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, didecylamine, methylethylamine, methylpropylamine, methylisopropylamine , Methylbutylamine, methylisobutylamine, methyl-sec-butylamine, methyl-t-butylamine, methylamylamine, methylisoamylamine, ethylpropylamine, ethylisopropylamine, ethylbutylamine, ethylisobutylamine, ethyl-sec-butylamine, ethyl Secondary alkyl amines such as isoamyl amine, propyl butyl amine, and propyl isobutyl amine; Ethylamine, triethylamine, tripropylamine, tributylamine, tripentylamine, dimethylethylamine, methyl diethylamine, and tertiary alkyl amines such as methyl dipropyl amine.

  As the alkanolamine, ethanolamine, N-methylethanolamine, N-ethylethanolamine, N-propylethanolamine, N-butylethanolamine, diethanolamine, isopropanolamine, N-methylisopropanolamine, N-ethylisopropanolamine, N -Propylisopropanolamine, 2-aminopropan-1-ol, N-methyl-2-amino-propan-1-ol, N-ethyl-2-amino-propan-1-ol, 1-aminopropan-3-ol N-Methyl-1-aminopropan-3-ol, N-ethyl-1-aminopropan-3-ol, 1-aminobutan-2-ol, N-methyl-1-aminobutan-2-ol, N-ethyl -1-aminobutan-2-ol, -Aminobutan-1-ol, N-methyl-2-aminobutan-1-ol, N-ethyl-2-aminobutan-1-ol, 3-aminobutan-1-ol, N-methyl-3-aminobutan-1-ol N-ethyl-3-aminobutan-1-ol, 1-aminobutan-4-ol, N-methyl-1-aminobutan-4-ol, N-ethyl-1-aminobutan-4-ol, 1-amino-2 -Methylpropan-2-ol, 2-amino-2-methylpropan-1-ol, 1-aminopentan-4-ol, 2-amino-4-methylpentan-1-ol, 2-aminohexane-1-ol -Ol, 3-aminoheptane-4-ol, 1-aminooctan-2-ol, 5-aminooctan-4-ol, 1-aminopropane-2,3-geo , 2-aminopropane-1,3-diol, tris (hydroxymethyl) aminomethane, 1,2-diaminopropan-3-ol, 1,3-diaminopropan-2-ol, 2- (2-aminoethoxy ) Ethanol, N-hydroxymethylethanolamine, N-hydroxymethylisopropanolamine, N, N-dihydroxymethylethanolamine, N-hydroxymethyldiethanolamine, diglycolamine, N-hydroxymethyl-N-methylethanolamine, N-hydroxy Methyl-N-ethylethanolamine, N-hydroxymethylaminoethoxyethanol, N-hydroxymethylmethylamine, N, N-dihydroxymethylmethylamine, N-hydroxymethyldimethylamine, N-hydroxymethylethylamine Min, N, N-dihydroxymethylethylamine, N-hydroxymethyldiethylamine, N-hydroxymethylpropylamine, N-hydroxymethylbutylamine, N-hydroxymethylformamide, N-hydroxymethylacetamide, N-hydroxymethyl-N-methylformamide , N-hydroxymethyl-N-methylacetamide, and N-hydroxymethylpropionamide.

In the general formula (1), R ¹ , R ² , and R ³ each independently have a hydrogen atom or a substituent represented by the following general formula (3) from the viewpoint of being superior to the residue removal performance. It is preferably a linear, branched or cyclic alkyl group which may be substituted.

In general formula (3), R represents a hydrogen atom. n represents 0, 1, or 2. The wavy line portion indicates the bonding position.
The linear, branched or cyclic alkyl group preferably has 1 to 6 carbon atoms.

The linear, branched or cyclic alkyl group which may have a substituent represented by the above-mentioned general formula (3), which R ¹ , R ² and R ³ represent, has, for example, 1 to 5 carbon atoms 6 alkyl group, hydroxyalkyl group having 1 to 6 carbon atoms, -CH ₂ OC ₂ H ₄ OH, -C ₂ H ₄ OC ₂ H ₄ OH, -CH ₂ OC ₂ H ₄ OC ₂ H ₄ OH, etc. It can be mentioned.

(Compound represented by formula (2))

In the general formula (2), R ⁴ , R ⁵ , R ⁶ and R ⁷ each independently represent a hydrogen atom, or a linear, branched or cyclic alkyl group, an alkenyl group, an alkynyl group, an acyl group, a linear group Or branched alkoxy group, amidyl group (-CNHNH ₂ ), benzyl group, aryl group, alkoxyalkyl group, alkylsulfonyl group, alkylsulfonyl group, hydroxy group, carboxy group, sulfonic acid group, and monovalent salts selected from the salts thereof And X ⁻ represents a counter anion. The monovalent organic group may further have a substituent. However, in the formula, the case where all of R ⁴ , R ⁵ , R ⁶ and R ⁷ are hydrogen atoms is excluded.

The linear, branched or cyclic alkyl group preferably has 1 to 6 carbon atoms, more preferably 4 to 6 carbon atoms, and still more preferably 4 to 5 carbon atoms.
As an alkenyl group, C1-C10 is preferable and C1-C6 is more preferable.
As an alkynyl group, C1-C10 is preferable and C1-C6 is more preferable.
As an acyl group, C1-C10 is preferable and C1-C6 is more preferable.
As a linear or branched alkoxy group, C1-C10 is preferable and C1-C6 is more preferable.
As an aryl group, C1-C10 is preferable.
As an alkoxy alkyl group, C1-C10 is preferable and C1-C6 is more preferable.
As an alkyl sulfonyl group, C1-C10 is preferable and C1-C6 is more preferable.
The carboxy group and the sulfonic acid group may each have a salt structure (eg, Na salt, K salt, etc.).
The monovalent organic group may further have a substituent. Examples of the substituent include a hydroxy group, a carboxy group (or a salt thereof), a sulfonic acid group (or a salt thereof), an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, and a combination thereof. The alkyl group, the alkenyl group and the alkynyl group may contain a hetero atom as a substituent.

Further, in the general formula (2), X ⁻ represents a counter anion, and is not particularly limited. For example, hydroxide ion (OH ⁻ ), halogen atom ion, and S atom, P atom, N atom, C And monovalent anions (eg, PF ₆ ^- etc.) containing at least one of atoms and F atoms, and the like, and hydroxide ion is preferable.

In the general formula (2), R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently an alkyl group having 1 to 6 carbon atoms (for example, a methyl group, an ethyl group, and It is preferable that it is a monovalent organic group selected from a butyl group and the like) and a hydroxyalkyl group having 1 to 6 carbon atoms (for example, a hydroxymethyl group, a hydroxyethyl group, a hydroxybutyl group and the like). Especially, a C1-C6 alkyl group and a hydroxyethyl group are more preferable.

Among the above-mentioned, as preferred examples, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, trimethylhydroxyethylammonium hydroxide, dimethyldi (hydroxyethyl) ammonium hydroxide, methyltri (hydroxyethyl) ammonium hydroxide And tetra (hydroxyethyl) ammonium hydroxide and choline.
Among them, tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, tetrabutyl ammonium hydroxide, dimethyl di (hydroxyethyl) ammonium hydroxide, and choline can be mentioned.

<Solvent>
The treatment liquid of the present invention contains at least one solvent selected from organic solvents and water. The content of at least one solvent selected from an organic solvent and water in the treatment liquid of the present invention is preferably 5 to 98 mass% with respect to the total mass of the treatment liquid, and is 20 to 95 mass. More preferably, it is%.

(Organic solvent)
As the organic solvent, it is preferable to contain a water-soluble organic solvent. The water-soluble organic solvent of the treatment liquid promotes solubilization of the additive component and the organic substance residue, and can further improve the corrosion prevention effect.
The water-soluble organic solvent is not particularly limited, and examples thereof include alcohol solvents, ketone solvents, ester solvents, ether solvents (for example, glycol diethers), and sulfoxide solvents and the like. Any of these can be used to effect.

  As the alcohol solvent, for example, alkane diol (including, for example, alkylene glycol), alkoxy alcohol (including, for example, glycol monoether), saturated aliphatic monohydric alcohol, unsaturated non-aromatic monohydric alcohol, and ring Low molecular weight alcohols containing structures are included.

  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-butane Diol, 1,2-butanediol, 2,3-butanediol, pinacol, alkylene glycol and the like can be mentioned.

  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, and 1-methoxy-2-butanol.

  As glycol monoether, for example, 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, 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 etc. Be

  As a saturated aliphatic monohydric alcohol, for example, methanol, ethanol, n-propyl alcohol, isopropyl alcohol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, 2-pentanol, t-pentyl alcohol, and 1-hexanol etc. are mentioned.

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

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

  Examples of ketone solvents include acetone, propanone, cyclobutanone, cyclopentanone, cyclohexanone, diacetone alcohol, 2-butanone, 5-hexanedione, 1,4-cyclohexanedione, 3-hydroxyacetophenone, N-methyl-pyrrolidone And 1,3-cyclohexanedione and cyclohexanone.

  As ester solvents, glycol monoesters such as ethyl acetate, ethylene glycol monoacetate and diethylene glycol monoacetate, and propylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol Examples thereof include glycol monoether monoesters such as monoethyl ether acetate.

  Examples of the sulfoxide solvents include dimethyl sulfoxide, diethyl sulfoxide, diphenyl sulfoxide, methylphenyl sulfoxide and the like.

Among these, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, N-methyl-pyrrolidone, dimethyl sulfoxide, or propylene glycol is preferable from the viewpoint of more excellent residue removal performance, and N-methyl-pyrrolidone, dimethyl sulfoxide, or propylene glycol Is more preferred.
The organic solvents may be used alone or in combination of two or more.

(water)
As water, ultrapure water used for semiconductor production is preferable. Although not particularly limited, it is preferable that the ion concentration of metal elements of Fe, Co, Na, K, Ca, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn be reduced. When used in the preparation of the treatment liquid of the present invention, those adjusted to the ppt order or less are preferable. Examples of the adjustment method include the methods described in paragraphs [0074] to [0084] of JP-A-2011-110515.

The treatment liquid of the present invention can be formulated to be either aqueous or organic solvent-based by adjusting the contents of water and the organic solvent contained in the treatment liquid.
(Water-based treatment liquid)
When using it as a water-based processing liquid, it is preferable to set it as 20-98 mass% with respect to the total mass of a processing liquid, and it is more preferable to set it as 40-98 mass%, and 65-98 mass%. It is more preferable to Moreover, it is preferable to set it as 0-30 mass% with respect to the total mass of a process liquid, and, as for content of an organic solvent, it is more preferable to set it as 0-20 mass%.

(Organic solvent processing liquid)
When using it as an organic-solvent type processing liquid, it is preferable to set it as 1-30 mass% with respect to the total mass of a processing liquid, and it is more preferable to set it as 1-20 mass%, and 10-20 It is more preferable to use mass%. Moreover, it is preferable to set it as 20-98 mass% with respect to the total mass of a process liquid, and, as for content of an organic solvent, it is more preferable to set it as 30-95 mass%.

(Corrosion inhibitor)
The treatment solution of the present invention preferably contains a corrosion inhibitor. The corrosion inhibitor has a function of eliminating over-etching of a metal film (for example, Co, Cu) to be a wiring film.
The corrosion inhibitor is not particularly limited. 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, diaminomethyl triazine, imidazoline thione, 4 -Methyl-4H-1,2,4-triazole-3-thiol, 5-amino-1,3,4-thiadiazole-2-thiol, benzothiazole, tritolyl phosphate, indazole, adenine, cytosine, guanine, thymine, Phosphate inhibitor , Pyrazoles, propanethiols, silanes, secondary amines, benzohydroxamic acids, heterocyclic nitrogen inhibitors, citric acid, ascorbic acid, thiourea, 1,1,3,3-tetramethylurea, urea Urea derivatives, uric acid, potassium ethylxanthogenate, glycine, dodecylphosphonic acid, iminodiacetic acid, acid, boric acid, malonic acid, succinic acid, nitrilotriacetic acid, sulfolane, 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 Colvin acid, ascorbic acid, catechol, t- butyl catechol, phenol, and pyrogallol.

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

The substituted or unsubstituted benzotriazole is, besides those described above, benzotriazole (BTA), 5-aminotetrazole, 1-hydroxybenzotriazole, 5-phenylthiol-benzotriazole, 5-chlorobenzotriazole, 4-chlorobenzo 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, 5- (1 ', 1', 3 ', 3'-tetramethylbutyl) benzotriazole, and the like.
The corrosion inhibitors may be used alone or in combination of two or more.

  As a corrosion inhibitor, from the viewpoint of further improving the corrosion resistance, compounds represented by the following general formula (A) to general formula (C), substituted or unsubstituted tetrazole, maleic anhydride, phthalic anhydride, fructose Ammonium thiosulfate, tetramethylguanidine, gallic acid ester, 2-mercapto-5-methylbenzimidazole, 2-mercaptothiazoline, 3- (2-aminophenylthio) -2-hydroxypropylmercaptan, and 3- (2-) It is preferable that it is at least one selected from hydroxyethylthio) -2-hydroxypropyl mercaptan. Especially, the compound represented by the following general formula (B) or general formula (C) is more preferable.

In General Formula (A), R ^{1A to} R ^5A each independently represent a hydrogen atom, a hydrocarbon group, a hydroxy group, a carboxy group, or a substituted or unsubstituted amino group. However, the structure contains at least one group selected from a hydroxy group, a carboxy group and an amino group.
In general formula (B), R ^{1B to} R ^5B each independently represent a hydrogen atom, a hydroxy group or a hydrocarbon group.
In formula (C), R ^1C , R ^2C and R ^N each independently represent a hydrogen atom or a hydrocarbon group. Also, R ^1C and R ^2C may combine to form a ring.
In the general formulas (A) to (C), the hydrocarbon group may have a substituent.

In the above general formula (A), as a hydrocarbon group represented by R ^{1A to} R ^5A , an alkyl group (the number of carbon atoms is preferably 1 to 12, more preferably 1 to 6, still more preferably 1 to 3), alkenyl Group (carbon number is preferably 2 to 12 and more preferably 2 to 6), alkynyl group (carbon number is preferably 2 to 12 and more preferably 2 to 6), aryl group (carbon number is 6 to 6) 22 is preferable, 6-14 is more preferable, 6-10 is further preferable, and an aralkyl group (the carbon number is preferably 7-23, more preferably 7-15, further preferably 7-11). Be
Moreover, as a substituent, for example, a hydroxy group, a carboxy group, or a substituted or unsubstituted amino group (as a substituent, an alkyl group having 1 to 6 carbon atoms is preferable, and an alkyl having 1 to 3 carbon atoms) Groups are more preferable).
In the general formula (A), a hydroxy group, a carboxy group and a substituted or unsubstituted amino group in the structure (as a substituent, an alkyl group having 1 to 6 carbon atoms is preferable, and 1 to 3 carbon atoms) And at least one group selected from the group consisting of

In the general 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, a hydroxy group and a carboxy group. Or a hydrocarbon group having 1 to 6 carbon atoms substituted with an amino group, and the like.
Examples of the compound represented by the general formula (A) include 1-thioglycerol, L-cysteine, thiomalic acid, and 3-mercapto-1,2-propanediol.

In the general formula (B), the hydrocarbon group and the substituent represented by R ^{1B to} R ^5B are the same as the hydrocarbon and the substituent represented by R ^{1A to} R ^5A in the general formula (A) described above, respectively. . Examples of the substituted or unsubstituted hydrocarbon group represented by R ^{1B to} R ^5B include hydrocarbon groups having 1 to 6 carbon atoms such as methyl group, ethyl group, propyl group, and t-butyl group. Be
Examples of the compound represented by formula (B) include catechol, t-butyl catechol, resorcinol, phenol, and pyrogallol.

As the hydrocarbon group and the substituent represented by R ^1C , R ^2C and R ^N in the general formula (C), the hydrocarbon and the substituent represented by R ^{1A to} R ^5A in the general formula (A) described above are respectively It is synonymous. Examples of the substituted or unsubstituted hydrocarbon group represented by R ^1C , R ^2C and R ^N include hydrocarbon groups having 1 to 6 carbon atoms such as methyl, ethyl, propyl and butyl. Be
In addition, R ^1C and R ^2C may combine to form a ring, and examples thereof include 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, a carboxy group, etc.).
Examples of the compound represented by the general formula (C) include 1H-1,2,3-triazole, benzotriazole, and carboxybenzotriazole 5-methyl-1H-benzotriazole.

  As a substituted or unsubstituted tetrazole, for example, unsubstituted tetrazole, and a hydroxy group as a substituent, a carboxy group, or a substituted or unsubstituted amino group (as a substituent, an alkyl group having 1 to 6 carbon atoms) Is preferable, and tetrazole having an alkyl group having 1 to 3 carbon atoms is more preferable.

  The content of the corrosion inhibitor in the treatment liquid is preferably 0.01 to 10% by mass, more preferably 0.05 to 5% by mass, based on the total mass of the treatment liquid. More preferably, it is 1 to 1% by mass.

(Chelating agent)
The treatment liquid of the present invention may further contain a chelating agent. The chelating agent chelates the oxidized metal contained in the residue. Therefore, the addition of the chelating agent further improves the recyclability. The term "recyclability" as used herein means that the treatment liquid can be repeatedly reused, as described later.
The chelating agent is not particularly limited, but is preferably polyaminopolycarboxylic acid.
The polyaminopolycarboxylic acid is a compound having a plurality of amino groups and a plurality of carboxylic acid groups. Examples of polyaminopolycarboxylic acids include mono- or polyalkylenepolyaminepolycarboxylic acids, polyaminoalkanepolycarboxylic acids, polyaminoalkanol polycarboxylic acids, and hydroxyalkyl ether polyamine polycarboxylic acids.

  Examples of polyaminopolycarboxylic acids include butylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid (DTPA), ethylenediaminetetrapropionic acid, triethylenetetramine hexaacetic 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, diaminopropane tetraacetic acid, 1,4,7,10-tetraazacyclododecane-tetraacetic acid , Diaminopropanol tetraacetic acid, and (hydroxyethyl ) Ethylenediamine triacetic acid, and the like. Among them, diethylenetriaminepentaacetic acid (DTPA), ethylenediaminetetraacetic acid (EDTA), or trans-1,2-diaminocyclohexanetetraacetic acid is preferable. These compounds can be blended alone or in combination of two or more.

  The content of the chelating agent in the treatment liquid is preferably 0.01 to 10% by mass, and more preferably 0.1 to 5% by mass, with respect to the total mass of the treatment liquid.

(Fe ion, Co ion)
The treatment liquid of the present invention preferably contains a trace amount of at least one ion selected from Fe ions and Co ions.
The content of Fe ions in the treatment solution is preferably 1 mass ppt to 10 mass ppm, more preferably 1 mass ppt to 1 mass ppm, and 1 mass ppt with respect to the total mass of the treatment liquid. More preferably, it is 1 mass ppb. By adjusting the content of Fe ions in the treatment solution to the above range, the residue removal performance and the corrosion prevention performance to the treatment object are further improved, and further, foreign matter adhesion to the treatment object and foreign matter Pattern defects caused as a result can be further reduced. Moreover, it is confirmed that it is excellent also in the recycling property of a processing liquid, and temporal stability by making content of Fe ion in a processing liquid into said range.

The content of Co ions in the treatment liquid is preferably 1 mass ppt to 10 mass ppm, and more preferably 1 mass ppt to 1 mass ppm, with respect to the total mass of the treatment liquid. By adjusting the content of Co ions in the treatment solution to the above range, the residue removal performance and the corrosion prevention performance for the treatment object are further improved, and further, foreign matter adhesion to the treatment object and foreign matter are eliminated. Pattern defects caused as a result can be further reduced. In addition, by setting the content of Co ions in the processing solution in the above range, it is also confirmed that the recyclability (particularly when using a substrate containing Co as a processing target) and the temporal stability are excellent. There is.
The content of Fe ions and Co ions with respect to the total mass of the treatment liquid in the treatment liquid can be measured by an inductively coupled plasma mass spectrometer (for example, Agilent 7500 cs manufactured by Yokogawa Analytical Systems).

<Counter to be counted>
In the treatment liquid of the present invention, the number of objects to be counted with a size of 0.05 μm or more, counted by a light scattering type liquid-in-liquid counter, is 1 to 2000 per 1 ml of treatment liquid.
Here, the object to be counted of the present invention is not particularly limited as long as it is detected as a size of 0.05 μm or more by the light scattering type liquid-in-liquid counter.
The light scattering type liquid particle counter emits a light beam to a sample fluid (processing liquid in the present invention) to form a particle detection area, and receives scattered light from the object to be counted which passes through the particle detection area. Light is received by means to detect the objects to be counted in the sample fluid, and the number of objects to be counted is counted.
The light scattering type liquid-in-liquids counter detects not only solid matter but also bubbles and the like containing gas (dissolved oxygen etc.) as an object to be counted.
Specifically, the object to be counted in the present invention is an impurity (for example, solid matter such as dust, dust, organic solid matter, and inorganic solid matter) contained in the raw material of the treatment liquid, and a contaminant during preparation of the treatment liquid Impurities (eg, solid matter such as dust, dirt, organic solid matter, inorganic solid matter, etc.) brought in as, air bubbles mixed in with the raw material of the treatment liquid, and air bubbles mixed in during the preparation of the treatment liquid, etc. Be done.

  As the light scattering type liquid particle counter, an apparatus according to liquid particle counter "KS-18F" (manufactured by Rion Co., Ltd.) is used. The measurement conditions of the treatment liquid by the light scattering type liquid-in-liquid counter are as described in the Examples section described later.

The number of objects to be counted with a size of 0.05 μm or more contained in the treatment liquid of the present invention is 1 to 2000 per 1 mL, preferably 1 to 1000, and preferably 1 to 500. The number is more preferably 1 to 300, and particularly preferably 10 to 100.
When the number of the objects to be counted is in the above range, the residue removal performance and the corrosion prevention performance of the treatment liquid are excellent. Furthermore, foreign matter adhesion to the substrate after processing and pattern defects resulting from the foreign matter can be reduced, and yield reduction of the processing object can be suppressed.

In the present invention, the size of the object to be counted counted by the light scattering type liquid-in-liquid counter is a size of 0.05 μm or more.
In addition, detection of a target object having a size of less than 0.05 μm involves technical difficulties.

It is preferable that the process liquid of this invention does not contain the particle | grains (specifically, coarse particles, such as an impurity etc.) of 0.1 micrometer or more in view of the use application. Thereby, it can suppress that the coarse particle contained in process liquid itself becomes a residue.
As a method of removing coarse particles, for example, processing such as filtering described later may be mentioned. In addition, particles of 10 μm or more can be measured using a laser diffraction type particle size distribution measuring apparatus.

<Other additives>
Other additives may be contained in the treatment liquid of the present invention as long as the effects of the present invention are exhibited. Other additives include, for example, surfactants, antifoaming agents, pH adjusters, and fluorides.

[Method of producing treatment liquid]
The treatment liquid of the present invention is not particularly limited for its production method. It can manufacture by fully mixing predetermined raw materials using stirrers, such as a mixing mixer.

The treatment liquid of the present invention has a predetermined number of objects to be counted, each having a size of 0.05 μm or more, counted by a light scattering type liquid particle counter after mixing predetermined raw materials, to a predetermined number per ml. It is preferable to have a process. The step for setting the number of objects to be counted with a size of 0.05 μm or more, counted by a light scattering type liquid-in-liquid counter, is a purification step such as filtration using a filter at the same time or At any time, the number of objects to be counted is counted by a light scattering type liquid particle counter, and the preparation of the treatment solution is terminated when the number of objects to be counted contained in the treatment solution reaches a desired value, etc. Can be implemented by As a filter used for filtration of the treatment liquid of the present invention, it is possible to efficiently remove an object to be counted which is often negatively charged in the treatment liquid of the present invention containing an alkali compound and water. In terms of point, positively charged nylon filters are preferred.
In addition, counting of the objects to be counted by the light scattering type liquid particle counter may be performed batchwise or inline type, that is, the light scattering type liquid particle counter is incorporated into the processing liquid production line to be continuous. You may count it.
In general, the number of objects to be counted with a size of 0.05 μm or more, which are counted by a light scattering type liquid-in-liquid counter, is generally more than 2000 per 1 ml of treatment liquid.

<Kit and Concentrate>
The treatment liquid of the present invention may be a kit obtained by dividing the raw material into a plurality of parts. For example, a liquid composition containing, as a first liquid, at least one hydroxylamine compound selected from hydroxylamine and hydroxylamine salt in a solvent is prepared, and a liquid composition containing another component as a second liquid is contained. The aspect to prepare is mentioned. As an example of its use, an embodiment is preferable in which both solutions are mixed to prepare a treatment solution, and then the solution is applied to the treatment in a timely manner. By doing so, the desired performance can be effectively exhibited without causing deterioration in liquid performance due to decomposition of the hydroxylamine compound or other components. 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.
Also, the treatment liquid may be prepared as a concentrate. In this case, it can be used by diluting with a solvent at the time of use.

<Container>
The treatment liquid of the present invention can be stored, transported, and used in any container, as long as corrosion and the like do not matter (whether or not it is a kit). The container is preferably one having high cleanliness and low elution of impurities for semiconductor applications. Examples of usable containers include, but are not limited to, “Clean Bottle” series manufactured by Icero Chemical Co., Ltd., “Pure Bottle” manufactured by Kodama Resin Industry Co., Ltd., and the like. The inner wall of the container or the container thereof is treated with a resin different from one or more resins selected from the group consisting of polyethylene resin, polypropylene resin, and polyethylene-polypropylene resin, or subjected to rust and metal elution prevention treatment. It is preferable to form from the metal which is
As the above different resin, a fluorine-based resin (perfluoro resin) can be particularly preferably used. As described above, by using the container in which the inner wall of the storage unit is a fluorine-based resin, ethylene and the inner wall of the storage unit are compared to the case using a container in which the polyethylene resin, polypropylene resin, or polyethylene-polypropylene resin is used. It is possible to suppress the occurrence of problems such as elution of propylene oligomers.
As a specific example of a container in which the inner wall of such a container part is a fluorine-based resin, for example, a FluoroPure PFA composite drum manufactured by Entegris can be mentioned. Also, the containers described on page 4 of JP-A-3-5026, page 3 of WO 2004/016526, etc. and pages 9 and 16 of WO 99/46309 etc. It can be used.

<Filtering>
The treatment liquid of the present invention is preferably filtered with a filter for the purpose of adjusting the number of objects to be counted to a desired number, and for the purpose of removing foreign matter or reducing defects.
The material of the filter is not particularly limited as long as it is conventionally used for filtration applications etc. For example, a fluorocarbon resin such as PTFE (polytetrafluoroethylene), a polyamide such as nylon, etc. Examples thereof include filters made of resins, and polyolefin resins (including high density and ultrahigh molecular weight) such as polyethylene and polypropylene (PP). Among these materials, polyethylene, polypropylene (including high density polypropylene), or nylon is preferable.
The pore diameter of the filter is preferably about 2 to 20 nm. By setting this range, it is possible to reliably remove fine foreign substances such as impurities and aggregates contained in the liquid while suppressing filter clogging.
When using filters, different filters may be combined.
At that time, filtering in each filter may be performed only once or may be performed twice or more. The two or more times of filtering means, for example, a case where the solution is circulated and the two or more times of filtering is performed by the same filter.

The filtering can also be performed by combining different filters as described above. When different filters are combined to perform filtering twice or more, it is preferable that the second and subsequent pore sizes be the same or smaller than the pore size of the first filtering. The first filters of different pore sizes may be combined within the range described above. The pore size here can refer to the nominal value of the filter manufacturer. As a commercially available filter, it is possible to select, for example, from various filters provided by Nippon Pall Co., Advantec Toyo Co., Ltd., Nippon Entegris Co., Ltd. (old Japan Microlith Co., Ltd.) or Kitz Micro Filter Co., Ltd.
The second filter can use a filter formed of the same material as the first filter described above. The pore diameter of the second filter is preferably about 1 to 10 nm. By setting it as this range, when the component particle is contained in the liquid, the foreign material mixed in the liquid can be removed with the component particle remaining.
For example, only a part of the components of the treatment solution to be finally prepared is mixed in advance to prepare a mixed solution, and the mixed solution is filtered by a first filter, and then the mixture is filtered by the first filter. The remaining components for forming the treatment solution may be added to the filtered mixture, and the mixture may be subjected to a second filtering.

<Metal concentration>
The treatment liquid of the present invention contains ions of metals (Na, K, Ca, Cu, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn, metal elements) other than Fe and Co contained as impurities in the liquid. The concentration is preferably 5 ppm or less (preferably 1 ppm or less). In particular, since it is assumed that a processing solution with higher purity is required in the manufacture of the most advanced semiconductor device, the metal concentration is lower than the ppm order, that is, less than the ppb order. More preferably, it is further preferred that the order is ppt (the above-mentioned concentrations are all based on mass), and it is particularly preferred that the composition is substantially free.

As a method for reducing the metal concentration, for example, a distillation and / or ion exchange resin is used in at least one of the stages of raw materials used in producing the treatment liquid and the stage after preparation of the treatment liquid. And sufficient filtration.
Another method of reducing the metal concentration is to use a container with a small amount of elution of impurities, as described in the section <Container> above, for the “container” that contains the raw materials used for producing the treatment liquid. Can be mentioned. Another example is a method of lining the inner wall of the pipe with a fluorine-containing resin so that the metal component does not elute from the "pipe" or the like at the time of preparation of the treatment liquid.

<Use>
The treatment liquid of the present invention is a treatment liquid for semiconductor devices. In the present invention, "for semiconductor devices" means that they are used in the manufacture of semiconductor devices. The processing liquid of the present invention can be used in any process for manufacturing a semiconductor device, and besides the cleaning and removing use of the dry etching residue and / or the dry ashing residue adhering to the substrate described above, For example, it can also be used as a stripping solution application. The form used as a stripping solution refers to a solution for removing various resist films for pattern formation, and removal from semiconductor substrates such as permanent films (for example, color filters, transparent insulating films, lenses made of resin, etc.) It corresponds to the case of using as a solution for Note that since the semiconductor substrate after removal of the permanent film may be used again for use of the semiconductor device, removal of the permanent film is included in the manufacturing process of the semiconductor device.
Among these, particularly, a substrate provided with a metal hard mask including any one or more of Cu, Co, W, AlOx, AlN, AlOxNy, WOx, Ti, TiN, ZrOx, HfOx and TaOx (hereinafter referred to as "mask" Can be suitably used for cleaning and removing the dry etching residue and the dry ashing residue attached to the substrate.

[Method of cleaning substrate]
The method for cleaning a substrate of the present invention
Process liquid preparation process A which prepares the above-mentioned process liquid,
A cleaning process for cleaning a substrate provided with a metal hard mask containing at least one of Cu, Co, W, AlOx, AlN, AlOxNy, WOx, Ti, TiN, ZrOx, HfOx and TaOx using the above processing solution And B. In addition, it is a number represented by x = 1-3, y = 1-2.

<Washing object>
The objects to be cleaned in the method for cleaning a substrate according to the present invention include Cu, Co, W, WOx, AlOx, AlN, AlOxNy, Ti, TiN, ZrOx, HfOx and TaOx (x = 1 to 3, y = 1 to 2) The substrate is not particularly limited as long as it is a substrate provided with a metal hard mask containing any at least one of the above.
The metal hard mask is formed in a pattern and has a predetermined opening.

The object to be cleaned of the method for cleaning a substrate of the present invention may be, for example, a laminate having a metal film, an interlayer insulating film, and a metal hard mask at least in this order on the substrate. The laminate further has a hole formed toward the substrate from the surface (opening) of the metal hard mask so as to expose the metal film surface by the dry etching process and the like.
The method for producing a laminate having holes as described above is not particularly limited, but in general, with respect to a pre-processed laminate having a substrate, a metal film, an interlayer insulating film, and a metal hard mask in this order, The dry etching process is performed using the metal hard mask as a mask, and the interlayer insulating film is etched to expose the surface of the metal film, thereby providing holes penetrating through the metal hard mask and the interlayer insulating film. Be
In addition, the manufacturing method in particular of a metal hard mask is not restrict | limited, For example, the metal film containing a predetermined | prescribed component is formed, and the resist film of a predetermined | prescribed pattern is formed on it. Next, there is a method of manufacturing a metal hard mask by etching a metal film using a resist film as a mask.
In addition, the laminate may have layers other than the above-mentioned layers, and examples thereof include an etching stop film, an antireflection layer, and the like.

FIG. 1 is a schematic cross-sectional view showing an example of a laminate which is an object to be cleaned in the substrate cleaning method of the present invention.
A laminate 10 shown in FIG. 1 includes a metal film 2, an etching stopper layer 3, an interlayer insulating film 4 and a metal hard mask 5 in this order on a substrate 1, and a metal at a predetermined position by a dry etching process and the like. A hole 6 is formed to expose the film 2. That is, the cleaning target shown in FIG. 1 includes the substrate 1, the metal film 2, the etching stop layer 3, the interlayer insulating film 4 and the metal hard mask 5 in this order, and the opening of the metal hard mask 5. At the position of the hole, the hole 6 penetrating from the surface to the surface of the metal film 2. The inner wall 11 of the hole 6 is composed of a cross-sectional wall 11a consisting of the etching stopper layer 3, the interlayer insulating film 4 and the metal hard mask 5 and a bottom wall 11b consisting of the exposed metal film 2; It is attached.

The method for cleaning a substrate of the present invention can be suitably used for cleaning for the purpose of removing these dry etching residues 12. That is, while being excellent in the removal performance of the dry etching residue 12, it is excellent also in the corrosion prevention performance with respect to the inner wall 11 (for example, metal film 2 grade | etc., Of a cleaning subject).
In addition, the method for cleaning a substrate of the present invention may be performed on a laminate on which a dry ashing process has been performed after a dry etching process.
Hereinafter, each layer constituent material of the laminated body mentioned above is demonstrated.

(Metal hard mask)
The metal hard mask is Cu, Co, W, AlOx, AlN, AlOxNy, WOx, Ti, TiN, ZrOx, HfOx and TaOx (numbers represented by x = 1 to 3, y = 1 to 2). It is not particularly limited as long as it contains at least one of them. Here, x and y are numbers represented by x = 1 to 3 and y = 1 to 2, respectively.
Examples of the material of the metal hard mask include TiN, WO ₂ and ZrO ₂ .

(Interlayer insulating film)
The material of the interlayer insulating film is not particularly limited. For example, preferably, the dielectric constant k is 3.0 or less, more preferably 2.6 or less.
Specific examples of the material of the interlayer insulating film include silicon-based materials such as SiO ₂ and SiOC, and organic-based polymers such as polyimide.

(Etching stop layer)
The material of the etching stopper layer is not particularly limited. Specific examples of the material of the etching stop layer include silicon-based materials such as SiN, SiON, and SiOCN, and metal oxides such as AlOx.

(Metal film)
The wiring material for forming the metal film is not particularly limited, and examples thereof include metals, metal nitrides, and alloys. Specifically, for example, copper, titanium, titanium-tungsten, titanium nitride, tungsten, cobalt, tantalum, a tantalum compound, chromium, chromium oxide, aluminum and the like can be mentioned. From the viewpoint of achieving the effects of the treatment liquid of the present invention, cobalt or copper is particularly preferable as the wiring material.

(substrate)
The term "substrate" as used herein includes, for example, a semiconductor substrate composed of a single layer and a semiconductor substrate composed of multiple layers.
The material constituting the semiconductor substrate consisting of a single layer is not particularly limited, and generally, it may be composed of a group III-V compound such as silicon, silicon germanium, and GaAs, or any combination thereof. preferable.
In the case of a multi-layered semiconductor substrate, its configuration is not particularly limited, for example, exposed integrated features such as interconnects such as metal lines and dielectric materials on a semiconductor substrate such as silicon described above It may have a circuit structure. Metals and alloys used in the interconnect structure include, but are not limited to, aluminum, aluminum alloyed with copper, copper, titanium, tantalum, cobalt and silicon, titanium nitride, tantalum nitride, tungsten etc. It is not a thing. In addition, layers such as an interlayer dielectric layer, silicon oxide, silicon nitride, silicon carbide, and carbon-doped silicon oxide may be provided on a semiconductor substrate.

The treatment liquid preparation step A and the washing step B will be described in detail below.
(Processing solution preparation step A)
The treatment liquid preparation step A is a step of preparing the treatment liquid.
The procedure of this step is not particularly limited, and, for example, a method of preparing a treatment liquid by adding a hydroxylamine compound, a nitrogen-containing compound, and other optional components to a solvent selected from water and an organic solvent and stirring and mixing. Can be mentioned. In addition, when adding each component to a solvent, you may add collectively and may divide and add over multiple times.
Moreover, it is preferable to use what is classified into a semiconductor grade, or each classified into a high purity grade according to it as each component contained in a process liquid. In addition, with respect to the component having many impurities at the time of the raw material, it is preferable to use one that has been subjected to removal of foreign matter by filtering and / or ion component reduction by an ion exchange resin or the like.
Furthermore, it is preferable to carry out the above-mentioned processing such as filtering so that the number of the objects to be counted contained in the treatment liquid falls within a desired range.

(Washing process B)
Examples of the mask-attached substrate to be cleaned in the cleaning step B include the above-described laminate, and as described above, the laminate having the hole subjected to the dry etching step is exemplified. The dry etching residue adheres to the inside of the hole on this laminate.
Note that the laminate subjected to the dry ashing process after the dry etching process may be an object to be cleaned.

  The method for bringing the processing solution into contact with the mask-provided substrate is not particularly limited. For example, the method for immersing the mask-provided substrate in the treatment liquid placed in a tank, the method for spraying the treatment liquid onto the mask-provided substrate, the mask-provided substrate Methods of flowing the treatment solution, and any combination thereof. From the viewpoint of removing the residue, a method of immersing the substrate with a mask in the treatment liquid is preferable.

  The temperature of the treatment liquid is preferably 90 ° C. or less, more preferably 25 to 80 ° C., still more 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 treatment liquid.
In the case of washing by the immersion batch method (batch method in which a plurality of objects to be cleaned are immersed and treated in the treatment tank), for example, it is within 60 minutes, preferably 1 to 60 minutes, and preferably 3 to 20 minutes. Is more preferably 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, and more preferably 15 seconds to 3 minutes, and 20 seconds to 5 minutes. More preferably, it is 2 minutes.

Furthermore, a mechanical stirring method may be used to further enhance the cleaning ability of the processing solution.
As a mechanical stirring method, for example, a method of circulating the treatment liquid on a mask-coated substrate, a method of passing or spraying the treatment liquid on the mask-coated substrate, and stirring the treatment liquid by ultrasonic waves or megasonics Methods etc.

(Rinse process B2)
The method for cleaning a substrate according to the present invention may further include, after the cleaning step B, a step (rinsing step B2) of cleaning the substrate with mask with a solvent for cleaning.
The rinse step B2 is performed continuously to the washing step B, and is preferably a step of rinsing with a rinse solvent for 5 seconds to 5 minutes. The rinsing step B2 may be performed using the above-mentioned mechanical stirring method.
The treatment liquid described above may be used as a rinse solvent in the rinse step B2.

Examples of rinse solvents include deionized (DI: De Ionize) water, methanol, ethanol, isopropyl alcohol, N-methyl pyrrolidinone, γ-butyrolactone, dimethyl sulfoxide, ethyl lactate and propylene glycol monomethyl ether acetate. It is not limited to Alternatively, aqueous rinses with pH> 8 (such as dilute aqueous ammonium hydroxide) may be used.
As the rinse solvent, ammonium hydroxide aqueous solution, DI water, methanol, ethanol or isopropyl alcohol is preferable, ammonium hydroxide aqueous solution, DI water or isopropyl alcohol is more preferable, ammonium hydroxide aqueous solution or DI More preferably, it is water.
As a method for bringing the rinse solvent into contact with the substrate with a mask, the method for bringing the treatment liquid into contact with the substrate with a mask can be similarly applied.
It is preferable that the temperature of the rinse solvent in rinse process B2 is 16-27 degreeC.

(Drying process B3)
The method for cleaning a substrate of the present invention may have a drying step B3 of drying the substrate with mask after the rinsing step B2.
The drying method is not particularly limited. As a drying method, for example, a spin drying method, a method of letting dry gas flow on a substrate with a mask, a method of heating a substrate by a heating means such as a hot plate or an infrared lamp, a marangoni drying method, a rotagoni drying method, IPA (Isopropyl alcohol) drying methods, or any combination thereof.
The drying time depends on the particular method used but is generally preferred to be 30 seconds to a few minutes.

(Metal ion removal process F, G)
In the method for cleaning a substrate of the present invention, metal ions are removed prior to the above-mentioned treatment liquid preparation step A, by removing at least one ion species selected from Fe ions and Co ions from at least one of hydroxylamine compounds and solvents. A metal which has a step F or which removes at least one ion species selected from Fe ions and Co ions in the treatment liquid after the treatment liquid preparation step A and before performing the washing step B It is preferable to have the ion removal step G.
By carrying out the metal ion removal step F or the metal ion removal step G, the content of Fe ions in the treatment liquid used in the washing step B is 1 mass ppt to 10 mass ppt with respect to the total mass of the treatment liquid It is preferable to be adjusted to Similarly, the content of Co ions in the treatment liquid is also preferably adjusted to 1 mass ppt to 10 mass ppt with respect to the total mass of the treatment liquid. In addition, about the suitable range of content of Fe ion and content of Co ion in a process liquid, it is as above-mentioned.
A specific method of the metal ion removal step F and the metal ion removal step G is not particularly limited, and examples thereof include distillation and / or purification with an ion exchange membrane.
By adjusting the content of Fe ions and the content of Co ions in the treatment solution to the above range, the residue removal performance and corrosion prevention performance of the treatment solution are more excellent, and foreign matter adhesion to the object to be cleaned, etc. Can further reduce the influence of Furthermore, the recyclability and the temporal stability are more excellent.

(Coarse particle removal process H)
The method for cleaning a substrate according to the present invention preferably includes a coarse particle removal step H for removing coarse particles in the treatment liquid after the treatment liquid preparation step A and before performing the washing step B.
By reducing or removing coarse particles in the processing liquid, the amount of coarse particles remaining on the masked substrate after the cleaning step B can be reduced. As a result, it is possible to suppress pattern damage caused by coarse particles on the substrate with a mask, and to suppress the reduction in yield of devices and the reduction in reliability.
As a specific method for removing coarse particles, for example, a method of filtering and purifying a treatment liquid which has passed through the treatment liquid preparation step A using a particle removal membrane of a predetermined particle diameter and the like can be mentioned.
In addition, about the definition of coarse particle, it is as above-mentioned.

(Discharge process I, J)
The method for cleaning a substrate according to the present invention includes the charge removal step I for discharging the solvent before the treatment liquid preparation step A described above, or after the treatment liquid preparation step A and the washing step Before performing B, it is preferable to have the static elimination process J which neutralizes with respect to the said process liquid.
The treatment liquid of the present invention has a function of reducing metal since it contains a hydroxylamine compound. For this reason, it is desirable that the material of the liquid contact portion for supplying the processing liquid to the substrate with mask be a resin that does not cause metal elution to the processing liquid. Such a resin material has low electrical conductivity and is insulating. For example, when the above-mentioned treatment liquid is passed through a pipe made of resin, or by using a resin-made particle removal membrane and a resin-made ion exchange resin membrane In the case of filtration and purification, the charge potential of the treatment liquid may be increased to cause electrostatic damage.
Therefore, in the method of cleaning a substrate according to the present invention, it is preferable to carry out the above-described charge removal step I or charge removal step J to reduce the charge potential. Further, by removing the charge, it is possible to further suppress adhesion of foreign matter (coarse particles and the like) to the substrate and damage (corrosion) to the substrate to be processed.
Specifically as a static elimination method, the method of making a solvent or a process liquid contact a conductive material is mentioned.
0.001 to 1 second is preferable and, as for the contact time which makes a solvent and a process liquid contact an electroconductive material, 0.01 to 0.1 second is more preferable.
Specific examples of the resin include high density polyethylene (HDPE), high density polypropylene (PP), 6,6-nylon, tetrafluoroethylene (PTFE), a copolymer of tetrafluoroethylene and perfluoroalkyl vinyl ether (PFA) ), Polychlorotrifluoroethylene (PCTFE), ethylene / chlorotrifluoroethylene copolymer (ECTFE), ethylene / tetrafluoroethylene copolymer (ETFE), and tetrafluoroethylene / hexafluoropropylene copolymer (FEP) and the like.
As the conductive material, stainless steel, gold, platinum, diamond, glassy carbon or the like is preferable.

In the method for cleaning a substrate using the treatment liquid of the present invention, when the treatment liquid of the present invention has a composition having recyclability (in particular, the treatment liquid contains a chelating agent or Fe ions and Co ions in a predetermined numerical range). In the case where it is included, it is possible to reuse the drainage of the processing solution used in the cleaning step B and further to clean other masked substrates.
The method for cleaning a substrate according to the present invention preferably comprises the following steps, in the case of a mode in which the drainage of the treatment liquid is reused.
Process liquid preparation process A which prepares the said process liquid,
It is the number represented by Cu, Co, W, AlOx, AlN, AlOxNy, WOx, Ti, TiN, ZrOx, HfOx and TaOx (x = 1 to 3, y = 1 to 2) using the above processing solution. A cleaning step B for cleaning a substrate provided with a metal hard mask including at least one of
A drainage recovery step C for recovering the drainage of the treatment liquid used in the cleaning step B;
Cu, Co, W, AlOx, AlN, AlOxNy, WOx, Ti, TiN, ZrOx, HfOx, and TaOx (x = 1 to 3, y = 1) newly prepared using the drainage of the recovered treatment liquid And a cleaning step D for cleaning a substrate provided with a metal hard mask containing at least one of the following:
And a drainage recovery step E for recovering the drainage of the treatment liquid used in the cleaning step D,
The washing step D and the drainage recovery step E are repeatedly performed.

  In the aspect of recycling the drainage, the treatment liquid preparation step A and the washing step B have the same meaning as the treatment liquid preparation step A and the washing step B described in the above-mentioned aspect, and the same applies to the preferable aspect. In addition, in the embodiment in which the above-described drainage is reused, it is preferable to have the metal ion removing steps F and G, the coarse particle removing step H, and the static elimination steps I and J described in the above embodiment.

The cleaning step D in which the substrate cleaning is performed using the drainage of the recovered processing liquid is the same as the cleaning step B in the above-described embodiment, and the preferable embodiment is also the same.
The drainage recovery means in the drainage recovery steps C and E is not particularly limited. The collected waste liquid is preferably stored in the above-described resin container in the charge removal step J, and at this time, the same charge removal step as the charge removal step J may be performed.

  Further, a step of adjusting the number of the objects to be counted contained in the recovered processing liquid before the washing step D after at least one of the drainage recovery step C and the drainage recovery step E It is preferable to carry out. The adjustment of the number of objects to be counted can be performed, for example, by filtering the collected treatment liquid.

[Method of manufacturing a semiconductor device]
The method for manufacturing a semiconductor device according to the present invention includes at least one selected from Cu, Co, W, AlOx, AlN, AlOxNy, WOx, Ti, TiN, ZrOx, HfOx, and TaOx by the above-described processing solution according to the present invention Including a cleaning step of cleaning the substrate with the metal hard mask. In addition, it is a number represented by x = 1-3, y = 1-2.
The method for manufacturing a semiconductor device of the present invention only needs to include at least the cleaning step, and the cleaning step is the same as the cleaning step B described above, and the preferred embodiment is also the same. The method of manufacturing a semiconductor device includes steps other than the cleaning step, and may include, for example, the above-described rinse step B2 and drying step B3.
Generally, after the cleaning step, after the metal hard mask which has become unnecessary is removed, one or more additional circuits are further formed on the substrate, or, for example, assembly (for example, dicing and bonding) And mounting (for example, chip sealing) are performed to form a semiconductor chip or the like.
As a semiconductor device, a flash memory, a logic device, etc. are mentioned, for example.

  Hereinafter, the present invention will be described in more detail based on examples. The materials, amounts used, proportions, treatment contents, treatment procedures and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Accordingly, the scope of the present invention should not be construed as limited by the following examples.

(1) Preparation of Treatment Liquid The treatment liquids (Examples 1 to 36, Comparative Examples 1 to 9) shown in Tables 1 and 2 were prepared. In each treatment liquid, the concentration of each of the various components used (in each case based on mass) is as described in the table. However, when Fe ions or Co ions are contained in the treatment liquid, the content of water as a solvent was adjusted so that the total amount of the treatment liquid was 100% by mass.

Here, each component shown in Table 1, Table 2, and Table 3 used what was classified into the semiconductor grade, or the thing classified into the high purity grade according to it.
In addition, with respect to the component having many impurities at the time of the raw material, foreign matter removal by filtering and / or ion component reduction by ion exchange resin or the like were performed.
The amount of Fe ions and the amount of Co ions in the treatment solutions shown in Examples in Table 1 and Table 2 and Comparative Examples were confirmed to be 10 ppm or less excluding Examples 18 to 21. Also, the amounts of Fe ions and Co ions described in Table 3 may be such that the hydroxylamine compound and solvent contained in the treatment solution are purified (metal ion removal step F), and / or the treatment solution after preparation is purified (The metal ion removal step G) was adjusted to the desired amount. Specifically, at a flow rate of 0.3 to 0.6 L / min for an ion exchange resin membrane (Nihon Pall Co., Ltd. Ion Clean SL product No. DFA1SRPESW44, surface area of membrane 1100 cm ² , number of filters: 1 to 2) It adjusted by pouring. The content of Fe ions and Co ions relative to the total mass of the treatment liquid in the treatment liquid was measured by an inductively coupled plasma mass spectrometer (manufactured by Yokogawa Analytical Systems, Agilent 7500cs type).

  The "water" used by the process liquid of a present Example and a comparative example used what was prepared using the method as described in stage of Unexamined-Japanese-Patent No. 2011-110515 using the method described in [0084]. In addition, this method includes a metal ion removal step, and it was confirmed that the amount of Fe ions and the amount of Co ions were each less than 1 mass ppt. The content of Fe ions and Co ions contained in water was measured by an inductively coupled plasma mass spectrometer (manufactured by Yokogawa Analytical Systems, Agilent 7500cs type).

In addition, about the above-mentioned process liquid, the liquid mixture obtained by mixing each component is refine | purified by circulation filtration, and after leaving still at room temperature for 1 day, light scattering type particle | grains in a liquid based on a dynamic light scattering method Using a counter (Rion Co., Ltd., model number: KS-18F, light source: semiconductor laser excited solid laser (wavelength 532 nm, rated output 500 mW), flow rate: 10 ml / min), contained in 1 ml of mixed solution 0.05 μm The count of the to-be-counted body of the above size was performed 5 times, and the average value was made into the measured value.
When the number of objects to be counted contained in the mixed solution reached a desired value, the mixed solution was filled in a recovery container (clean bottle manufactured by Eisero Chemical Co., Ltd.). The mixed solution thus filled in the recovery container was used as each treatment solution of the example and the comparative example. In addition, the size of the to-be-counted body contained in the process liquid adjusted by said method was 0.05 micrometer or more and less than 0.1 micrometer.
Here, the light scattering type in-liquid particle counter was used after being calibrated with a PSL (Polystyrene Latex) standard particle liquid. Also, the number of counted objects to be counted is shown in Table 1, Table 2 and Table 3 as "the number of objects to be counted in liquid".

The various components used for the process liquid are shown below.
<Reductant>
HA: hydroxylamine (manufactured by BASF)
HAS: hydroxyl ammonium sulfate (manufactured by BASF)
N, N-diethylhydroxylamine (Wako Pure Chemical Industries, Ltd.)

<Compound Represented by General Formula (1)>
MEA: Monoethanolamine (made by Tokyo Chemical Industry Co., Ltd.)
Diglycolamine (made by Tokyo Chemical Industry Co., Ltd.)

<Compound Represented by General Formula (2)>
TMAH: tetramethyl ammonium hydroxide (made by Seichem)
TBAH: Tetrabutylammonium hydroxide (made by Seichem)
Colin: made by Seychem

<Organic solvent>
EGBE: ethylene glycol butyl ether (manufactured by Wako Pure Chemical Industries, Ltd.)
DEGBE: diethylene glycol monobutyl ether (manufactured by Wako Pure Chemical Industries, Ltd.)
DMSO: dimethyl sulfoxide (manufactured by Wako Pure Chemical Industries, Ltd.)
PG: Propylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.)

<Corrosion inhibitor>
5-methyl-1H-benzotriazole (corresponding to general formula (C), manufactured by Tokyo Chemical Industry Co., Ltd. (corresponding to 5M-BTA in the table))
Benzotriazole (corresponding to general formula (C), manufactured by Tokyo Chemical Industry Co., Ltd. (corresponding to BTA in the table))
Catechol (equivalent to general formula (B), manufactured by Kanto Chemical Co., Ltd.)
1H-1,2,3-triazole (corresponding to general formula (C), manufactured by Tokyo Chemical Industry Co., Ltd. (corresponding to 1,2,3-triazole in the table))
4-tert-butyl catechol (corresponding to general formula (B), manufactured by Kanto Chemical Co., Ltd. (corresponding to t-butyl-catechol in the table))

Chelating agent
DPTA: Diethylenetriaminepentaacetic acid (manufactured by Chubu Kyrest Co., Ltd.)
EDTA: ethylenediaminetetraacetic acid (manufactured by Chubu Kyrest Corporation)

(2) Evaluation The various evaluations shown below were performed about each processing solution prepared above.
<Evaluation of residue removal performance>
Evaluation of the residue removal performance was performed using each prepared treatment liquid. In the following evaluation, a model film made of TiO ₂ which is a kind of residue generated when plasma etching MHM (metal hard mask) is prepared, and the etching rate is evaluated to evaluate the residue removal performance. Was evaluated. That is, when the etching rate is high, the residue removal performance is excellent, and when the etching rate is low, the residue removal performance is inferior.
Incidentally, the model layer (TiO ₂ layer) made of TiO ₂ is provided with a film thickness of 1000Å on a Si substrate.

After preparing each processing solution of the example and the comparative example, the etching process of the TiO ₂ film was performed. Specifically, the TiO ₂ film was immersed for 5 minutes in the treatment solutions of Examples and Comparative Examples, and the etching rate (Å / minute) was calculated based on the difference in film thickness before and after immersion of the treatment solution.
In addition, the film thickness of the TiO ₂ film before and after the treatment is a measurement range of 250 to 1000 nm and a measurement angle of 70 using ellipsometry (spectroscopic ellipsometer, trade name "Vase", manufactured by JA Woollam Japan). It measured on the conditions of degree and 75 degrees.
The calculated etching rate (ER) of the TiO ₂ film was evaluated according to the following evaluation criteria. In addition, in the following evaluation criteria, if it is AC, the requirements on practical use will be satisfy | filled.
"A": 5 (Å / min) <ER
“B”: 3 (Å / min) <ER ≦ 5 (Å / min)
“C”: 1 (Å / min) <ER ≦ 3 (Å / min)
“D”: ER ≦ 1 (Å / min)

<Corrosion prevention performance (Co anticorrosion ability, Cu anticorrosion ability)>
After preparing each processing liquid of an Example and a comparative example, etching processing was performed about each Co film and Cu film (model film of metal used as electrode materials, such as wiring). Specifically, each film is immersed for 10 minutes in the treatment liquid of the example and the comparative example, and the amount of change in sheet resistance (Ω / □) before and after immersion in the treatment liquid (( Sheet resistance value-(sheet resistance value of each film before immersion) was converted to a film thickness difference, and the corrosion prevention performance was evaluated by calculating the etching rate (Å / min). Evaluation criteria are as follows.
The sheet resistance value (Ω / □) is measured using a sheet resistance measuring instrument (manufactured by Hitachi Kokusai Electric Engineering Co., Ltd., model number: body VR-120S, four probe probe KS-TC-200-MT-200g) It was calculated based on the voltage value when a current of 30 mA was applied to each film.
When the change amount of the sheet resistance value is small, the corrosion prevention performance is excellent, and when the change amount of the sheet resistance value is high, the corrosion prevention performance is inferior. In addition, in the following evaluation criteria, if it is AC, the requirements on practical use will be satisfy | filled.
“A”: not dissolve at all “B”: ER ≦ 1 (Å / min)
“C”: 1 (Å / min) <ER ≦ 5 (Å / min)
“D”: 5 (Å / min) <ER ≦ 10 (Å / min)
"E": 10 (Å / min) <ER

<Number of treated substrate defects>
Next, after the silicon substrate of 300 mm in diameter was washed using each processing solution of the example and the comparative example, the number of particles (the number of substrate defects to be treated) adhered on the substrate after washing was measured.
Specifically, it is performed according to the following procedure and conditions using a light scattering type foreign matter inspection device (manufactured by KLA Tencor Co., model number: SP-1 TBI), and the number of surface defects after processing of a silicon substrate The difference (the number of defects increased) obtained by subtracting the initial number of surface defects of the silicon substrate was calculated as the number of substrate defects to be treated.
In the measurement of surface defects by the above light scattering type foreign matter inspection device, calibration was carried out using a silicon substrate coated with PSL standard particles, and the number of surface defects counted as 0.065 μm or more was counted.

(Procedure 1) Measure the initial number of surface defects of silicon substrate (Procedure 2) Set a silicon substrate to a spinner in a cleaning apparatus (Procedure 3) Process with processing solution shown in Example and Comparative example
(Procedure 4) Ultra pure water rinse 2 L / min, 1 min
(Procedure 5) N ₂ blow drying 50 NLM, 1 min
(Procedure 6) The number of surface defects after processing of the silicon substrate is measured. The evaluation criteria are as follows. In addition, in the following evaluation criteria, if it is AC, the requirements on practical use will be satisfy | filled.

“A”: defect increase number 10 / substrate or less “B”: defect increase number 11 to 100 / substrate “C”: defect increase number 101 to 1,000 / substrate “D”: defect increase number 1 , 001 to 2,000 pieces / substrate “E”: increase in number of defects 2,001 pieces / substrate or more

It was confirmed that the processing solutions of the examples shown in Tables 1 and 2 were all excellent in the residue removal performance and the corrosion prevention performance. Furthermore, it was confirmed that the object to be cleaned using the processing solution of the example has a small number of substrate defects (that is, adhesion of foreign matter is suppressed).
On the other hand, it was confirmed that all of the processing solutions of the comparative examples shown in Tables 1 and 2 can not establish the residue removal performance, the corrosion prevention performance, and the number of substrate defects.
Specifically, in Comparative Examples 1 to 4 of the system containing the compound represented by the general formula (2) as the nitrogen-containing compound, the number of objects to be counted in the treatment liquid in the liquid is 0 per 1 mL. In some cases, although the number of substrate defects was a good result, the residue removal performance and the corrosion prevention performance did not meet the desired requirements. On the other hand, when the number of objects to be counted in the processing solution in the solution is 3,000 or 10,000 per mL, although the residue removal performance is excellent, corrosion to Co and Cu, which are metal films, occurs, and the substrate The amount of foreign matter attached to the skin increased.
Furthermore, the same tendency was observed also in Comparative Examples 5 to 9 of a system including the compound represented by General Formula (1) as the nitrogen-containing compound. Specifically, when the number of objects to be counted in the processing solution in the solution is zero per 1 mL, the number of defects on the substrate to be treated was a good result, but the residue removal performance and the corrosion prevention performance It did not meet the desired requirements. On the other hand, when the number of objects to be counted in the processing solution in the solution is 10000 per 1 mL, although the residue removal performance is excellent, the desired requirements are not satisfied in the corrosion prevention performance and the number of substrate defects. The

From the comparison of Examples 1 to 4, the number of objects to be counted in the treatment solution is 1 to 2000 (preferably 1 to 1000, more preferably 1 to 500, still more preferably 1 to 300) per mL, particularly When it is preferably 10 to 100, it has been confirmed that the residue removal performance and the corrosion prevention performance are more excellent and the number of treated substrate defects is small.
Moreover, also in the contrast of Examples 13-16 which changed the nitrogen-containing compound, the result of the tendency similar to Examples 1-4 was observed.

Further, from the comparison of Examples 27 to 30, 34, and 36 shown in Table 3, the content of Fe ions in the treatment liquid is 1 mass ppt to 10 mass ppm (preferable to the total mass of the treatment liquid) Is 1 mass ppt to 1 mass ppm, preferably 1 mass ppt to 1 mass ppb), the resulting treatment liquid is more excellent in residue removal performance and corrosion prevention performance, and further reduces the number of treated substrate defects more It was confirmed that
Further, from the comparison of Examples 31 to 33, 35, and 36, the content of Co ions in the treatment liquid is 1 mass ppt to 10 mass ppm (preferably 1 mass ppt to the total mass of the treatment liquid). By setting it as 1 mass ppb), it was confirmed that the processing solution obtained is more excellent in residue removal performance and corrosion prevention performance, and further reduces the number of treated substrate defects more. From this result, the same effect is expected even when the step of removing metal ions is applied to the treatment liquid after the treatment liquid is prepared.

  In addition, although not shown in the table, all of the processing solutions in the examples are dry substrates provided with a metal hard mask including any of AlOx, AlN, AlOxNy, Ti, TiN, ZrOx, HfOx, or TaOx. It has been confirmed that excellent residue removal performance is exhibited even for etching residues.

<Elimination evaluation>
With respect to the treatment solutions of Example 17 and Example 28, various evaluations of the residue removal performance, the Co anticorrosion ability, and the Cu anticorrosion ability are carried out in the same manner except that the material SUS316 earthed to ground is used for charge removal and the immersion time is 20 minutes. Did.

As a result of the evaluation, the residue removal performance does not change between any of the processing solutions through the above-mentioned charge removal step and the treatment without the same, and in the various evaluations of Co anticorrosion ability and Cu anticorrosion ability, In addition, the result that corrosion resistance is more excellent was obtained.
From this result, it was found that the anticorrosion property is more excellent by passing through the static elimination step.

<Recycling test>
For each treatment solution of Examples 28, 29, 32, and 33, each treatment of the above <Evaluation of residue removal performance> and <corrosion prevention performance (Co anticorrosion ability, Cu anticorrosion ability)> was carried out with the same treatment liquid. It went on a series of times. Thereafter, the collected liquid is put back into the tank, and the same processing and evaluation as in Examples 28, 29, 32 and 33 are repeated (<Evaluation of residue removal performance> and <Corrosion prevention performance (Co anticorrosion ability) , Cu anticorrosion ability))) and evaluated the residue removal performance, Co anticorrosion ability, and Cu anticorrosion ability (that is, 25 objects to be treated are continuously treated without changing the treatment solution, The various performances were evaluated by performing the above-described evaluation on the second object to be processed.

As a result of the evaluation, it was found that the evaluations of residue removal performance, Co anticorrosion ability, and Cu anticorrosion ability did not change in the case of the recycling test and in the case of non-recycling test. On the other hand, with the treatment solutions of 29 and 33, 29 was a residue removal performance B, 33 was a residue removal performance C, and 29 and 33 were Cu when recycled and not tested. Similar results were obtained except that the corrosion resistance was C in all cases.
From these results, it was found that the treatment liquid of the present invention can be used with almost no change in performance even when the substrate is repeatedly treated, and is excellent in recyclability.

Reference Signs List 1 substrate 2 metal film 3 etching stop layer 4 interlayer insulating film 5 metal hard mask 6 hole 10 laminate 11 inner wall 11 a cross sectional wall 11 b bottom wall 12 dry etching residue

Claims (16)

At least one hydroxylamine compound selected from hydroxylamine and hydroxylamine salts;
At least one nitrogen-containing compound selected from a compound represented by the following general formula (1) and a compound represented by the following general formula (2);
At least one solvent selected from an organic solvent and water;
Processing solution for semiconductor devices including
The treatment liquid, wherein the number of objects to be counted with a size of 0.05 μm or more counted by a light scattering type liquid-in-liquid counter in the treatment liquid is 1 to 2,000 per 1 mL.
General formula (1):

In the general formula (1), R ¹ , R ² and R ³ each independently represent a hydrogen atom, or a linear, branched or cyclic alkyl group, an alkenyl group, an alkynyl group, an acyl group, a linear or branched group And a monovalent organic group selected from an alkoxy group, an amidyl group, an alkoxyalkyl group, an alkylsulfonyl group, a carboxy group, and a sulfonic acid group, and salts thereof.
General formula (2):

In the general formula (2), R ⁴ , R ⁵ , R ⁶ and R ⁷ each independently represent a hydrogen atom, or a linear, branched or cyclic alkyl group, an alkenyl group, an alkynyl group, an acyl group, a linear group or branched alkoxy group, amidyl group, a benzyl group, an aryl group, an alkoxyalkyl group, an alkylsulfonyl group, a carboxy group, and a sulfonic acid group, and represents a monovalent organic group selected from the salts thereof, X ^- Represents a counter anion. The monovalent organic group may further have a substituent. However, in the formula, the case where all of R ⁴ , R ⁵ , R ⁶ and R ⁷ are hydrogen atoms is excluded.   The processing liquid according to claim 1, wherein the organic solvent contains at least one selected from N-methyl-pyrrolidone, dimethyl sulfoxide, and propylene glycol. With respect to the total mass of the treatment liquid,
The water content is 20 to 98% by mass,
The process liquid of Claim 1 or Claim 2 whose content of the said organic solvent is 0-30 mass%. With respect to the total mass of the treatment liquid,
The content of the water is 1 to 30% by mass,
The process liquid of Claim 1 or Claim 2 whose content of the said organic solvent is 20-98 mass%.   Furthermore, the process liquid of any one of Claims 1-4 containing a corrosion inhibitor.   The treatment liquid according to any one of claims 1 to 5, further comprising a chelating agent. The said corrosion inhibitor is a compound represented by the following general formula (A)-general formula (C), substituted or unsubstituted tetrazole, maleic anhydride, phthalic anhydride, fructose, ammonium thiosulfate, tetramethyl guanidine, gallic acid Ester, 2-mercapto-5-methylbenzimidazole, 2-mercaptothiazoline, 3- (2-aminophenylthio) -2-hydroxypropylmercaptan, and 3- (2-hydroxyethylthio) -2-hydroxypropylmercaptan The processing liquid according to claim 5, which is at least one selected from the group consisting of

In formula (A), R ^{1A to} R ^5A each independently represent a hydrogen atom, a hydrocarbon group, a hydroxy group, a carboxy group or an amino group. However, the structure contains at least one group selected from a hydroxy group, a carboxy group and an amino group.
In general formula (B), R ^{1B to} R ^5B each independently represent a hydrogen atom, a hydroxy group or a hydrocarbon group.
In formula (C), R ^1C , R ^2C and R ^N each independently represent a hydrogen atom or a hydrocarbon group. Also, R ^1C and R ^2C may combine to form a ring.
In the general formulas (A) to (C), the hydrocarbon group may have a substituent.   Furthermore, the processing liquid of any one of Claims 1-7 containing 1 mass ppt-10 mass ppm of Fe ions with respect to the total mass of the said processing liquid.   The treatment liquid according to any one of claims 1 to 8, further comprising 1 mass ppt to 10 mass ppm of Co ions with respect to the total mass of the treatment liquid. In the general formula (1), each of R ¹ , R ² and R ³ independently may be a hydrogen atom or a linear group optionally having a substituent represented by the following general formula (3) The processing liquid according to any one of claims 1 to 9, which is a branched or cyclic alkyl group.

In general formula (3), R represents a hydrogen atom. n represents 0, 1, or 2. The wavy line portion indicates the bonding position. In the general formula (2), each of R ⁴ , R ⁵ , R ⁶ and R ⁷ is independently and independently selected from an alkyl group having 1 to 6 carbon atoms and a hydroxyalkyl group having 1 to 6 carbon atoms. of an organic group, X ^- is a hydroxide ion, the processing liquid according to any one of claims 1 to 10. Process liquid preparation process A which prepares the process liquid of any one of Claims 1-11,
A cleaning process for cleaning a substrate provided with a metal hard mask containing at least one of Cu, Co, W, AlOx, AlN, AlOxNy, WOx, Ti, TiN, ZrOx, HfOx and TaOx using the processing solution And B. a method of cleaning a substrate.
In addition, it is a number represented by x = 1-3, y = 1-2. Process liquid preparation process A which prepares the process liquid of any one of Claims 1-11,
A cleaning process for cleaning a substrate provided with a metal hard mask containing at least one of Cu, Co, W, AlOx, AlN, AlOxNy, WOx, Ti, TiN, ZrOx, HfOx and TaOx using the processing solution B,
A drainage recovery step C for recovering the drainage of the treatment liquid used in the cleaning step B;
Metal hard containing at least one selected from Cu, Co, W, AlOx, AlN, AlOxNy, WOx, Ti, TiN, ZrOx, HfOx, and TaOx newly prepared using the drainage of the recovered treatment liquid A cleaning step D for cleaning a substrate provided with a mask;
And a drainage recovery step E for recovering the drainage of the treatment liquid used in the cleaning step D,
The substrate cleaning method according to claim 12, wherein the cleaning process D and the drainage recovery process E are repeatedly performed to recycle the drainage of the processing solution. Before the treatment liquid preparation step A, a metal ion removal step F for removing at least one kind of ion species selected from Fe ion and Co ion from at least one of the hydroxylamine compound and the solvent, or
It has a metal ion removing step G for removing at least one kind of ion species selected from Fe ions and Co ions in the processing solution after the processing solution preparation step A and before performing the cleaning step B. A method of cleaning a substrate according to claim 12 or claim 13. Before the treatment liquid preparation step A, it has a charge removal step I for discharging the solvent, or
The substrate according to any one of claims 12 to 14, further comprising a diselectrification step J of diselectrifying the processing liquid after the processing liquid preparation step A and before performing the cleaning step B. How to wash A metal hard containing at least one of Cu, Co, W, AlOx, AlN, AlOxNy, WOx, Ti, TiN, ZrOx, HfOx, and TaOx with the treatment liquid according to any one of claims 1 to 11. A method of manufacturing a semiconductor device, comprising the step of cleaning a substrate provided with a mask.
In addition, it is a number represented by x = 1-3, y = 1-2.