KR20180088452A - Process liquid, substrate cleaning method, and semiconductor device manufacturing method - Google Patents

Abstract

An object of the present invention is to provide a treatment liquid which has excellent remnant removal performance and system performance, and which has excellent remnant removal performance and system performance after repeated temperature environment changes. It is another object of the present invention to provide a method of cleaning a substrate and a method of manufacturing a semiconductor device. The treatment liquid of the present invention is a treatment liquid for a semiconductor device, which comprises at least one hydroxylamine compound selected from hydroxylamine and a hydroxylamine salt, water, and a corrosion inhibitor, , The number of the coefficient bodies of the size of 0.05 탆 or more is 1 to 2000 per 1 ml of the treatment liquid.

Description

Process liquid, substrate cleaning method, and semiconductor device manufacturing method

The present invention relates to a process liquid, a substrate cleaning method, and a semiconductor device manufacturing method.

BACKGROUND ART A semiconductor device such as a charge-coupled device (CCD) or a memory is manufactured by forming a fine electronic circuit pattern on a substrate by using a photolithography technique. Specifically, a photoresist film is formed on a laminate having a metal film (for example, Co and W) serving as a wiring material, an etching stopper film, and an interlayer insulating film on a substrate, and a photolithography process and a dry etching process For example, a plasma etching treatment), a semiconductor device is manufactured.

If necessary, a dry ashing process (for example, a plasma ashing process) for removing the resist film is performed.

In the substrate subjected to the dry etching process, residues such as dry etching residues adhere to the metal film and / or the interlayer insulating film. As a result, a process of removing these residues by the treatment liquid is generally performed.

For example, Patent Document 1 discloses the use of a composition containing water, a hydroxylamine salt compound and a corrosion inhibitor as the treatment liquid (claim 1, etc.).

Patent Document 1: Japanese Patent Publication No. 4880416

The treatment liquid may be used for removing residues adhered on the metal film and / or the interlayer insulating film as described above. Therefore, first, the treatment liquid is required to have an excellent capability of removing the residue (the removal performance of the residue). The treatment liquid is also required to suppress the occurrence of corrosion of the metal film or the interlayer insulating film at the time of removing the residue (excellent corrosion prevention performance).

The treatment liquid is stored in a refrigerated state at a predetermined temperature when not in use, and the treatment liquid is taken out of the refrigerated storage at the time of use and returned to room temperature to be used. Therefore, even after such temperature environment changes are repeatedly performed, it is required that the processing solution has excellent residue removal performance and system performance.

DISCLOSURE OF THE INVENTION However, the present inventors have found that, after preparing a treatment liquid with reference to the method and composition described in Patent Document 1, after the temperature environment change of the treatment liquid is repeatedly performed, the residual solution removal performance and system performance of the treatment liquid become insufficient I found that.

Accordingly, it is an object of the present invention to provide a treatment liquid which has excellent remnant removing performance and system performance, and which has excellent remnant removing performance and system performance after repeated temperature environment changes. It is another object of the present invention to provide a method of cleaning a substrate and a method of manufacturing a semiconductor device.

As a result of intensive investigation into the above problems, the inventor of the present invention found that a desired performance can be obtained by using a treating solution containing a corrosion inhibitor and having a water count of 1 to 2000 per 1 ml of the treating solution Thus, the present invention has been accomplished.

That is, the present inventor has found that the above problems can be solved by the following constitution.

[One]

1. A processing solution for a semiconductor device,

At least one hydroxylamine compound selected from a hydroxylamine and a hydroxylamine salt, water, and a corrosion inhibitor,

Wherein the number of the coefficient bodies having a size of 0.05 m or more, counted by the light scattering type submerged particle counter, is 1 to 2000 per 1 ml of the treatment liquid.

[2]

Wherein the corrosion inhibitor is at least one compound selected from the group consisting of a triazole compound, a mercapto group-containing compound, maleic anhydride, phthalic anhydride, ammonium thiosulfate, tetramethylguanidine and a glycolic acid ester. The described treatment liquid.

[3]

Wherein the corrosion inhibitor comprises a triazole compound,

The treatment liquid according to the above [1] or [2], wherein the triazole compound comprises at least one compound selected from benzotriazole, carboxybenzotriazole, 5-methylbenzotriazole, and triazole.

[4]

Wherein the corrosion inhibitor comprises a triazole compound and a mercapto group-containing compound,

Wherein the triazole compound comprises at least one compound selected from benzotriazole, carboxybenzotriazole, 5-methylbenzotriazole, and triazole,

Wherein the mercapto group-containing compound is at least one selected from the group consisting of 2-mercapto-5-methylbenzimidazole, 3-mercapto-1,2-propanediol, 2-mercaptothiazoline, 3- 1] to [3] above, wherein the compound [1] comprises at least one compound selected from the group consisting of 3- (2-hydroxyethylthio) To the processing solution.

[5]

The treatment liquid according to any one of [2] to [4] above, wherein the triazole compound comprises 5-methylbenzotriazole.

[6]

Wherein the corrosion inhibitor comprises a triazole compound and a mercapto group-containing compound,

The treatment liquid according to any one of [1] to [5], wherein the mass ratio of the mercapto group-containing compound to the triazole compound is 0.1 to 50.

[7]

The treatment liquid according to any one of [1] to [6], further comprising 10 mass ppm to 10 mass ppm of Fe ions.

[8]

1] to [4], wherein the metal hard mask is used for cleaning a substrate having a metal hard mask containing at least one of Cu, Co, W, AlOx, AlN, AlOxNy, WOx, Ti, TiN, ZrOx, HfOx and TaOx. [7] The treatment liquid according to any one of [1] to [7].

[9]

A treatment liquid preparation step A for preparing the treatment liquid according to any one of [1] to [8]

A cleaning step of cleaning a substrate having a metal hard mask containing at least one of Cu, Co, W, AlOx, AlN, AlOxNy, WOx, Ti, TiN, ZrOx, HfOx and TaOx RTI ID = 0.0 > B. ≪ / RTI >

[10]

A discharged-liquid recovery step C for recovering the discharged liquid of the treatment liquid used in the cleaning step B,

A substrate having a metal hard mask containing at least one of Cu, Co, W, AlOx, AlN, AlOxNy, WOx, Ti, TiN, ZrOx, HfOx and TaOx, A cleaning step D,

Further comprising a discharged-liquid collecting step E for collecting the discharged liquid used in the washing step D,

The cleaning method according to the above-mentioned [9], wherein the cleaning step D and the discharged liquid recovery step E are repeated to recycle the discharged liquid.

[11]

The metal ion removing step F for removing Fe ions from at least one of the hydroxylamine compound and the water prior to the treatment liquid preparation step A,

The method for cleaning a substrate according to the above [9] or [10], further comprising a metal ion removing step G for removing Fe ions in the treatment solution after the treatment solution preparation step A and before the cleaning step B is performed.

[12]

Before the treatment liquid preparation step A, there is provided a discharging step I in which electricity is discharged to the water,

The cleaning method for a substrate according to any one of the above [9] to [11], further comprising a discharging step J for discharging the treating liquid after the treating liquid preparing step A and before the cleaning step B.

[13]

A metal containing at least one of Cu, Co, W, AlOx, AlN, AlOxNy, WOx, Ti, TiN, ZrOx, HfOx, and TaOx by the treatment liquid according to any one of [1] to [ A method for manufacturing a semiconductor device, comprising: a step of cleaning a substrate having a hard mask.

As described below, according to the present invention, it is possible to provide a treatment liquid which has excellent remnant removing performance and system performance, and which has excellent remnant removing performance and system performance after repeated temperature environment changes. According to the present invention, it is also possible to provide a method of cleaning a substrate and a method of manufacturing a semiconductor device.

1 is a schematic cross-sectional view showing an example of a laminate applicable to a cleaning method of a substrate of the present invention.

Hereinafter, the treatment liquid of the present invention will be described.

In the present invention, the numerical range indicated by "to" means a range including numerical values described before and after "to " as a lower limit value and an upper limit value.

In the present invention, 1 Å (angstrom) corresponds to 0.1 nm.

In the notation of the group (atom group) in the present specification, the notations in which substitution and non-substitution are not described include those having no substituent group and having a substituent group as long as the effect of the present invention is not impaired . For example, the "alkyl group" includes not only an alkyl group having no substituent (an unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). This is also true for each compound.

The term "radiation " in the present specification means, for example, a line spectrum of a mercury lamp, far ultraviolet ray, extreme ultraviolet ray (EUV light) represented by an excimer laser, X-ray or electron ray. In the present specification, light means an actinic ray or radiation. The term "exposure" in this specification refers to not only exposure by deep ultraviolet rays such as mercury lamps and excimer lasers, X-rays, EUV light, etc., but also imaging by particle beams such as electron beams and ion beams, .

In the present specification, the term "(meth) acrylate" refers to both or either acrylate and methacrylate, and "(meth) acrylate " refers to both acrylate and methacrylate.

In the present specification, the terms "monomer" and "monomer" are synonyms. Monomers in the present specification are distinguished from oligomers and polymers, and unless otherwise stated, refer to compounds having a weight average molecular weight of 2,000 or less. In the present specification, the polymerizable compound means 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 the present specification, the term "preparation" is meant to include procuring a predetermined article by purchase or the like in addition to providing a specific material by synthesis or combination.

[Treatment liquid]

The treatment liquid of the present invention is a treatment liquid for a semiconductor device, which comprises at least one hydroxylamine compound selected from hydroxylamine and a hydroxylamine salt, water, and a corrosion inhibitor, The number of the coefficient bodies of the size of 0.05 탆 or more in the treatment liquid is 1 to 2000 per 1 ml of the treatment liquid.

The treatment liquid of the present invention is excellent in the remnant removal performance and system performance and is excellent in the residual removal performance and system performance after repeated environmental temperature changes.

Although the details of this reason are not yet clear, it is presumed to be approximately as follows.

Although the details of the subject matter of a predetermined size included in the treatment liquid will be described later, the subject matter contained in the treatment liquid of the present invention can be various solid matter (for example, organic solids or inorganic solids) , Bubbles containing dissolved oxygen), and the like.

In the present invention, it is presumed that the object to be plucked of a predetermined size included in the treatment liquid has excellent residue removal performance of the treatment liquid, and has excellent residue removal performance after repeated environmental temperature changes. Particularly, since the organic solid matter and the bubbles containing dissolved oxygen function as an oxidizing agent, it is presumed that the treatment liquid containing the above-mentioned coefficient of the above-mentioned kind of material has better remnant removal performance.

Further, in the case where solid matter exists as one of the above-mentioned coefficient bodies in the treatment liquid, bubbles containing dissolved oxygen adhere to the solid matter and tend to remain in the treatment liquid. It is presumed that the solids are easy to reach the residues, and if the solids are contained in the treatment liquid as a kind of the coefficient to be measured, the function as the oxidant of the dissolved oxygen adhered to the solids tends to be exerted.

As described above, the treatment liquid containing a predetermined number of the predetermined coefficients of the water coefficient is excellent in the removal performance of the residue. Therefore, when the residue adhering to the metal film or the interlayer insulating film is removed by using the present process solution, the dissolved substance of the residue is contained in the treatment solution at a high concentration. Thus, it is considered that the components constituting the metal film or the interlayer insulating film can be prevented from being eluted into the treatment liquid. As a result, it is presumed that the process performance of the treatment liquid is excellent and the performance of the system after repeated environmental temperature changes is excellent.

On the other hand, the inventors of the present invention have found that if the number of the units to be measured is more than 2000, the performance of the system becomes insufficient, and the performance of remnant removal and the performance of the system after repeated environmental temperature changes become insufficient. The reason why the performance of the method is insufficient and the performance of the system after repeated environmental temperature changes becomes insufficient is that the component contained in the metal film or the interlayer insulating film of the coefficient multiplier attached to the metal film or the interlayer insulating film is eluted This is thought to be due to the stronger action of The reason why the residual object removal performance after repeated environmental temperature changes becomes insufficient is that the number of the subject units increases due to the repetition of temperature environment changes and the increased coefficient of affix is attached to the metal film and / , It is thought to be due to the new residue.

Further, the inventors have found that when the number of the coefficients to be counted is zero, the performance of remnant removal and the performance of the system become insufficient, or the performance of the system after repeated environmental temperature changes becomes insufficient. The reason why the residual object removing performance becomes insufficient is considered to be that the function of removing the residue by the coefficient to be measured does not function. It is considered that the reason for the inadequate performance of the system is that components constituting the metal film or the interlayer insulating film tend to elute into the processing solution because the amount of dissolved residue in the processing solution is reduced. Further, it is considered that the reason why the performance of the system after the environmental temperature change is repeated is insufficient is due to the deterioration of performance of the processing solution due to the environmental temperature change.

Hereinafter, the components contained in the treatment liquid and the components that may be contained are described.

<Hydroxylamine Compound>

The treatment liquid of the present invention contains at least one hydroxylamine compound selected from a hydroxylamine and a hydroxylamine salt. The hydroxylamine compound accelerates the decomposition and solubilization of the residue, and can suppress the corrosion of the object to be cleaned.

Here, the "hydroxylamine" in relation to the hydroxylamine and hydroxylamine salt of the treatment liquid of the present invention refers to a wide range of hydroxylamines including substituted or unsubstituted alkylhydroxylamine and the like, The effect of the present invention can be obtained.

The hydroxylamine is not particularly limited, but preferred examples thereof include an unsubstituted hydroxylamine and a hydroxylamine derivative.

Examples of the hydroxylamine derivative include, but are not limited to, O-methylhydroxylamine, O-ethylhydroxylamine, N-methylhydroxylamine, N, N-dimethylhydroxylamine, N, Methylhydroxylamine, N-ethylhydroxylamine, N, N-diethylhydroxylamine, N, O-diethylhydroxylamine, O, N, Ethylhydroxylamine, N, N-disulfoethylhydroxylamine, and the like.

The salt of the hydroxylamine is preferably an inorganic acid salt or an organic acid salt of the hydroxylamine described above, more preferably a salt of an inorganic acid formed by combining a base metal such as Cl, S, N, P with hydrogen, , And nitric acid.

Examples of the salt of the hydroxylamine used to form the treatment liquid of the present invention 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 ), Hydroxylammonium phosphate, N, N-diethylhydroxylammonium sulfate, N, N-diethylhydroxylammonium nitrate, and mixtures thereof are preferred.

An organic acid salt of hydroxylamine can also be used, and examples thereof include hydroxylammonium citrate, hydroxylammonium oxalate, and hydroxylammonium fluoride.

In addition, the treatment liquid of the present invention may be in a form containing both hydroxylamine and its salt. These compounds may be used singly or in combination of two or more.

Of these, hydroxylamine and hydroxyl ammonium sulfate are preferable, and hydroxyl ammonium sulfate is more preferable from the viewpoint that the desired effect of the present invention is remarkably obtained.

The content of the hydroxylamine compound is preferably 0.01 to 30 mass%, more preferably 0.1 to 25 mass%, and further preferably 1 to 20 mass% with respect to the total mass of the treatment liquid. Within the above range, the desired effect of the present invention is remarkably obtained.

<Water>

The treatment liquid of the present invention contains water as a solvent. The content of water is not particularly limited, but is generally 20 to 98% by mass, preferably 60 to 98% by mass, and more preferably 70 to 95% by mass with respect to the mass of the whole treatment liquid.

As the water, ultrapure water used for semiconductor production is preferable.

<Corrosion inhibitor>

The treatment liquid of the present invention contains a corrosion inhibitor. The corrosion inhibitor can suppress the corrosion of the metal film and the interlayer insulating film when the residue is removed.

The corrosion inhibitor is preferably selected from the group consisting of triazole compounds, mercapto group-containing compounds, maleic anhydride, phthalic anhydride, ammonium thiosulfate, tetramethylguanidine and gallic acid ester from the viewpoint that the performance of the treatment solution can be further improved. Is at least one kind of compound.

The corrosion inhibitor may be used alone or in combination of two or more.

Among these corrosion inhibitors, the treatment liquid preferably contains a triazole compound from the viewpoint of further improving the system performance of the treatment liquid. It is presumed that the triazole compound has a planar structure and adheres to the metal film and the interlayer insulating film in this planar structure portion, so that the adhesion to the metal film and the interlayer insulating film is excellent. As a result, it is presumed that the system performance of the treatment liquid becomes easy to be exerted.

It is more preferable that the treatment liquid contains both a triazole compound and a mercapto group-containing compound. As a result, the system performance of the processing solution is further improved, and the processing performance of the processing solution after the temperature environment change is repeated is improved. For this reason, it is presumed that the mercapto groups contained in the mercapto group-containing compounds are more likely to exert the system performance of the treatment solution by complementing the adhesion force of the triazole compound.

The triazole compound includes, for example, a triazole compound having a benzene ring structure (i.e., a benzotriazole compound), and a triazole compound having no benzene ring structure.

Examples of the benzotriazole compound include benzotriazole (BTA), carboxybenzotriazole, 1-hydroxybenzotriazole, 5-phenylthiol-benzotriazole, 5-chlorobenzotriazole, 4-chlorobenzo Benzothiazole, 5-bromobenzotriazole, 5-fluorobenzotriazole, 4-fluorobenzotriazole, naphthotriazole, tolyltriazole, 5-phenyl-benzotriazole, 4-nitrobenzotriazole, 2- (5-amino-pentyl) -benzotriazole, 1-amino-benzotriazole, 5-methyl-benzotriazole, benzotriazole 5-ethylbenzotriazole, 5-ethylbenzotriazole, 5-ethylbenzotriazole, 5-ethylbenzotriazole, 5-ethylbenzotriazole, 5-ethylbenzotriazole, -Isopropylbenzotriazole, 4-n-butylbenzotriazole, 5-n- Isobutylbenzotriazole, 5-pentylbenzotriazole, 5-pentylbenzotriazole, 5-pentylbenzotriazole, 5-hexylbenzotriazole, 5-isobutylbenzotriazole, 5- Benzotriazole, 5-hydroxybenzotriazole, dihydroxypropylbenzotriazole, 1- [N, N-bis (2-ethylhexyl) aminomethyl] Benzotriazole, 5- (1 ', 1', 3'-trimethylbutyl) benzotriazole, 5-n-octylbenzotriazole, 5- And 5- (1 ', 1', 3 ', 3'-tetramethylbutyl) benzotriazole.

Examples of the triazole compound having no benzene ring structure include triazole (specifically, 1,2,3-triazole and 1,2,4-triazole), 3-amino-1,2,4-triazole, 3,5-diamino-1,2,4-triazole, 3-amino-5-mercapto-1,2,4-triazole, Methyl-1,2,3-triazole, 3-mercapto-1,2,4-triazole, 3-mercapto-4-methyl- 1,2,4-triazole, and 3-isopropyl-1,2,4-triazole.

The treatment liquid preferably contains at least one compound selected from benzotriazole, carboxybenzotriazole, 5-methylbenzotriazole, and triazole from the viewpoint that the performance of the system is further improved, and 5-methyl -Benzotriazole. &Lt; / RTI &gt;

In the case of containing a triazole compound as a corrosion inhibitor, the content of the triazole compound is preferably 0.001 to 10 mass%, more preferably 0.01 to 5 mass%, with respect to the total mass of the treatment liquid. When the content of the triazole compound is within the above range, the performance of the process is further improved.

Examples of the mercapto group-containing compound include 2-mercapto-5-methylbenzimidazole, 3-mercapto-1,2-propanediol, 2-mercaptothiazoline, 3- 2-mercapto benzimidazole (2-MBI), 1-phenyl-5-thiophene -Mercaptotetrazole, 5-amino-1,3,4-thiadiazol-2-thiol, and 2,5-dimercapto-1,3-thiadiazolesacobic acid.

Among these mercapto group-containing compounds, the treatment liquid is preferably at least one selected from the group consisting of 2-mercapto-5-methylbenzimidazole, 3-mercapto-1,2-propanediol, 2- Aminophenylthio) -2-hydroxypropylmercaptan, and 3- (2-hydroxyethylthio) -2-hydroxypropylmercaptan.

By using these preferable mercapto group-containing compounds in combination with the above-mentioned triazole compounds (particularly, at least one compound selected from benzotriazole, carboxybenzotriazole, 5-methyl-benzotriazole, and triazole) The performance of the liquid system is further improved and the performance of the treatment liquid after the temperature environment change is repeated is improved.

The mercapto group-containing compound of the present invention does not contain a compound having a mercapto group and a triazole group. In the present invention, the compound having a mercapto group and a triazole group is classified as the above-mentioned triazole compound.

In the case of containing a mercapto group-containing compound as a corrosion inhibitor, the content of the mercapto group-containing compound is preferably 0.001 to 10 mass%, more preferably 0.01 to 5 mass%, based on the total mass of the treatment liquid. When the content of the mercapto group-containing compound is within the above range, the performance performance is further improved.

In the case where the corrosion inhibitor comprises the triazole compound and the mercapto group-containing compound, the mass ratio of the mercapto group-containing compound to the triazole compound (mass content of the mercapto group-containing compound / mass content of the triazole compound) More preferably from 0.1 to 50, more preferably from 0.1 to 20, and even more preferably from 0.1 to 10. When the mass ratio is within the above range, the residue removal performance and system performance after preserving the processing solution for a long period of time are excellent.

The content of the corrosion inhibitor is preferably 0.01 to 5% by mass, more preferably 0.05 to 5% by mass, and even more preferably 0.1 to 3% by mass based on the total mass of the treatment liquid. When the content of the corrosion inhibitor is within the above range, the effect exhibited by containing the corrosion inhibitor is further exerted.

&Lt; Pieces >

In the present invention, the number of the coefficient bodies to be counted by the light scattering type submicron particle counter is 0.05 to 2,000 per ml of the treated liquid.

Here, the coefficient to be measured of the present invention is not particularly limited as long as it is detected as a size of 0.05 m or more by a light scattering type submerged particle counter.

In the light scattering type in-liquid particle counter, a particle detecting area is formed by irradiating a sample fluid (a treatment liquid in the present invention) with a light beam, and scattered light by the object to be measured passing through the particle detecting area is received by a light receiving means , And the number of the units to be counted is counted.

In the light scattering type submerged particle counter, bubbles and the like containing a gas (dissolved oxygen, etc.) are also detected as an object to be measured in addition to solids.

Specifically, the object to be plucked in the present invention is to be impregnated (for example, dust, dirt, organic solid matter, solid matter such as inorganic solid matter) contained in the raw material of the treatment liquid, It is assumed that impurities (for example, dust, dirt, organic solids, solids such as inorganic solids), bubbles mixed in the raw material of the treatment liquid, bubbles incorporated during the preparation of the treatment liquid, and the like.

As the light scattering type submerged particle counter, an apparatus according to the submerged particle counter "KS-18F" (manufactured by RON CORPORATION) is used. Measurement conditions of the treatment liquid by the light scattering type submerged particle counter are as described in the following examples.

The number of the coefficient bodies of 0.05 탆 or more in size contained in the treatment liquid of the present invention is 1 to 2000, preferably 1 to 1000, more preferably 1 to 400, and more preferably 1 to less than 300 More preferably from 1 to 100 carbon atoms.

When the number of the enumerated coefficients is within the above range, the performance and system performance of the treatment solution are excellent, and the residual solution removal performance and system performance of the treatment solution after repeated environmental temperature changes are excellent.

On the other hand, if the number of the above-mentioned coefficients is zero, the performance and performance of the remnant removing function and the performance of the processing solution become insufficient, or the processing performance of the processing solution after repeated environmental temperature changes becomes insufficient. In addition, if the number of the above-mentioned coefficient bodies is more than 2,000, the performance of the processing solution becomes insufficient, and the performance and system performance of the processing solution after repeatedly changing the environmental temperature become insufficient.

In the present invention, the size of the coefficient to be counted by the light scattering type submicron particle counter is 0.05 μm or more.

The upper limit value of the size of the counted coefficient to be counted is not particularly limited, but is usually 10 μm or less. Further, technical difficulties arise in the detection of the coefficient to be measured having a size of less than 0.05 mu m.

It is preferable that the treatment liquid of the present invention does not contain particles of 0.1 m or more (concretely, coarse particles such as impurities) in consideration of its use. As a result, the coarse particles contained in the treatment liquid itself can be prevented from becoming residues.

Examples of the method for removing coarse particles include a treatment such as filtering described later. The particles having a particle size of 10 탆 or more can be measured using a laser diffraction particle size distribution measuring apparatus.

<Fe ion>

The treatment liquid of the present invention preferably contains 10 mass ppm to 10 mass ppm of Fe ions. Thus, even after the treatment liquid is stored for a long period of time, it is excellent in removing residuals of the treatment liquid. The reason for this is presumed to be that the Fe ions acted as the oxidizing agent and the performance of removing the residue of the treatment solution was maintained.

The content of Fe ions is preferably 10 parts by mass to 10 parts by mass per 100 parts by mass of the total mass of the treatment liquid, more preferably 10 parts by mass to 1000 parts by mass, more preferably 10 parts by mass or more but less than 1000 parts by mass Do.

<Other components>

The treatment liquid of the present invention may contain other components than the above. Examples of the other components include a chelating agent, a water-soluble organic solvent, a pH adjuster, quaternary ammonium hydroxides, alkanolamines and the like.

(Chelating agent)

The treatment liquid may contain a chelating agent. The chelating agent is chelated with the oxidized metal contained in the residue. As a result, the recyclability is further improved by adding a chelating agent.

The chelating agent is not particularly limited, but is preferably a polyaminopolycarboxylic acid.

The polyaminopolycarboxylic acid is a compound having a plurality of amino groups and a plurality of carboxylic acid groups, and examples thereof include mono- or polyalkylene polyamine polycarboxylic acids, polyaminoalkane polycarboxylic acids, polyaminoalkanol polycarboxylic acids, and hydroxyalkyl ethers Polyamine polycarboxylic acid.

Suitable polyaminopolycarboxylic acid chelating agents include, for example, butylanediamine diacetic acid, diethylene triamine o acetic acid (DTPA), ethylenediaminetetra propionic acid, triethylenetetramine hexacetic acid, 1,3-diamino-2 (EDTA), trans-1,2-diaminocyclohexaneacetic acid, ethylene diamine diacetate, ethylene diamine tetraacetic acid, ethylene diamine tetraacetic acid, N, N ', N'-tetraacetic acid, N, N-bis (2-hydroxybenzyl) ethylenediamine-N, Diacetoxyacetic acid, N-i acetic acid, diaminopropaneacetic acid, 1,4,7,10-tetraazacyclododecane-sacetic acid, diaminopropanolacetic acid, and (hydroxyethyl) ethylenediamine triacetic acid . Among them, diethylene triamine o acetic acid (DTPA), ethylenediamine diacetic acid (EDTA) and trans-1,2-diaminocyclohexane diacetic acid are preferable. These compounds may be used alone or in combination of two or more.

The content of the chelating agent in the treatment liquid is preferably 0.01 to 5% by mass, more preferably 0.01 to 3% by mass with respect to the total mass of the treatment liquid of the present invention.

(Water-soluble organic solvent)

The treatment liquid of the present invention may contain a water-soluble organic solvent. By containing the water-soluble organic solvent in the treatment liquid, the solubilization of the additive component and the organic matter remnants can be promoted, and the corrosion-preventing effect can be further improved.

The water-soluble organic solvent is not particularly limited, and examples thereof include water-soluble alcohols, water-soluble ketones, water-soluble esters, and water-soluble ethers (for example, glycol diethers). In order to obtain the desired effect of the present invention, All are available.

The water-soluble alcohol includes, for example, alkane diols (including alkylene glycol), alkoxy alcohols (including, for example, glycol monoether), saturated aliphatic monohydric alcohols, unsaturated Non-aromatic monohydric alcohols, and low molecular weight alcohols including cyclic structures.

Examples of the alkene diol include glycols, 2-methyl-1,3-propanediol, 1,3-propanediol, 2,2- 4-butanediol, 1,3-butanediol, 1,2-butanediol, 2,3-butanediol, pinacol, and alkylene glycol.

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

Examples of the alkoxy alcohols include 3-methoxy-3-methyl-1-butanol, 3-methoxy-1-butanol, 1-methoxy- .

Examples of glycol monoethers include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono n-propyl ether, ethylene glycol monoisopropyl ether, Ethylene glycol mono n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 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- Ethoxy-1-propanol, propylene glycol mono-n-propyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether Tri-propylene glycol monoethyl ether, tripropylene glycol monomethyl ether and ethyl Article may be a site on the emitter glycol monobenzyl, diethylene glycol monobenzyl.

Examples of the saturated aliphatic monohydric alcohols include alcohols such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, Alcohols, and 1-hexanol.

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

Examples of low molecular weight alcohols including cyclic structures include tetrahydrofuranyl alcohol, furfuryl alcohol, and 1,3-cyclopentane diol.

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

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

Among these, ethylene glycol monobutyl ether, tri (propylene glycol) methyl ether and diethylene glycol monoethyl ether are preferable.

Of the water-soluble organic solvents, water-soluble alcohols are more preferable, alkane diols, glycols and alkoxy alcohols are more preferable, and alkoxy alcohols are particularly preferable from the viewpoint of further improving the corrosion preventing effect.

The water-soluble organic solvent may be used singly or in combination of two or more.

The content of the water-soluble organic solvent is preferably 0.1 to 15 mass%, more preferably 1 to 10 mass%, based on the total mass of the treatment liquid of the present invention.

(pH adjusting agent)

The pH of the treatment liquid of the present invention is not particularly limited, but is preferably at least the pKa of the conjugate acid of the hydroxylamine and the hydroxylamine salt. The pKa of the conjugate acid of the hydroxylamine and the hydroxylamine salt is higher than that of the conjugate acid, the residue removing performance is remarkably improved. In other words, when the ratio of the hydroxylamine and the hydroxylamine salt existing in the molecular state in the treatment liquid is large, the effect of the present invention is remarkably obtained. For example, the conjugate acid of hydroxylamine has a pKa of about 6.

The pH of the treatment liquid of the present invention is preferably 3 to 11. In order to keep the pH of the treatment liquid within the above range, it is preferable that the treatment liquid contains a pH adjuster.

If the pH of the treatment liquid is within the above range, both the corrosion rate and the removal performance of the residue are better.

The pH can be measured by a known pH meter.

As the pH adjusting agent, known ones can be used. In general, it is preferable not to include a metal ion, and examples thereof include ammonium hydroxide, monoamines, imines (for example, 1,8-diazabicyclo [5.4.0 Ene), 1,4-diazabicyclo [2.2.2] octane, guanidine salts (for example, carbonic acid Guanidine), and the like, and all of them can be used in order to obtain the desired effect of the present invention. Among them, ammonium hydroxide, imines (for example, 1,8-diazabicyclo [5.4.0] undec-7-ene, 1,5-diazabicyclo [4.3.0] Is preferable in view of obtaining a desired effect of the present invention remarkably.

The pH adjusting agent may be used singly or in combination of two or more.

The amount of the pH adjusting agent to be added is not particularly limited as long as a desired pH of the treating solution can be attained. Generally, the treating solution is preferably contained in a concentration of 0.1 to 5% by mass with respect to the total mass of the treating solution, And more preferably 0.1 to 2% by mass.

(Quaternary ammonium hydroxides)

The treatment liquid of the present invention may contain quaternary ammonium hydroxide. The addition of quaternary ammonium hydroxide can further improve the removal performance of the residue, and can also function as a pH adjuster.

The quaternary ammonium hydroxide is preferably a compound represented by the following general formula (4).

[Chemical Formula 1]

(In the formula (4), R ^4A to R ^4D each independently represent an alkyl group having 1 to 6 carbon atoms, a hydroxyalkyl group having 1 to 6 carbon atoms, a benzyl group or an aryl group.)

In the formula (4), R ^4A to R ^4D each independently represent an alkyl group having 1 to 6 carbon atoms (for example, methyl group, ethyl group or butyl group), a hydroxyalkyl group having 1 to 6 carbon atoms (for example, A benzyl group, or an aryl group (e.g., a phenyl group, a naphthyl group, a naphthalene group, etc.). Among them, an alkyl group, a hydroxyethyl group and a benzyl group are preferable.

Specific examples of the compound represented by the formula (4) include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, trimethylhydroxyethylammonium hydroxide, methyltri (hydroxyethyl) It is preferably at least one quaternary ammonium hydroxide selected from the group consisting of ammonium hydroxide, tetra (hydroxyethyl) ammonium hydroxide, trimethylbenzylammonium hydroxide, and choline. Among them, it is more preferable to use at least one selected from the group consisting of tetramethylammonium hydroxide, tetraethylammonium hydroxide, benzyltrimethylammonium hydroxide, and choline in the present invention. Quaternary ammonium hydroxides may be used singly or in combination of two or more.

The content of the quaternary ammonium hydroxide in the treatment liquid is preferably 0.1 to 15 mass%, more preferably 0.5 to 10 mass%, and more preferably 0.5 to 5 mass% with respect to the total mass of the treatment liquid of the present invention. Is more preferable.

(Alkanolamines)

From the standpoint of accelerating the solubilization of the additive component and the organic residue in the treatment liquid and preventing corrosion, alkanolamines may be contained.

The alkanolamines may be either primary amines, secondary amines or tertiary amines, preferably monoamines, diamines, or triamines, more preferably monoamines. The alkanol group of the amine preferably has 1 to 5 carbon atoms.

In the treatment liquid of the present invention, a compound represented by the following formula (5) is preferable.

(5): R ¹ R ² -N-CH ₂ CH ₂ -OR ³

(In the formula (5), R ¹ and R ² each independently represent a hydrogen atom, a methyl group, an ethyl group or a hydroxyethyl group, and each R ³ independently represents a hydrogen atom or a hydroxyethyl group. , Wherein at least one of the alkanol groups is included.

Specific examples of the alkanolamines include monoethanolamine, diethanolamine, triethanolamine, tert.butyldiethanolamine, isopropanolamine, 2-amino-1-propanol, 3-amino- 2-amino-2-ethoxy-propanol, also known as diglycolamine, and 2-amino-2-ethoxy-ethanol, also known as diglycolamine. The alkanolamines may be used singly or in combination of two or more.

The content of the alkanolamines in the treatment liquid is preferably 0.1 to 80 mass%, more preferably 0.5 to 50 mass%, and more preferably 0.5 to 20 mass%, based on the total mass of the treatment liquid of the present invention More preferable.

(Other additives)

The treatment liquid of the present invention may contain other additives in the range of exhibiting the effects of the present invention. Examples of other additives include surfactants and antifoaming agents.

<Kit and concentrate>

The treatment liquid in the present invention may be a kit in which the raw material is divided into a plurality of parts. For example, a liquid composition containing a hydroxylamine compound in water as a first liquid is prepared, and a liquid composition containing other ingredients in water as a second liquid is prepared. As a use example thereof, it is preferable that the treatment liquid is mixed by mixing the two liquids, and then the liquid is applied to the treatment in a timely manner. Organic solvents and the like may be contained in either of them. By doing so, the deterioration of the liquid performance due to the decomposition of the hydroxylamine compound or other components does not occur, and the desired action can be effectively exerted. 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.

The treatment liquid may be prepared as a concentrated liquid. In this case, it can be diluted with water at the time of use.

<Container>

The treatment liquid in the present invention can be stored in any container, stored, transported, and used, so long as it is not corrosive (regardless of whether or not the kit is a kit). As the container, it is preferable to use a semiconductor with high cleanliness and little elution of impurities. Examples of containers that can be used include a "clean bottle" series manufactured by Iceland Kagaku Co., Ltd., and a "pure bottle" manufactured by Kodama Kogyo Kogyo Co., Ltd. However, the present invention is not limited thereto. The container or the inner wall of the container is formed of a resin different from at least one resin selected from the group consisting of a polyethylene resin, a polypropylene resin, and a polyethylene-polypropylene resin, or a metal subjected to anti- .

As the other resin, a fluororesin (perfluororesin) can be particularly preferably used. By using the container in which the inner wall of the accommodating portion is made of the fluorine resin, compared with the case of using a container made of polyethylene resin, polypropylene resin or polyethylene-polypropylene resin as the inner wall of the accommodating portion, elution of oligomers of ethylene or propylene The occurrence of a problem can be suppressed.

Specific examples of the container in which the inner wall of the accommodation portion is a fluororesin include Fluoro Pure PFA composite drum manufactured by Entegris. It is also possible to use containers described in International Patent Publication No. Hei 3-502677, page 4, etc., International Publication No. 2004/016526, page 3, pages 9 and 16 of International Publication No. 99/46309 have.

<Filtering>

The treatment liquid in the present invention is preferably filtered with a filter for the purpose of adjusting the aforementioned coefficient to a desired number, for the purpose of removing foreign matter or reducing defects. So long as it is conventionally used for filtration applications and the like. For example, a filter made of a fluororesin such as PTFE (polytetrafluoroethylene), a polyamide resin such as nylon, a polyolefin resin (including high density, ultrahigh molecular weight) such as polyethylene and polypropylene (PP) . Of these materials, polypropylene (including high-density polypropylene) and nylon are preferred.

When using a filter, other filters may be combined. At this time, the filtering by the first filter may be performed once, or may be performed twice or more. When filtering is performed two or more times in combination with other filters, it is preferable that the hole diameters of the second and subsequent times are larger than or equal to the hole diameters of the first filtering. The hole diameter here can refer to the nominal value of the filter manufacturer. As a commercially available filter, there may be selected, for example, various filters provided by Nippon Oil Corporation, Advantech Toyokawa Co., Ltd., Nippon Integrity Corporation (formerly Nihon Micro-Roller Corporation) or Kitsch Microfilter .

The second filter may be a filter formed of the same material as the first filter described above.

For example, the filtering with the first filter may be performed by a mixed solution containing a part of the processing solution, and after the processing solution is prepared by mixing the remaining components with the second solution, the second filtering may be performed.

<Metal concentration>

The treatment liquid in the present invention is a treatment liquid containing ions of a metal (metal elements of Co, Na, K, Ca, Cu, Mg, Mn, Li, Al, Cr, Ni and Zn) The concentration is preferably 5 ppm or less (preferably 1 ppm or less). Particularly, in the production of a state-of-the-art semiconductor device, it is more desirable that the metal concentration is lower than the ppm order, that is, ppb order or less, Are all preferably in a mass basis), and it is particularly preferable that they are substantially free.

Examples of the method for reducing the metal concentration include a method of sufficiently performing filtration using distillation or an ion exchange resin in at least one of steps of a raw material used for producing the treatment liquid and a step after the treatment liquid is prepared .

As another method of reducing the metal concentration, there is a method in which a container containing a raw material to be used in the production of a treatment liquid is subjected to a treatment with a small amount of impurities, And the like. A method of lining a fluorine resin on the inner wall of the pipe so that the metal component does not elute from the "pipe" or the like at the time of preparation of the treatment liquid can be used.

<Applications>

The treatment liquid of the present invention is a treatment liquid for a semiconductor device. In the present invention, the term "for a semiconductor device" means used for manufacturing a semiconductor device. The treatment liquid of the present invention can be used in any process for manufacturing a semiconductor device and is used, for example, for treatment of a resist film, an etching residue, an antireflection film, and an ashing residue existing on a substrate.

Specifically, the treatment liquid is a cleaning liquid (rinsing liquid) used for removing residues such as etching residues adhered on a metal film or interlayer insulating film, a solution used for removing various resist film for pattern formation, (For example, a color filter, a transparent insulating film, a lens made of resin) or the like from a semiconductor substrate. In addition, since the semiconductor substrate after removal of the permanent film may be used again in the use of the semiconductor device, the removal of the permanent film is included in the manufacturing process of the semiconductor device.

The treatment liquid of the present invention is a substrate having a metal hard mask including at least one of Cu, Co, W, AlOx, AlN, AlOxNy, WOx, Ti, TiN, ZrOx, HfOx, Quot; mask-attached substrate ").

<Process for Producing Treatment Liquid>

The method of producing the treatment liquid of the present invention is not particularly limited. And mixing the predetermined raw materials sufficiently by using an agitator such as a mixer or the like. It is also possible to use a method in which the pH is adjusted to a set pH in advance, or a method in which the pH is adjusted to a set pH after mixing. It is also possible to prepare a concentrate containing the above compound, dilute it in use, and adjust it to a predetermined concentration. Alternatively, the concentrate may be used after being adjusted to the set pH after dilution. In addition, a predetermined amount of pure water for dilution may be added to the concentrated liquid, or a predetermined amount of concentrated liquid may be added to the pure water for dilution.

It is preferable that the treatment liquid of the present invention has a step of mixing a predetermined raw material and thereafter carrying out a predetermined number of the counted coefficients of the size of 0.05 탆 or more counted by the light scattering type submerged particle counter. The step of making the number of the subject units of the size of 0.05 탆 or more, which is counted by the light scattering type submerged particle counter, may be a step of performing a purification step such as filtration using a filter, Counting the number of the units to be counted by the number of units to be treated, and finishing the preparation of the treatment liquid at the time when the number of the units to be contained in the treatment liquid reaches a desired value. As the filter used in the purification of the treatment liquid of the present invention, it is preferable to use an alkali compound and water in the treatment liquid of the present invention, , And positively charged nylon filters are preferable.

The coefficient of the object to be measured by the light scattering type submerged particle counter may be batchwise or it may be continuously counted by introducing the fluorescence particle counter of the light scattering type into the manufacturing line of the treatment liquid .

In general, the number of the coefficient bodies of a size of 0.05 m or more, which is counted by a light scattering type submerged particle counter, is often more than 2000 per 1 ml of the treatment liquid.

The treatment liquid in the present invention may be a kit in which the raw material is divided into a plurality of parts. For example, a liquid composition containing an alkaline compound in water as a first liquid is prepared, and a liquid composition containing other ingredients in water as a second liquid is prepared. As a use example thereof, it is preferable that the treatment liquid is mixed by mixing the two liquids, and then the liquid is applied to the treatment in a timely manner. Organic solvents and the like may be contained in either of them. By doing so, the deterioration of the liquid performance due to the decomposition of the alkali compound or other components is not caused, and the effect of the present invention can be effectively exerted. 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.

[Cleaning Method of Substrate]

The method of cleaning a substrate of the present invention is characterized by comprising a treatment liquid preparation step A for preparing the treatment liquid and a treatment liquid preparation step A for preparing a treatment liquid containing at least one of Cu, Co, W, AlOx, AlN, AlOxNy, WOx, Ti, TiN, ZrOx, HfOx And a cleaning step B for cleaning a substrate having a metal hard mask containing at least one of TaOx and TaOx.

<Objects to be cleaned>

The object to be cleaned in the cleaning method of the substrate of the present invention is a substrate provided with a metal hard mask containing at least one of Cu, Co, W, WOx, AlOx, AlN, AlOxNy, Ti, TiN, ZrOx, HfOx and TaOx And is not particularly limited.

The metal hard mask is formed in a pattern shape and has a predetermined opening.

The object to be cleaned by the cleaning method of the substrate of the present invention may be, for example, a laminate on which a metal film, an interlayer insulating film, and a metal hard mask are provided in this order. The laminate further has holes formed from the surface (opening portion) of the metal hard mask toward the substrate so as to expose the metal film surface by a dry etching process or the like.

A method for producing a laminate having holes as described above is not particularly limited, but a metal hard mask is usually applied to a pre-treatment laminate having a substrate, a metal film, an interlayer insulating film, and a metal hard mask in this order, A dry etching process is performed to etch the interlayer insulating film so that the surface of the metal film is exposed to provide a hole penetrating through the metal hard mask and the interlayer insulating film.

The method of manufacturing the metal hard mask is not particularly limited. For example, first, a metal film containing a predetermined component is formed, and a resist film of a predetermined pattern is formed thereon. Next, a method of producing a metal hard mask by etching the metal film using the resist film as a mask can be mentioned.

The laminate may have a layer other than the above-described layer, and examples thereof include an etching stopper film and an antireflection layer.

1 is a schematic cross-sectional view showing an example of a laminate which is an object to be cleaned in the method of cleaning a substrate of the present invention.

The laminate 10 shown in Fig. 1 has 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, A hole 6 through which the metal film 2 is exposed at a predetermined position is formed by a dry etching process or the like. 1 includes a substrate 1, a metal film 2, an etching stopper layer 3, an interlayer insulating film 4, and a metal hard mask 5 in this order , And a hole (6) penetrating from the surface to the surface of the metal film (2) at the position of the opening of the metal hard mask (5). The inner wall 11 of the hole 6 is formed by the end wall 11a made of the etching stopper layer 3, the interlayer insulating film 4 and the metal hard mask 5 and the bottom wall 11b made of the exposed metal film 2, (11b), and the dry etching residue (12) is attached.

The substrate cleaning method of the present invention can be suitably used for cleaning for the purpose of removing these dry etching residues 12. [ That is, the removal performance of the dry etching residue 12 is excellent, and the performance performance against the inner wall 11 (for example, the metal film 2) of the object to be cleaned is excellent.

The substrate cleaning method of the present invention may be carried out on a laminate subjected to a dry ashing process after the dry etching process.

Hereinafter, the constituent materials of the respective layers of the above-mentioned laminate will be described.

(Metal hard mask)

The metal hard mask is not particularly limited as long as it contains at least one of Cu, Co, W, AlOx, AlN, AlOxNy, WOx, Ti, TiN, ZrOx, HfOx and TaOx. 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, the dielectric constant k is preferably 3.0 or less, and more preferably 2.6 or less.

Specific examples of the material of the interlayer insulating film include SiO ₂ , SiOC-based materials, organic polymers such as polyimide, and the like.

(Etching stop layer)

The material of the etching stop layer is not particularly limited. Specific examples of the material of the etch stop layer include SiN, SiON, SiOCN-based materials, 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. Specific examples thereof include copper, titanium, titanium-tungsten, titanium nitride, tungsten, cobalt, tantalum, tantalum compounds, chromium, chromium oxide, aluminum and the like. From the viewpoint of obtaining the effect of the treatment liquid of the present invention, cobalt and tungsten are particularly preferable as the wiring material.

(Board)

Here, the "substrate" 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 made of a single layer is not particularly limited, and it is generally preferable that it is made of a III-V group compound such as silicon, silicon germanium, GaAs, or any combination thereof.

In the case of a multi-layered semiconductor substrate, the structure is not particularly limited. For example, an exposed integrated circuit structure such as interconnect features such as a metal line and a dielectric material on a semiconductor substrate such as the above- . Examples of metals and alloys used for the interconnect structure include, but are not limited to, aluminum, aluminum alloyed with copper, copper, titanium, tantalum, cobalt, silicon, titanium nitride, tantalum nitride, and tungsten . Further, a layer such as an interlayer dielectric layer, silicon oxide, silicon nitride, silicon carbide and carbon-doped silicon oxide may be provided on the semiconductor substrate.

Hereinafter, the process liquid preparation process A and the cleaning process B will be described in detail.

(Treatment liquid preparation step A)

The treatment liquid preparation step A is a step of preparing the treatment liquid. The components used in the present step are as described above.

The order of this step is not particularly limited, and for example, there can be mentioned a method of adding a hydroxylamine compound, a corrosion inhibitor, and other optional components to water and stirring and mixing to prepare a treatment liquid. In the case where each component is added to water, it may be added in a batch or may be added in divided portions a plurality of times.

It is preferable that each component contained in the treatment liquid is classified into a semiconductor grade or a high purity grade corresponding thereto. It is preferable to use a material having a large amount of impurities at the starting point of the raw material, which is subjected to removal of impurities by filtration and reduction of an ion component by an ion exchange resin or the like.

It is also preferable to perform the above-described filtering or the like so that the number of the coefficients to be contained in the treatment liquid becomes a desired range.

(Cleaning step B)

Examples of the substrate with a mask to be cleaned in the cleaning step B include the above-mentioned laminate, and a laminate having holes formed by a dry etching process as described above is exemplified. In this laminate, dry etching residues are attached in the holes.

Further, the laminate subjected to the dry ashing process after the dry etching process may be used as an object to be cleaned.

The method of bringing the treatment liquid into contact with the masked substrate is not particularly limited, and examples thereof include a method of immersing the substrate with the mask in the treatment liquid put in the tank, a method of spraying the treatment liquid onto the substrate with the mask, A method of flowing the treatment liquid, or any combination thereof. From the viewpoint of the removability of the residue, it is preferable to immerse the substrate with the mask in the treatment liquid.

The temperature of the treatment liquid is preferably 90 占 폚 or lower, more preferably 25 占 폚 to 80 占 폚, still more preferably 30 占 폚 to 75 占 폚, and particularly preferably 40 占 폚 to 65 占 폚.

The cleaning time can be adjusted depending on the cleaning method used and the temperature of the treatment liquid.

In the case of cleaning by an immersion arrangement method (a batch method in which a plurality of objects to be cleaned are immersed in a treatment tank), the cleaning time is preferably within a range from 60 minutes to 1 to 60 minutes, More preferably from 4 to 15 minutes.

In the case of cleaning in a sheet-like manner, the cleaning time is, for example, 10 seconds to 5 minutes, preferably 15 seconds to 4 minutes, more preferably 15 seconds to 3 minutes, and more preferably 20 seconds to 2 minutes .

Further, in order to further enhance the cleaning ability of the treatment liquid, a mechanical stirring method may be used.

Examples of the mechanical stirring method include a method of circulating a treatment liquid on a substrate with a mask, a method of flowing or spraying a treatment liquid on a substrate with a mask, a method of stirring the treatment liquid by ultrasonic waves or megasonic .

(Rinsing step B2)

The cleaning method of the substrate of the present invention may further include a step (rinse step B2) of cleaning the masked substrate with a solvent after the cleaning step B to clean the substrate.

The rinsing step B2 is preferably performed in succession to the cleaning step B and rinsing with a rinsing agent for 5 seconds to 5 minutes. The rinsing step B2 may be performed using the above-described mechanical stirring method.

Examples of the rinsing solvent include deionized water, methanol, ethanol, isopropyl alcohol, N-methylpyrrolidinone,? -Butyrolactone, dimethylsulfoxide, ethyl lactate and propylene glycol Monomethyl ether acetate, but are not limited thereto. Alternatively, an aqueous rinse solution of pH &gt; 8 (dilute aqueous ammonium hydroxide or the like) may be used.

The rinsing agent is preferably an aqueous solution of ammonium hydroxide, DI water, methanol, ethanol and isopropyl alcohol, more preferably aqueous ammonium hydroxide solution, DI water and isopropyl alcohol, more preferably ammonium hydroxide aqueous solution and DI water.

As a method of bringing the rinsing solvent into contact with the mask-adhered substrate, a method of bringing the treating solution into contact with the mask-adhered substrate can be similarly applied.

The temperature of the rinsing solvent in the rinsing step B2 is preferably 16 to 27 占 폚.

The above-mentioned treatment liquid may be used as a rinsing solvent in the rinsing step B2.

(Drying step B3)

The cleaning method of the substrate of the present invention may have a drying step B3 for drying the mask-attached substrate after the rinsing step B2.

The drying method is not particularly limited. Examples of the drying method include a spin drying method, a method of flowing a dry gas onto 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 drying method of Marangoni, a drying method of Rotagoni, Propyl alcohol) drying method, or any combination thereof.

The drying time depends on the specific method to be used, but it is generally preferably 30 seconds to several minutes.

(Metal ion removal processes F and G)

The cleaning method of the substrate of the present invention may further comprise a metal ion removing step F for removing Fe ions from at least one of the hydroxylamine compound and water before the above-mentioned treatment liquid preparation step A, It is preferable to have a metal ion removing step G for removing Fe ions in the treatment liquid after the cleaning step A and before the cleaning step B.

It is preferable that the Fe ion content in the treatment liquid used in the cleaning step B is adjusted to 10 mass ppm to 10 mass ppm with respect to the total mass of the treatment liquid by performing the metal ion removing process F or the metal ion removing process G Do.

A specific method of the metal ion removing process F and the metal ion removing process G is not particularly limited, and examples thereof include distillation and purification using an ion exchange membrane.

By adjusting the content of Fe ions in the treatment liquid to the above range, the cleaning performance of the treatment liquid can be maintained satisfactorily even after aging, and the recyclability is also excellent. In addition, by suitably adjusting the content ratio of the total content of Fe ions and the content of the hydroxylamine compound in the treatment liquid, the performance of removing the residue of the treatment solution is further improved, and the recyclability is also superior.

(Coarse particle removing step H)

The substrate cleaning method of the present invention preferably has a coarse particle removing step H for removing coarse particles in the treatment liquid after the treatment liquid preparation step A and before the cleaning step B is performed.

By reducing or eliminating coarse particles in the treatment liquid, the amount of coarse particles remaining on the mask-attached substrate after the cleaning process B can be reduced. As a result, the pattern damage caused by the coarse particles on the mask-attached substrate can be suppressed, and the influence on the yield reduction and the reliability reduction of the device can be suppressed.

As a specific method for removing coarse particles, for example, a method of filtering and purifying a treatment solution through a treatment liquid preparation step A using a particle removal membrane having a predetermined particle removal diameter, and the like can be given.

The definition of coarse particles is as described above.

(Static elimination process I, J)

The substrate cleaning method of the present invention is characterized in that before the above-mentioned treatment liquid preparation step A, there is a charge elimination step I for discharging water, or after the treatment liquid preparation step A and before the cleaning step B , And a discharge step J for discharging the treatment liquid.

The treatment liquid of the present invention has a function of reducing a metal in that it contains a hydroxylamine compound. Due to this, it is preferable that the material of the liquid-contact portion for supplying the treatment liquid to the substrate with the mask is made of a resin which does not elute metal with respect to the treatment liquid. Such a resin has low electric conductivity and is insulative. Therefore, for example, when the treatment liquid is passed through a pipe made of resin, or when the resin is filtered and purified by a particle removing film made of resin or an ion exchange resin film made of resin , There is a possibility that the electrostatic potential of the treatment liquid increases and electrostatic disaster may occur.

Therefore, in the cleaning method of the substrate of the present invention, it is preferable that the electrification step I or the electrification step J described above is carried out to reduce the electrification potential of the treatment liquid. In addition, by carrying out the charge elimination, it is possible to further suppress adhesion of foreign matter (coarse particles) to the substrate and damage to the substrate (corrosion).

As the erasing method, specifically, a method in which water or a treatment liquid is brought into contact with a conductive material may be mentioned.

The contact time for bringing the water or the treatment liquid into contact with the conductive material is preferably 0.001 to 1 second, more preferably 0.01 to 0.1 second.

Specific examples of the resin include high density polyethylene (HDPE), high density polypropylene (PP), 6,6-nylon, tetrafluoroethylene (PTFE), copolymers of tetrafluoroethylene and perfluoroalkyl vinyl ethers (PFA) , Ethylene chlorotrifluoroethylene copolymer (ECTFE), ethylene-tetrafluoroethylene copolymer (ETFE), tetrafluoroethylene-hexafluoropropylene copolymer (FEP) .

As the conductive material, stainless steel, gold, platinum, diamond, and gracicarbon are preferable.

In the cleaning method of the substrate using the treatment liquid of the present invention, when the treatment liquid of the present invention has a recyclable composition, the discharged liquid of the treatment liquid used in the cleaning step B is reused, It is possible to use.

The cleaning method of the substrate of the present invention preferably comprises the following steps when the discharged liquid of the treatment liquid is reused.

The process liquid preparation step A,

The cleaning step B,

A discharged-liquid recovery step C for recovering the discharged liquid of the treatment liquid used in the cleaning step B,

A metal hard mask including at least one of Cu, Co, W, AlOx, AlN, AlOxNy, WOx, Ti, TiN, ZrOx, HfOx and TaOx newly prepared by using the discharged liquid of the recovered process liquid A cleaning step D for cleaning the substrate,

And a discharged-liquid recovery step E for recovering the discharged liquid of the treatment liquid used in the cleaning step D,

The cleaning step D and the discharged liquid recovery step E are repeatedly performed.

In the embodiment in which the discharged liquid is reused, the process liquid preparation process A and the cleaning process B are the same as the process liquid preparation process A and the cleaning process B described in the above embodiments, and the same is also true for the preferable mode. Also, in the aspect of reusing the above-mentioned discharged liquid, it is preferable to have the metal ion removing process F, G, coarse particle removing process H, and discharging process I, J described in the above embodiment.

The cleaning process D for cleaning the substrate by using the discharged liquid of the recovered process liquid is the same as the cleaning process B in the above-described mode, and the preferred embodiment is also the same.

The discharged liquid recovery means in the discharged liquid recovery process C or E is not particularly limited. The recovered discharged liquid is preferably stored in the above-described resin container in the discharging step J, and the discharging step same as the discharging step J may be performed at this time.

It is preferable to carry out a step of preparing the number of the subject to be counted contained in the recovered treatment liquid after at least one of the discharged liquid recovery step C and the discharged liquid recovery step E and before the cleaning step D . The number of the units to be counted can be adjusted, for example, by a filtering treatment of the recovered treatment liquid.

[Method of Manufacturing Semiconductor Device]

The method for manufacturing a semiconductor device according to the present invention is a method for manufacturing a semiconductor device which comprises at least one of Cu, Co, W, AlOx, AlN, AlOxNy, WOx, Ti, TiN, ZrOx, HfOx and TaOx And a cleaning step of cleaning the substrate having the metal hard mask.

The manufacturing method of the semiconductor device of the present invention may include at least the above-described cleaning step, and this cleaning step is in agreement with the above-described cleaning step B, and the preferred embodiment is also the same. The semiconductor device manufacturing method has a process other than the cleaning process, and may include, for example, the rinsing process B2 and the drying process B3 described above.

Typically, after the cleaning step, one or more additional circuitry is further formed on the substrate after the unnecessary metal hard mask is removed, or the substrate is further processed by, for example, assembling (e.g., dicing and bonding) For example, chip sealing) is performed to form a semiconductor chip or the like.

Examples of the semiconductor device include a flash memory and a logic device.

Example

Hereinafter, the treatment liquid of the present invention will be described in detail with reference to examples. However, the present invention is not limited thereto.

&Lt; Preparation of treatment liquid &

First, the components shown in Tables 1 and 2 were mixed in the ratios shown in Tables 1 and 2 to obtain a mixed solution. In the first and second tables, the concentration (mass%) of each component used is as described in the table, and the balance is water.

Here, all the components shown in Tables 1 and 2 were all classified as semiconductor grades or classified into high purity grades corresponding thereto. With regard to the components having many impurities at the starting point of the raw material, the removal of impurities by filtration and the reduction of ion components by ion exchange resins were performed.

The water (ultrapure water) used was prepared by the method described in paragraphs 0074 to 0084 of Japanese Laid-Open Patent Publication No. 2011-110515. Further, this method includes a metal ion removing step, and it was confirmed that the Fe ion amount is 1 mass ppt or less. The content of Fe ions was measured by an inductively coupled plasma mass spectrometer (Agilent 7500cs, manufactured by Yokogawa Analytical Systems Co., Ltd.).

Then, the obtained mixed solution was refined by circulation filtration, and a liquid particle counter (product number: KS-18F, light source: semiconductor laser excitation solid laser (wavelength 532 nm, rated output 500 mW) Min) was used to carry out the coefficient of the water coefficient of 0.05 m or more in size contained in 1 ml of the mixed solution.

When the number of the plies contained in the mixture solution reached a desired value, the mixture solution was charged into a recovery container (a clean bottle made by Iceland Kagaku). The mixed solution filled in the recovery container in this manner was used as the treatment solution in each of Examples and Comparative Examples. In addition, the size of the coefficient to be contained in the treatment liquid (mixed liquid) adjusted by the above method was 0.05 탆 or more and less than 0.1 탆.

Here, the liquid particle counter was used after calibrating with a PSL (Polystyrene Latex) standard particle liquid. In addition, the number of the counted coefficients to be counted is shown in Tables 1 and 2 as "the number of the counted coefficients of the combination day ".

The treatment liquids of the examples in Table 2 were obtained by purifying the hydroxylamine compound and the solvent contained in the treatment liquid (metal ion removal step F) and purifying the treatment liquid after preparation And step G), the Fe ion concentration was adjusted to a desired value.

Specifically, a treatment liquid was applied to an ion exchange resin membrane (Ion Clean SL Product No. DFA1SRPESW44, manufactured by Nippon Polyurethane Industry Co., Ltd., film surface area 1100 cm ² , number of filters: 1 to 2) at a flow rate of 0.3 to 0.6 L / .

The content of Fe ions with respect to the total mass of the treatment liquid in the treatment liquid was measured by an inductively coupled plasma mass spectrometer (Model: Agilent 7500cs, manufactured by Yokogawa Analytical Systems).

The components used in the treatment liquid are shown below.

<Water>

Ultrapure water

<Hydroxylamine Compound>

HA: Hydroxylamine (manufactured by BASF)

HAS: Hydroxyl ammonium sulfate (manufactured by BASF)

HAC: Hydroxylammonium hydrochloride (manufactured by Wako Pure Chemical Industries, Ltd.)

HAN: Hydroxylammonium nitrate (manufactured by Sigma-Aldrich)

<Corrosion inhibitor 1, corrosion inhibitor 2>

5M-BTA (5-methyl-1H-benzotriazole, manufactured by Tokyo Kasei Kogyo Co., Ltd.)

BTA (benzotriazole, manufactured by Tokyo Kasei Kogyo Co., Ltd.)

Carboxybenzotriazole (manufactured by Tokyo Kasei Kogyo Co., Ltd.)

Phthalic anhydride (manufactured by Tokyo Kasei Kogyo Co., Ltd.)

Tetramethylguanidine (manufactured by Tokyo Kasei Kogyo Co., Ltd.)

3- (2-aminophenylthio) -2-hydroxypropylmercaptan (manufactured by Tokyo Kasei Kogyo Co., Ltd.)

3-mercapto-1,2-propanediol (manufactured by Tokyo Kasei Kogyo Co., Ltd.)

&Lt; Evaluation test >

(Evaluation of Residual Removal Performance)

Using each of the prepared treatment solutions, the residue removing performance was evaluated. In the following evaluation, a model film made of TiO ₂ , which is a kind of residue, was prepared, and the etching removal rate was evaluated to evaluate the residue removal performance. That is, when the etching rate is high, the remnant removing performance is excellent, and when the etching rate is low, the remnant removing performance is inferior.

In addition, the model film (TiO ₂ film) is formed of TiO _2, is provided to a thickness of 1000Å on a Si substrate.

(a) Evaluation of residue removal performance within 24 hours after bathing

Each of the treatment solutions of Examples and Comparative Examples was used within 24 hours after the preparation to etch the TiO ₂ film. Specifically, the TiO ₂ film was immersed in the treatment solutions of Examples and Comparative Examples for 5 minutes, and the etching rate (Å / minute) was calculated based on the difference in film thickness of the TiO ₂ film before and after the immersion of the treatment solution.

The film thickness of the TiO ₂ film before and after the treatment was measured using a ellipsometry (spectroscopic ellipsometer, trade name "Vase", J · A Woollam Japan) at a measurement range of 250 to 1000 nm, 75 DEG C.

The etch rate (ER) of the calculated TiO ₂ film was evaluated according to the following evaluation criteria.

A: 5 (Å / min) ≦ ER

B: 3 (Å / min) ≦ ER <5 (Å / min)

C: 1 (Å / min) ≦ ER <3 (Å / min)

D: ER &lt; 1 (A / min)

(b) Evaluation of residue removal performance after thermocycle test

Each treatment liquid was enclosed in a container (ICELOGAGAGUCHE clean bottle). Next, the container filled with the treatment liquid was allowed to stand under the condition of 5 占 폚 for 12 hours, and then the container filled with the treatment liquid was allowed to stand under the condition of 30 占 폚 for 12 hours. Cycle test. The thermocycling test in the example is a corresponding test by repeating the change in the temperature environment.

An evaluation test of the residue remover performance was carried out in the same manner as in "(a) Evaluation of residue removal performance within 24 hours after conditioning operation" using the treatment liquid after the thermocycling test. In addition, the evaluation standard is the same as the above-mentioned "(a) Evaluation of the residue removal performance within 24 hours after conditioning."

(c) Evaluation of residue removal performance after long-term refrigerated storage

With respect to each of the treatment solutions described in Table 2, the performance of removing the residue after long-term refrigerated storage was evaluated.

Specifically, each treatment liquid described in Table 2 was filled in a container (a clean bottle made by Iceloggan Kagaku). Next, the container in which the treatment liquid was sealed was allowed to stand for 6 months at 5 DEG C, and long-term refrigerated storage was performed.

An evaluation test of the residue remover performance was carried out in the same manner as in "(a) Evaluation of residue remover performance within 24 hours after conditioning operation" In addition, the evaluation standard is the same as the above-mentioned "(a) Evaluation of the residue removal performance within 24 hours after conditioning."

(Evaluation of performance of the system)

The performance of the system was evaluated using each treatment liquid prepared as described above. In the following evaluation, a film (a wiring model, hereinafter also referred to as a " Cu film ") consisting of a film made of SiO _x (a model of an insulating film), a film made of Co (Wiring model, hereinafter also referred to as "W film") composed of W (tungsten) and W (tungsten).

The film thickness of each film is 1000 angstroms.

(a) Evaluation of the performance of the system within 24 hours after conditioning

· SiOx film

The etching solutions of the SiOx films were used within 24 hours after the preparation of each of the treatment solutions of Examples and Comparative Examples. Specifically, the SiOx film was immersed in the treatment solutions of the examples and the comparative example for 10 minutes, and the etching rate (Å / min) was calculated based on the difference in film thickness of the SiOx film before and after the immersion of the treatment solution.

The film thickness of the SiOx film before and after the treatment was measured using a ellipsometry (spectroscopic ellipsometer, trade name "Vase", J · A Woollam Japan) Under the conditions shown in Fig.

The etch rate (ER) of the calculated SiOx film was evaluated according to the following evaluation criteria. When the etching rate is low, the performance is excellent, and when the etching rate is high, the performance of the method is inferior.

A: ER? 1 (? / Min)

B: 1 (Å / min) <ER ≤ 3 (Å / min)

C: 3 (Å / min) <ER ≤ 6 (Å / min)

D: 6 (Å / min) <ER ≤ 10 (Å / min)

E: 10 (Å / min) <ER ≤ 30 (Å / min)

F: 30 (Å / min) <ER (Å / min)

Co film, Cu film, W film

Each of the treatment solutions of Examples and Comparative Examples was used within 24 hours after the preparation, and each of the Co film, the Cu film and the W film was etched. Specifically, the respective films were immersed in the treatment liquids of the examples and the comparative example for 10 minutes, and the amount of change (sheet resistance value of each film after immersion) of the sheet resistance value (? /?) Of each film before and after immersion of the treatment liquid- (Sheet resistance value of each film before immersion)) was converted into film thickness difference, and etching rate (Å / minute) was calculated to evaluate system performance.

The sheet resistance value (? /?) Was measured using a sheet resistance meter (product number: main body VR-120S, 4 probe probe KS-TC-200-MT-200g, manufactured by Hitachi Kokusai Denki Engineering Co., , And the voltage value when a current of 30 mA was passed through each film was calculated.

When the etching rate is low, the system performance is excellent, and when the etching rate is high, the system performance is inferior.

A: ER? 1 (? / Min)

B: 1 (Å / min) <ER ≤ 3 (Å / min)

C: 3 (Å / min) <ER ≤ 6 (Å / min)

D: 6 (Å / min) <ER ≤ 10 (Å / min)

E: 10 (Å / min) <ER ≤ 30 (Å / min)

F: 30 (Å / min) <ER (Å / min)

(b) Evaluation of the performance of the system after the thermocycle test

Each treatment liquid was enclosed in a container (ICELOGAGAGUCHE clean bottle). Next, the vessel filled with the treatment liquid was allowed to stand under the condition of 5 hours at 12 占 폚, and then the vessel filled with the treatment liquid was allowed to stand at 30 占 폚 for 12 hours. A thermocycle test was conducted.

Evaluation of the performance of the system was carried out in the same manner as in "(a) Evaluation of the performance of the system within 24 hours after conditioning" by using the treatment liquid after the thermocycling test. The evaluation standard is also the same as the above "(a) Evaluation of the performance of the system within 24 hours after conditioning."

(c) Evaluation of system performance after long-term refrigerated storage

For each of the treatment solutions described in Table 2, the performance of the system after long-term refrigerated storage was evaluated.

Specifically, each treatment liquid described in Table 2 was filled in a container (a clean bottle made by Iceloggan Kagaku). Next, the container in which the treatment liquid was sealed was allowed to stand for 6 months at 5 DEG C, and long-term refrigerated storage was performed.

Evaluation of the performance of the system was carried out in the same manner as in "(a) Evaluation of system performance within 24 hours after conditioning" by using the treatment liquid after long-term refrigerated storage. In addition, the evaluation standard is the same as the above-mentioned "(a) Evaluation of the performance of the system within 24 hours after conditioning."

&Lt; Evaluation result >

The results of the evaluation test are shown in Tables 1 and 2.

[Table 1]

[Table 2]

All of the treatment solutions of the examples shown in Table 1 were subjected to repeated changes of the temperature environment (evaluation of the treatment solution within 24 hours after the conditioning solution) ) And the performance of the method.

From the comparison of Examples 1, 5, 11, and 13 to 16, it was found that the method performance was superior by using the triazole compound as the corrosion inhibitor (Examples 1, 5, 11, and 13). From the comparison of Examples 1, 5, 11 and 13, it was found that the combination of the triazole compound and the mercapto group-containing compound as the corrosion inhibitor (Examples 1 and 5) exhibited better performance. From the comparison between Example 1 and Example 5 and from the comparison between Example 11 and Example 13, it can be seen that among the triazole compounds, 5-methylbenzotriazole was used (Examples 1 and 11) Appeared.

From the contrast between Example 1 and Example 11 and the contrast between Example 5 and Example 13, it was found that by using a combination of a triazole compound and a mercapto group-containing compound as corrosion inhibitors (Examples 1 and 5) And the performance of the system after the operation is more excellent.

From the comparison of Examples 1 to 3, it was found that when the number of the processed matter contained in the treatment liquid was in the range of 1 to 1000 pieces / ml (Examples 1 and 2), the afterglow removal performance .

From the comparison of Examples 1 to 3, it was found that when the number of predetermined coefficients to be contained in the treatment liquid was in the range of 1 to 1000 pieces / ml (Examples 1 and 2), the system performance was better, (Example 1) showed that the method performance was particularly excellent when the number of the counted coefficients in the range of 1 to 100 / ml.

All of the treatment solutions of the examples shown in Table 2 showed excellent residue removal performance and system performance (evaluation of the treatment solution within 24 hours after the tank solution).

Although not shown in Table 2, the treatment liquids of the examples shown in Table 2 were confirmed to have excellent residue removal performance and system performance after repeated temperature environment changes (evaluation of the treatment liquid after the thermocycling test) .

From the comparison of Examples 17 to 24 as in the evaluation results of Table 2, it is understood that when the concentration of Fe ions contained in the treatment liquid is within the range of 10 mass ppm to 10 mass ppm (Examples 17, 18, 20, 21, 22, 24), and it was found that the residual remnant removal performance after long-term refrigerated storage was excellent. Further, when the concentration of Fe ions contained in the treatment liquid was in the range of 10 mass ppt to 1000 mass ppb (Examples 17, 18, 21, and 22), it was found that the residue removal performance after the long-term refrigerated storage was excellent. Further, when the concentration of Fe ions contained in the treatment liquid is in the range of 10 mass ppt or more and less than 1000 mass ppt (Examples 17 and 21), it has been found that the residue removal performance after the long-term refrigerated storage is further improved. From this result, even when the step of removing metal ions is applied to the treatment liquid after the treatment liquid is prepared, the same effect is expected.

(Mass ratio) (mass of the mercapto group-containing compound / mass of the triazole compound) of the mercapto group-containing compound relative to the triazole compound contained as the corrosion inhibitor in the treatment liquid is 0.1 - 50 (Examples 26, 27, and 28), it was found that the residue removing performance and system performance after long-term refrigerated storage were further improved. Further, when the content ratio is in the range of 0.1 to 20 (Examples 26 and 27), it has been found that the residue removing performance and system performance after long-term refrigerated storage are further improved. Further, when the content ratio is in the range of 0.1 to 10 (Example 26), it has been found that the residue removing performance and the performance performance after preserving the long-term refrigerated state are further improved.

Although not shown in the table, it is confirmed that all of the processing solutions of the examples exhibit excellent residue removing performance even for a metal hard mask containing any one of AlOx, AlN, AlOxNy, Ti, TiN, ZrOx, HfOx and TaOx I could.

On the other hand, since the treatment liquid of Comparative Example 1 contained no corrosion inhibitor, the system performance was poor (evaluation of the treatment liquid within 24 hours after the liquid bath).

Since the treatment liquid of Comparative Example 2 contained no predetermined coefficient of constant, the residue remover performance and system performance were inferior (evaluation of the treatment solution within 24 hours after the tank solution), and the temperature environment change was repeated (The evaluation of the treatment liquid after the thermocycling test) was inadequate.

<Antistatic Evaluation>

The treatment solutions of Example 5 and Example 6 were evaluated in the same manner as in Example 1 except that the grounded material SUS316 was used and the immersion time was 20 minutes, , And the system performance (Co film, W film, SiOx film) within 24 hours after the liquid was evaluated.

As a result of the evaluation, in the case where the treatment solution was subjected to the elimination step or not, any residual solution removal performance did not change. On the other hand, regarding various evaluations of the performance of the Co film, the performance of the W film, and the performance of the SiOx film, the performance of the antifouling process was better than that of the antifriction process.

From these results, it was found that the processing performance of the treatment liquid was superior by the elimination step.

<Recycling test>

Using the treatment liquid of Example 1, the operation described in the evaluation of the residue removal performance within 24 hours after the liquid conditioning was performed 25 times in succession. At this time, each time one film was treated, 25 films were immersed one by one in the same treatment solution without changing the treatment solution.

Thereafter, the treatment liquid of Example 1 was recovered in a tank, and the residue removal performance within 24 hours after the liquid was again evaluated. This series of treatments is referred to as a recycle test (residual product removal performance).

Also, for the treatment solutions of Examples 3, 17, and 20, the same recycling test (removal of the residue) as that of the treatment solution of Example 1 was performed.

Further, the treatment described in the evaluation of the system performance (only the Co film, the W film, and the SiOx film) within 24 hours after the liquid conditioning was carried out 25 times in succession using the treatment liquid of Example 1. At this time, each time one film was treated, 25 films were immersed one by one in the same treatment solution without changing the treatment solution.

Thereafter, the treatment liquid of Example 1 was recovered in a tank, and evaluation of the system performance (only the Co film, the W film, and the SiOx film was performed) within 24 hours after the liquid was again evaluated. This series of processing is referred to as a recycling test (method performance).

Also, for the treatment liquids of Examples 3, 17, and 20, the same recycling test (system performance) as that of the treatment liquid of Example 1 was performed.

As a result of the evaluation of the recycling test, in the treatment liquids of Examples 1 and 17, in the case of performing the recycle test and in the case of not carrying out the recycle test, an evaluation of the residual object removal performance within 24 hours after the liquid conditioning, (Co film, W film, and SiOx film) within a predetermined period of time can be judged to be the same.

On the other hand, in the case of the treatment liquid of Example 3, the same results as those in the case where the recycle test was not performed were obtained, except that the remnant removing performance and the system performance of the Co film were changed to "B ".

In the case of the treatment liquid of Example 20, the same results were obtained as in the case where the recycle test was not performed, except that the remnant removing performance and the performance performance of the Co film and the W film were changed to "B " lost.

From these results, it was found that the treatment liquid of the present invention can suppress the deterioration of performance even when the substrate is repeatedly treated, and is excellent in recyclability.

1 substrate
2 metal film
3 etch stop layer
Fourth interlayer insulating film
5 Metal Hard Mask
6 holes
10 laminate
11 inner wall
11a single wall
11b bottom wall
12 Dry etching residues

Claims (13)

1. A processing solution for a semiconductor device,
At least one hydroxylamine compound selected from a hydroxylamine and a hydroxylamine salt, water, and a corrosion inhibitor,
Wherein the number of the coefficient bodies having a size of 0.05 m or more, counted by the light scattering type submerged particle counter, is 1 to 2000 per 1 ml of the treatment liquid. The method according to claim 1,
Wherein the corrosion inhibitor is at least one compound selected from the group consisting of a triazole compound, a mercapto group-containing compound, maleic anhydride, phthalic anhydride, ammonium thiosulfate, tetramethylguanidine and a glycolic acid ester. The method according to claim 1 or 2,
Wherein the corrosion inhibitor comprises a triazole compound,
Wherein the triazole compound comprises at least one compound selected from benzotriazole, carboxybenzotriazole, 5-methylbenzotriazole, and triazole. The method according to any one of claims 1 to 3,
Wherein the corrosion inhibitor comprises a triazole compound and a mercapto group-containing compound,
Wherein the triazole compound comprises at least one compound selected from benzotriazole, carboxybenzotriazole, 5-methylbenzotriazole, and triazole,
Wherein the mercapto group-containing compound is at least one selected from the group consisting of 2-mercapto-5-methylbenzimidazole, 3-mercapto-1,2-propanediol, 2-mercaptothiazoline, 3- ) -2-hydroxypropylmercaptan, and 3- (2-hydroxyethylthio) -2-hydroxypropylmercaptan. The method according to any one of claims 2 to 4,
Wherein the triazole compound comprises 5-methylbenzotriazole. The method according to any one of claims 1 to 5,
Wherein the corrosion inhibitor comprises a triazole compound and a mercapto group-containing compound,
Wherein the mass ratio of the mercapto group-containing compound to the triazole compound is from 0.1 to 50. The method according to any one of claims 1 to 6,
Further comprising 10 parts by mass to 10 parts by mass of Fe ions. The method according to any one of claims 1 to 7,
Wherein the substrate is used for cleaning a substrate having a metal hard mask including at least one of Cu, Co, W, AlOx, AlN, AlOxNy, WOx, Ti, TiN, ZrOx, HfOx and TaOx. A process A for preparing the process liquid according to any one of claims 1 to 8,
A cleaning step of cleaning a substrate having a metal hard mask containing at least one of Cu, Co, W, AlOx, AlN, AlOxNy, WOx, Ti, TiN, ZrOx, HfOx and TaOx RTI ID = 0.0 &gt; B. &Lt; / RTI &gt; The method of claim 9,
A discharged-liquid recovery step C for recovering the discharged liquid of the treatment liquid used in the cleaning step B,
A substrate having a metal hard mask containing at least one of Cu, Co, W, AlOx, AlN, AlOxNy, WOx, Ti, TiN, ZrOx, HfOx and TaOx, A cleaning step D,
Further comprising a discharged-liquid collecting step E for collecting the discharged liquid used in the washing step D,
The cleaning step D and the discharged liquid recovery step E are repeated to recycle the discharged liquid. The method according to claim 9 or 10,
The metal ion removing step F for removing Fe ions from at least one of the hydroxylamine compound and the water prior to the treatment liquid preparation step A,
And a metal ion removal step (G) for removing Fe ions in the treatment solution after the treatment solution preparation step (A) and before the cleaning step (B) is performed. The method according to any one of claims 9 to 11,
Before the treatment liquid preparation step A, there is provided a discharging step I in which electricity is discharged to the water,
And a discharging step (J) for discharging the treatment liquid after the treatment liquid preparation step (A) and before the cleaning step (B) is performed. A metal hard mask including at least one of Cu, Co, W, AlOx, AlN, AlOxNy, WOx, Ti, TiN, ZrOx, HfOx, and TaOx by the treatment liquid according to any one of claims 1 to 8. And a cleaning step of cleaning the substrate with the cleaning liquid.

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