TWI790196B - Cleaning liquid, method for cleaning substrate, and method for manufacturing semiconductor device - Google Patents

Abstract

The object of the present invention is to provide a cleaning solution for a substrate containing Cu, Co, W, AlOx, AlN, AlOxNy, a substrate cleaning method using the cleaning solution, and a method of manufacturing a semiconductor device. , WOx, Ti, TiN, ZrOx, HfOx and TaOx any one or more metal hard mask substrates have excellent residue removal performance and excellent corrosion resistance to cleaning objects. The cleaning solution of the present invention is a cleaning solution for a substrate having a metal hard mask containing any one or more of Cu, Co, W, AlOx, AlN, AlOxNy, WOx, Ti, TiN, ZrOx, HfOx, and TaOx, and includes At least one selected from hydroxylamine and hydroxylamine salts and water. In addition, x and y are numbers represented by x=1-3 and y=1-2, respectively.

Description

Cleaning solution, substrate cleaning method, and semiconductor device manufacturing method

In particular, the present invention relates to a device containing Cu, Co, W, AlOx, AlN, AlOxNy, WOx, Ti, TiN, ZrOx, HfOx and TaOx (moreover, x, y are respectively represented by x=1~3, y=number represented by 1 to 2) any one or more of metal hard mask substrate cleaning solution and substrate cleaning method.

In detail, the present invention relates to a manufacturing step of a semiconductor element, and in particular relates to a method for removing components containing Cu, Co, W, AlOx, AlN, AlOxNy, WOx, Ti, TiN in the manufacture of a semiconductor element. , ZrOx, HfOx, and TaOx (moreover, x, y are numbers represented by x=1~3, y=1~2, respectively) The dry type existing on the substrate of the metal hard mask A cleaning solution for etching residues and the like, and a substrate cleaning method using the cleaning solution.

Furthermore, this invention also relates to the manufacturing method of the semiconductor element using the said cleaning liquid.

Semiconductor components such as Charge-Coupled Devices (CCD) and memories use photolithography technology to form tiny electronic circuits on the substrate. Road pattern to manufacture. Specifically, a resist film is applied on a laminated film having a metal film (such as Co, W) as a wiring material, an etching stopper film, and an interlayer insulating film formed on a substrate, and subjected to photolithography. steps and dry etching steps (such as plasma etching process) to manufacture. In addition, a photoresist stripping step for stripping components mainly derived from organic substances such as photoresist is performed by stripping means such as a dry ashing step (for example, plasma ashing treatment) as needed.

After the dry etching process, residues such as dry etching residues adhere to the wiring film or the interlayer insulating film of the substrate, and a cleaning solution is usually used to remove these residues.

For example, Patent Document 1 discloses a substrate cleaning method using HF (hydrogen fluoride).

[Prior art literature] [Patent Document]

[Patent Document 1] Japanese Patent Laid-Open No. 2013-4760

On the other hand, recently, in order to achieve further miniaturization, the use of a metal material-based resist film such as TiN, AlOx (so-called metal hard mask) as a resist film has been studied.

When a metal hard mask is used as a resist film, a dry etching step (such as a plasma etching process) is generally performed using the metal hard mask as a mask, followed by forming holes in a pattern shape based on the metal hard mask. Exposing the metal film surface that becomes the wiring film step.

The inventors of the present invention prepared the HF-containing cleaning solution described in Patent Document 1 and applied it to a form using a metal hard mask. As a result of research, it became clear that although the dry etching residue removal performance is excellent, the There is a problem of corroding wiring metals (metals, metal nitrides, or alloys, such as Co and W used as wiring metals) and interlayer insulating films which are objects to be cleaned.

Therefore, an object of the present invention is to provide a cleaning solution for a substrate having a metal hard mask containing a predetermined component, which has excellent residue removal performance and excellent corrosion resistance to objects to be cleaned.

Another object of the present invention is to provide a method of cleaning a substrate using the cleaning solution, and a method of manufacturing a semiconductor element.

As a result of diligent research to achieve the above-mentioned object, the inventors of the present invention found that the above-mentioned object can be solved by a cleaning solution containing hydroxylamine or a salt thereof as a reducing agent, and completed the present invention.

That is, it was found that the object can be achieved by the following configurations.

(1) A cleaning solution for a substrate provided with a metal hard mask containing any one or more of Cu, Co, W, AlOx, AlN, AlOxNy, WOx, Ti, TiN, ZrOx, HfOx, and TaOx , which includes: at least one hydroxylamine compound selected from hydroxylamine and hydroxylamine salts, and water.

In addition, x and y are numbers represented by x=1~3 and y=1~2, respectively.

(2) The cleaning solution as described in (1), which further includes 1 mass ppm to 10 mass ppm of Fe ions.

(3) The cleaning solution as described in (1) or (2), which further includes 1 mass ppm to 10 mass ppm of Co ions.

(4) The cleaning solution according to any one of (1) to (3), which further includes an anti-corrosion agent.

(5) The cleaning solution as described in any one of (1) to (4), wherein the anticorrosion agent is selected from compounds represented by formula (A) to formula (C) described later, and substituted or Any of the unsubstituted tetrazoles.

(6) The cleaning solution according to any one of (1) to (5), which further includes a chelating agent.

(7) The cleaning solution according to any one of (1) to (6), which further includes a water-soluble organic solvent.

(8) The cleaning solution according to any one of (1) to (7), which further includes a pH adjuster.

(9) The cleaning solution according to any one of (1) to (8), which further includes quaternary ammonium hydroxides.

(10) The cleaning solution according to any one of (1) to (9), which further includes a fluoride.

(11) The cleaning solution according to any one of (1) to (10), which has a pH of 6 to 11.

(12) A substrate cleaning method, comprising: Cleaning solution preparation step A, preparing a cleaning solution containing at least one hydroxylamine compound selected from hydroxylamine and hydroxylamine salts and water; and cleaning step B, using the cleaning solution to clean the equipment containing Cu, A substrate of any one or more of Co, W, AlOx, AlN, AlOxNy, WOx, Ti, TiN, ZrOx, HfOx, and TaOx metal hard mask.

In addition, x and y are numbers represented by x=1~3 and y=1~2, respectively.

(13) The substrate cleaning method as described in (12), which includes: cleaning solution preparation step A, preparing a cleaning solution containing at least one hydroxylamine compound selected from hydroxylamine and hydroxylamine salts and water; Cleaning step B, using the cleaning solution to clean the substrate with a metal hard mask containing any one or more of Cu, Co, W, AlOx, AlN, AlOxNy, WOx, Ti, TiN, ZrOx, HfOx and TaOx; Drainage recovery step C, recovering the drainage of the cleaning solution used in the cleaning step B; cleaning step D, using the recovered cleaning solution drainage, washing the re-prepared equipment containing Cu, Co , W, AlOx, AlN, AlOxNy, WOx, Ti, TiN, ZrOx, HfOx and TaOx any one or more metal hard mask substrate; Draining of the cleaning solution; and repeatedly implementing the cleaning step D and the drainage recovery step E to recycle the drainage of the cleaning solution.

(14) The substrate cleaning method described in (12) or (13), wherein Before the clean liquid preparation step A, there is a metal ion removal step F of removing at least one ion species selected from Fe ions and Co ions from at least one of the hydroxylamine compound and the water, or during the cleaning After the liquid preparation step A and before the cleaning step B, there is a metal ion removal step G of removing at least one ion species selected from Fe ions and Co ions in the cleaning liquid.

(15) The substrate cleaning method as described in any one of (12) to (14), which has a destaticizing step I for destaticizing the water before the cleaning liquid preparation step A, or After the cleaning solution preparation step A and before performing the cleaning step B, there is a static removal step J of removing electricity from the cleaning solution.

(16) A method of manufacturing a semiconductor element, which comprises using the cleaning solution described in any one of (1) to (10) to clean a device containing Cu, Co, W, AlOx, AlN, AlOxNy, WOx, The step of substrate of any one or more metal hard masks of Ti, TiN, ZrOx, HfOx and TaOx.

In addition, x and y are numbers represented by x=1~3 and y=1~2, respectively.

According to the present invention, there can be provided a cleaning solution for a substrate provided with a metal hard mask containing a predetermined component, and a substrate cleaning method using the same, and a method for manufacturing a semiconductor element. Excellent removal performance, and excellent corrosion resistance to the object to be cleaned.

1: Substrate

2: Metal film

3: Etch stop layer

4: Interlayer insulating film

5: Metal hard mask

6: hole

10: laminate

11: inner wall

11a: section wall

11b: bottom wall

12: Dry etching residue

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

Hereinafter, the present invention will be described in detail.

The description of the constituent requirements described below may be based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.

In addition, in this specification, the numerical range represented using "~" means the range which includes the numerical value described before and after "~" as a lower limit and an upper limit.

In addition, in the expression of the group (atom group) in this specification, within the range that does not impair the effect of the present invention, the expressions of substituted and unsubstituted include a group (atom group) without a substituent, and also A group (group of atoms) having a substituent is included. For example, the term "hydrocarbon group" includes not only a hydrocarbon group having no substituent (unsubstituted hydrocarbon group), but also a hydrocarbon group having a substituent (substituted hydrocarbon group). The same applies to the meaning of each compound.

In addition, in this specification, when referring to "preparation", it means not only preparing by synthesizing or blending a specific material, but also including preparing a predetermined substance by purchasing or the like.

In the present invention, dry etching residues are by-products produced by performing dry etching (such as plasma etching), for example, organic residues derived from photoresists, Si-containing residues, and metal-containing residues. residue etc. Furthermore, in the following description, the dry etching residue may also be simply referred to as "residue".

In addition, in the present invention, dry ashing residue is a by-product generated by performing dry ashing (such as plasma ashing), for example, it refers to organic residues derived from photoresists, residues containing Si , and metal-containing residues, etc.

[washing liquid]

The cleaning solution of the present invention is a substrate (hereinafter, also referred to simply as "" A cleaning solution for a substrate with a mask"), which includes: at least one hydroxylamine compound selected from hydroxylamine and hydroxylamine salts, and water. In addition, x and y are numbers represented by x=1~3 and y=1~2, respectively.

The cleaning liquid of the present invention has excellent residue removal performance and excellent corrosion resistance to objects to be cleaned by having the above configuration.

In addition, as will be described later, the present inventors have found that by including a trace amount of at least one ion species selected from Fe ions and Co ions in the cleaning solution in a predetermined amount, the cleaning solution can be maintained well over time. The cleaning performance of the cleaning solution (“there is little change in cleaning solution performance after 24 hours”). Furthermore, it was also confirmed that by adjusting at least one ion species selected from Fe ions and Co ions in the cleaning solution to a predetermined range as described above, and adjusting the content of hydroxylamine and its salts as a reducing agent with Fe ions When the content of Co ions and Co ions is set at a predetermined ratio, not only the cleaning performance of the cleaning solution can be maintained well over time, but also the residue removal performance can be further improved, and the corrosion resistance to the cleaning object can be further improved.

In addition, it was confirmed that by containing at least one ion species selected from Fe ions and Co ions in the cleaning solution, the decline in cleaning ability over time was suppressed and reusability was exhibited ("cleaning performance after cleaning 25 tablets") Changes" are small. Hereinafter, it is also referred to as "reuse sex").

In addition, it was further confirmed that the residue removal performance is improved by including anticorrosion agents, chelating agents, water-soluble organic solvents, pH adjusters, quaternary ammonium hydroxides, alkanolamines, and/or fluorides in the cleaning solution. and the improvement of either the anti-corrosion effect on the object to be cleaned, and the cleaning performance of the cleaning solution can be maintained well over time ("the change in the performance of the cleaning solution after 24 hours" is small), or Suppresses degradation of detergency over time and exhibits reusability (“change in detergency after washing 25 tablets” is small).

Various components that may be contained in the cleaning solution of the present invention will be described in detail below.

<water>

The cleaning solution of the present invention contains water as a solvent. The water content is usually 20% by mass to 98% by mass, preferably 60% by mass to 98% by mass, more preferably 70% by mass to 95% by mass, relative to the mass of the entire cleaning solution.

As water, ultrapure water used in semiconductor production is preferable. Although it is not particularly limited, it is preferably Fe, Co, Na, K, Ca, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn whose ion concentration is reduced, when used in the present invention When adjusting the cleaning liquid, it is better to adjust it to ppt level or below. As a method of adjustment, the methods described in paragraphs [0074] to [0084] of JP-A-2011-110515 may be mentioned.

<Hydroxylamine compound>

The cleaning solution of the present invention contains at least one hydroxylamine compound selected from hydroxylamine and hydroxylamine salts. The hydroxylamine compound promotes the decomposition and solubilization of residues, and prevents corrosion of objects to be cleaned.

Here, "hydroxylamine" in the hydroxylamine and hydroxylamine salts of the cleaning solution of the present invention refers to hydroxylamines in a broad sense including substituted or unsubstituted alkylhydroxylamines, and the present invention can be obtained regardless of any of them. The effect of the invention.

It does not specifically limit as a hydroxylamine, Unsubstituted hydroxylamine and a hydroxylamine derivative are mentioned.

The hydroxylamine derivative is not particularly limited, and examples include: O-methylhydroxylamine, O-ethylhydroxylamine, N-methylhydroxylamine, N,N-dimethylhydroxylamine, N,O- Dimethylhydroxylamine, N-ethylhydroxylamine, N,N-diethylhydroxylamine, N,O-diethylhydroxylamine, O,N,N-trimethylhydroxylamine, N,N-diethylhydroxylamine Carboxyethylhydroxylamine, N,N-disulfoethylhydroxylamine, etc.

The salt of hydroxylamine is preferably an inorganic acid salt or an organic acid salt of the hydroxylamine, more preferably a salt of an inorganic acid formed by bonding nonmetals such as Cl, S, N, and P to hydrogen, particularly preferably A salt of an acid selected from the group consisting of any one of hydrochloric acid, sulfuric acid, and nitric acid.

As the salt of hydroxylamine used to form the cleaning solution of the present invention, preferred are hydroxylammonium nitrate (also known as HAN), hydroxylammonium sulfate (also known as HAS), hydroxylammonium hydrochloride (also known as HAC), hydroxyammonium phosphate, N,N-diethylhydroxyammonium sulfate, N,N-diethylhydroxyammonium nitrate, and mixtures of these.

In addition, organic acid salts of hydroxylamine can also be used, and examples thereof include hydroxylammonium citrate, hydroxylammonium oxalate, and hydroxylammonium fluoride.

Furthermore, the cleaning solution of the present invention may also be in the form of containing hydroxylamine and its salt.

A hydroxylamine compound may be used individually, and may be used in combination of 2 or more types suitably.

Among them, hydroxylamine or hydroxylammonium sulfate is preferred, and hydroxylammonium sulfate is more preferred, from the viewpoint that the desired effects of the present invention can be remarkably obtained.

In the cleaning solution, the content of the hydroxylamine compound is not particularly limited, but relative to the total mass of the cleaning solution of the present invention, it is preferably in the range of 0.01% by mass to 30% by mass, more preferably 0.1% by mass to 15% by mass. % by mass, and more preferably 0.5% by mass to 10% by mass. By setting it as the said range, the desired effect of this invention can be acquired remarkably.

<Fluoride>

The cleaning solution of the present invention may contain fluoride. Fluoride promotes the decomposition and solubilization of residues.

The fluoride is not particularly limited, and examples thereof include hydrofluoric acid (HF), fluorosilicic acid (H ₂ SiF ₆ ), fluoroboric acid, ammonium fluorosilicate ((NH ₄ ) ₂ SiF ₆ ), hexafluorophosphoric acid Tetramethylammonium, ammonium fluoride, ammonium fluoride salt, ammonium hydrogen fluoride salt, quaternary ammonium tetrafluoroborate represented by formula NR ₄ BF ₄ , and quaternary phosphonium tetrafluoroborate represented by formula PR ₄ BF ₄ wait. In order to obtain the desired effects of the present invention, any of these fluorides may be used.

Furthermore, in the quaternary ammonium tetrafluoroborate represented by the formula NR ₄ BF ₄ and the quaternary phosphonium tetrafluoroborate represented by the formula PR ₄ BF ₄ , R may be the same or different from each other. Examples of R include hydrogen, straight-chain, branched, or cyclic alkyl groups having 1 to 6 carbon atoms (such as methyl, ethyl, propyl, butyl, pentyl, and hexyl), and 6 carbon atoms. Aryl groups of ~10 etc. These may further contain substituents.

Examples of the quaternary ammonium tetrafluoroborate represented by NR ₄ BF ₄ include tetramethylammonium tetrafluoroborate, tetraethylammonium tetrafluoroborate, tetrapropylammonium tetrafluoroborate, and tetrabutylammonium tetrafluoroborate. Ammonium base (TBA-BF ₄ ), etc.

A fluoride may be used individually, and may be used in combination of 2 or more types suitably.

Among the above, ammonium fluoride or fluorosilicate is preferable from the viewpoint that the desired effects of the present invention can be remarkably obtained.

In the cleaning solution, the content of fluoride is not particularly limited, but relative to the total mass of the cleaning solution of the present invention, it is preferably 0.01% by mass to 30% by mass, more preferably 0.1% by mass to 15% by mass, and then More preferably, it is 0.1% by mass to 5% by mass.

<Fe ion, Co ion>

In the cleaning liquid of the present invention, relative to the total mass of the cleaning liquid of the present invention, the content of Fe ions is preferably 1 mass ppm to 10 mass ppm, more preferably 1 mass ppt to 1 mass ppm, and more preferably 10 mass ppt~5 mass ppb, the best is 1 mass ppb~5 mass ppb.

In particular, when the content of Fe ions is 1 ppt to 1 ppm by mass relative to the total mass of the cleaning solution of the present invention, the cleaning performance of the cleaning solution can be maintained well over time. In addition, in the cleaning solution of the present invention, when the content of Fe ions is 1 mass ppt to 1 mass ppm relative to the total mass of the cleaning solution of the present invention (preferably 10 mass ppt to 5 mass ppb, more preferably 1 mass ppb to 5 mass ppb), further improving the residue removal performance and the corrosion resistance to the object to be cleaned.

Furthermore, it turns out that the cleaning liquid of this invention is also excellent in the recyclability mentioned later, when content of Fe ion is the said range.

In the cleaning solution of the present invention, relative to the total mass of the cleaning solution of the present invention, the content of Co ions is preferably 1 ppt by mass to 10 ppm by mass, more preferably 1 ppt by mass to 1 ppm by mass, and even more preferably 10 quality ppt~5 quality ppb, the best is 1 quality Quantity ppb~5 mass ppb.

In particular, when the content of Co ions is 1 ppt to 1 ppm by mass relative to the total mass of the cleaning solution of the present invention, the cleaning performance of the cleaning solution can be maintained well over time. In addition, in the cleaning solution of the present invention, when relative to the total mass of the cleaning solution of the present invention, the content of Co ions is 1 mass ppt ~ 1 mass ppm (preferably 10 mass ppt ~ 5 mass ppb, more preferably 1 mass ppb to 5 mass ppb), further improving the residue removal performance and the corrosion resistance to the object to be cleaned.

Furthermore, it was found that in the cleaning solution of the present invention, when the content of Co ions is in the above range, the recyclability described later (especially when a substrate containing Co is used as the object to be cleaned) is also excellent.

Furthermore, it is preferable to combine the content of at least one ion species selected from Fe ions and Co ions (the total amount when Fe ions and Co ions are contained together) and the content of hydroxylamine compounds (when multiple hydroxylamine compounds are contained) The content ratio (mass ratio) of the total amount) is adjusted to the following range.

In terms of mass ratio, relative to the content of at least one ion species selected from Fe ions and Co ions (it is the total amount when Fe ions and Co ions are contained at the same time), the content of hydroxylamine compounds (when containing multiple hydroxylamine compounds when the total amount) is preferably set at 5×10 ² to 5×10 ¹⁰ . That is, the content of hydroxylamine compounds (the total amount when multiple hydroxylamine compounds are contained)/the content of at least one ion species selected from Fe ions and Co ions (the total amount when Fe ions and Co ions are contained at the same time) ) is 5×10 ² ~5×10 ¹⁰ . The content ratio is more preferably 5×10 ⁴ to 5×10 ¹⁰ , further preferably 1×10 ⁷ to 5×10 ⁹ , particularly preferably 1×10 ⁷ to 1×10 ⁸ , most preferably 1×10 ⁷ ~5×10 ⁷ .

This time, it was confirmed that by adjusting the content ratio in this way, not only the cleaning performance of the cleaning solution can be maintained well over time, but also the residue removal performance of the cleaning solution and the corrosion resistance to the object to be cleaned are further improved , and the reusability is also more excellent. In particular, the effect is remarkable due to Fe ions.

During repeated use, when washing is repeated, a slight amount of metal ions derived from the metal hard mask is eluted into the washing liquid. It can be seen that due to the accumulation of these ions, there are cases where the residue removal performance and the corrosion resistance to the object to be cleaned are changed. ratio), the change is small and the reusability is excellent. The reason for this is presumed to be that these ions are particularly likely to interact with hydroxylamine compounds compared to other metal ions.

Fe ions and Co ions are generally components that may be contained in solvents, chemicals, and the like as impurities. Therefore, by purifying the solvent contained in the cleaning solution and/or the prepared cleaning solution by distillation, ion exchange resin, etc., a desired amount can be prepared.

The amount of Fe ions and Co ions in the cleaning solution can be measured by an inductively coupled plasma mass spectrometer (manufactured by Yokogawa Analytical Systems, Agilent 7500cs model).

<Anticorrosion agent>

The cleaning solution of the present invention preferably contains an anti-corrosion agent. The anticorrosion agent has a function of eliminating excessive etching of the metal (for example, Co, W) used as the wiring film.

It is not particularly limited as an anti-corrosion agent, for example, 1,2,4-triazole (Trazole, TAZ), 5-aminotetrazole (Aminotetrazole, ATA), 5-amino -1,3,4-thiadiazole-2-thiol, 3-amino-1H-1,2,4-triazole, 3,5-diamino-1,2,4-triazole, toluene Triazole, 3-amino-5-mercapto-1,2,4-triazole, 1-amino-1,2,4-triazole, 1-amino-1,2,3-triazole, 1-amino-5-methyl-1,2,3-triazole, 3-mercapto-1,2,4-triazole, 3-isopropyl-1,2,4-triazole, naphthotri azole, 1H-tetrazole-5-acetic acid, 2-mercaptobenzothiazole (2-Mercaptobenzothiazole, 2-MBT), 1-phenyl-2-tetrazol-5-thione, 2-mercaptobenzimidazole ( 2-Mercaptobenzidazole, 2-MBI), 4-methyl-2-phenylimidazole, 2-mercaptothiazoline, 2,4-diamino-6-methyl-1,3,5-triazine, thiazole, Imidazole, benzimidazole, triazine, methyltetrazole, bismuth thiol I, 1,3-dimethyl-2-imidazolidinone, 1,5-pentamethylenetetrazole, 1-phenyl- 5-mercaptotetrazole, diaminomethyltriazine, imidazolinethione, 4-methyl-4H-1,2,4-triazole-3-thiol, 5-amino-1,3,4 -thiadiazole-2-thiol, benzothiazole, tricresyl phosphate, indazole, adenine, cytosine, guanine, thymine, phosphate inhibitors, amines, pyrazoles, propanethiol, Silanes, secondary amines, benzohydroxamic acids, heterocyclic nitrogen inhibitors, citric acid, ascorbic acid, thiourea, 1,1,3,3-tetramethylurea, urea, urea derivatives, uric acid , potassium ethyl xanthate, glycine, dodecylphosphonic acid, iminodiacetic acid, acid, boric acid, malonic acid, succinic acid, nitrilotriacetic acid, cyclobutane, 2,3,5 -trimethylpyrazine, 2-ethyl-3,5-dimethylpyrazine, quinoxaline, acetylpyrrole, pyridazine, histadine, pyrazine, glutathione (reduced type), cysteine, cystine, thiophene, mercaptopyridine N-oxide, thiamine HCl, tetraethylthiuram disulfide, 2,5-dimercapto-1,3-thiadiazole Ascorbic acid, catechol, tertiary butyl catechol, phenol, and gallol, etc.

Further, containing substituted or unsubstituted benzotriazoles as corrosion inhibitors Also better. As the substituted benzotriazole, for example, a benzotriazole substituted with an alkyl group, an aryl group, a halogen group, an amino group, a nitro group, an alkoxy group, or a hydroxyl group is preferable. Furthermore, one or more aryl groups (such as phenyl) or heteroaryl groups may be condensed with the substituted benzotriazole.

In addition to those mentioned above, examples of substituted or unsubstituted benzotriazoles include: benzotriazole (Benzotriazole, BTA), 1-hydroxybenzotriazole, 5-phenylthiol-benzotriazole , 5-chlorobenzotriazole, 4-chlorobenzotriazole, 5-bromobenzotriazole, 4-bromobenzotriazole, 5-fluorobenzotriazole, 4-fluorobenzotriazole, naphthalene Triazole, tolyltriazole, 5-phenyl-benzotriazole, 5-nitrobenzotriazole, 4-nitrobenzotriazole, 2-(5-amino-pentyl)-benzene Triazole, 1-amino-benzotriazole, 5-methyl-1H-benzotriazole, benzotriazole-5-carboxylic acid, 4-methylbenzotriazole, 4-ethylbenzene Triazole, 5-ethylbenzotriazole, 4-propylbenzotriazole, 5-propylbenzotriazole, 4-isopropylbenzotriazole, 5-isopropylbenzotriazole , 4-n-butylbenzotriazole, 5-n-butylbenzotriazole, 4-isobutylbenzotriazole, 5-isobutylbenzotriazole, 4-pentylbenzotriazole, 5-pentylbenzotriazole, 4-hexylbenzotriazole, 5-hexylbenzotriazole, 5-methoxybenzotriazole, 5-hydroxybenzotriazole, dihydroxypropylbenzotriazole Azole, 1-[N,N-bis(2-ethylhexyl)aminomethyl]-benzotriazole, 5-tert-butylbenzotriazole, 5-(1',1'-dimethyl propyl)-benzotriazole, 5-(1',1',3'-trimethylbutyl)benzotriazole, 5-n-octylbenzotriazole, and 5-(1', 1',3',3'-tetramethylbutyl)benzotriazole, etc.

The anticorrosion agents may be used alone or in combination of two or more kinds as appropriate.

As an anti-corrosion agent, in terms of further improving anti-corrosion properties, it is preferably selected from compounds represented by the following formula (A) to formula (C), and substituted or unsubstituted tetrazoles. at least one of the group.

In the formula (A), R ^1A to R ^5A each independently represent a hydrogen atom, a substituted or unsubstituted hydrocarbon group, a hydroxyl group, a carboxyl group, or a substituted or unsubstituted amine group. Among them, at least one group selected from a hydroxyl group, a carboxyl group, and a substituted or unsubstituted amino group is contained in the structure.

In the formula (B), R ^1B to R ^4B each independently represent a hydrogen atom, a substituted or unsubstituted hydrocarbon group.

In the formula (C), R ^1C , R ^2C and R ^N each independently represent a hydrogen atom, a substituted or unsubstituted hydrocarbon group. In addition, R ^1C and R ^2C may be bonded to form a ring.

In the formula (A), as the hydrocarbon groups represented by R ^1A to R ^5A , there may be mentioned: alkyl (the number of carbons is preferably 1 to 12, more preferably 1 to 6, particularly preferably 1 to 3), alkenes Radical (preferably 2~12 carbon number, more preferably 2~6), alkynyl (preferably 2~12 carbon number, more preferably 2~6), aryl (preferably 6~22 carbon number , more preferably 6~14, more preferably 6~10), and aralkyl (the carbon number is preferably 7~23, more preferably 7~15, even more preferably 7~11).

In addition, as a substituent, for example, a hydroxyl group, a carboxyl group, or a substituted or unsubstituted amino group (as a substituent, preferably an alkyl group having 1 to 6 carbon atoms, more preferably is an alkyl group with 1 to 3 carbons).

Furthermore, in the formula (A), the structure contains at least one selected from hydroxyl, carboxyl, and substituted or unsubstituted amino groups (as a substituent, preferably an alkyl group with 1 to 6 carbon atoms, more preferably preferably an alkyl group with 1 to 3 carbon atoms).

In formula (A), as the substituted or unsubstituted hydrocarbon groups represented by R ^1A to R ^5A , for example, unsubstituted hydrocarbon groups with 1 to 6 carbon atoms, and substituted by hydroxyl, carboxyl or amino groups Hydrocarbon groups with 1 to 6 carbon atoms, etc.

As a compound represented by formula (A), 1-thioglycerol, L-cysteine, thiomalic acid, etc. are mentioned, for example.

In formula (B), the hydrocarbon groups and substituents represented by R ^1B to R ^4B have the same meanings as the hydrocarbon groups and substituents represented by R ^1A to R ^5A in formula (A). Examples of the substituted or unsubstituted hydrocarbon groups represented by R ^1B to R ^4B include hydrocarbon groups having 1 to 6 carbon atoms such as methyl, ethyl, propyl, and tert-butyl.

As a compound represented by formula (B), catechol, tert-butylcatechol, etc. are mentioned, for example.

In formula (C), the hydrocarbon groups and substituents represented by R ^1C , R ^2C and R ^N have the same meanings as the hydrocarbon groups and substituents represented by R ^1A to R ^5A in formula (A). Examples of the substituted or unsubstituted hydrocarbon groups represented by R ^1C , R ^2C and R ^N include hydrocarbon groups having 1 to 6 carbon atoms such as methyl, ethyl, propyl, and butyl.

In addition, R ^1C and R ^2C may be bonded to form a ring, for example, a benzene ring is mentioned. When R ^1C and R ^2C are bonded to form a ring, it may further have a substituent (for example, a hydrocarbon group having 1 to 5 carbon atoms).

As a compound represented by formula (C), 1H-1,2,3-triazole, benzotriazole, 5-methyl-1H-benzotriazole, etc. are mentioned, for example.

As the substituted or unsubstituted tetrazole, for example, in addition to the unsubstituted tetrazole, there can be mentioned a hydroxyl group, a carboxyl group, or a substituted or unsubstituted amino group (as a substituent, preferably a carbon number of 1~ 6 alkyl, more preferably an alkyl having 1 to 3 carbons) tetrazole as a substituent.

In the cleaning liquid, relative to the total mass of the cleaning liquid of the present invention, the content of the anti-corrosion agent is preferably 0.01% by mass to 5% by mass, more preferably 0.05% by mass to 5% by mass, and even more preferably 0.1% by mass ~3% by mass.

<chelating agent>

The cleaning solution may further contain a chelating agent. The chelating agent chelates the oxidized metal contained in the residue. Therefore, by adding a chelating agent, the reusability is further improved.

Although it does not specifically limit as a chelating agent, Polyaminopolycarboxylic acid is preferable.

Polyaminopolycarboxylic acid is a compound having a plurality of amine groups and a plurality of carboxylic acid groups. Examples of polyaminopolycarboxylic acids include mono- or polyalkylene polyamine polycarboxylic acids, polyaminoalkane polycarboxylic acids, polyaminoalkanol polycarboxylic acids, and hydroxyalkylether polyamine polycarboxylic acids. carboxylic acid.

Examples of polyaminopolycarboxylic acids include butanediaminetetraacetic acid, diethylenetriaminepentaacetic acid (Diethylenetriamine Pentaacetic Acid, DTPA), ethylenediaminetetrapropionic acid, triethylenetetraminehexaacetic acid, 1,3- Diamino-2-hydroxypropane-N,N,N',N'-tetraacetic acid, propylenediaminetetraacetic acid, ethylenediaminetetraacetic acid (EDTA), trans-1,2-di Aminocyclohexanetetraacetic acid, ethylenediamine Diacetic acid, ethylenediaminedipropionic acid, 1,6-hexamethylene-diamine-N,N,N',N'-tetraacetic acid, N,N-bis(2-hydroxybenzyl)ethylenediamine -N,N-diacetic acid, diaminopropane tetraacetic acid, 1,4,7,10-tetraazacyclododecane-tetraacetic acid, diaminopropanol tetraacetic acid, and (hydroxyethyl)ethylene diacetate Amine triacetic acid, etc. Among them, diethylenetriaminepentaacetic acid (DTPA), ethylenediaminetetraacetic acid (EDTA), or trans-1,2-diaminocyclohexanetetraacetic acid are preferred.

A chelating agent may be used individually, and may be used in combination of 2 or more types suitably.

In the cleaning solution, relative to the total mass of the cleaning solution of the present invention, the content of the chelating agent is preferably 0.01% by mass to 5% by mass, more preferably 0.01% by mass to 3% by mass.

<Water-soluble organic solvent>

The cleaning solution of the present invention preferably contains a water-soluble organic solvent. In addition to promoting the solubilization of added components and organic residues, water-soluble organic solvents can further enhance the anti-corrosion effect.

The water-soluble organic solvent is not particularly limited, for example, water-soluble alcohols, water-soluble ketones, water-soluble esters, and water-soluble ethers (such as glycol diethers), etc., in order to obtain the desired effect of the present invention, Any of these water-soluble organic solvents can be used.

Examples of water-soluble alcohols include alkylene glycols (for example, including alkylene glycols), diols, alkoxy alcohols (for example, including glycol monoethers), saturated aliphatic monohydric alcohols, unsaturated non-aromatic monohydric alcohols, Alcohols, and low-molecular-weight alcohols containing ring structures.

Examples of alkanediol include 2-methyl-1,3-propanediol, 1,3-propanediol, 2,2-dimethyl-1,3-diol, 1,4-butanediol, 1 , 3-butanediol, 1,2-butanediol, 2,3-butanediol, pinacol, and alkylene glycol, etc.

As alkylene glycol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tetraethylene glycol, etc. are mentioned, for example.

As alkoxy alcohol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-1-butanol, 1-methoxy-2-butanol, etc. are mentioned, for example.

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 monobutyl ether, and ethylene glycol monobutyl ether. 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 Alcohol monoethyl ether, triethylene glycol monobutyl ether, 1-methoxy-2-propanol, 2-methoxy-1-propanol, 1-ethoxy-2-propanol, 2- Ethoxy-1-propanol, propylene glycol mono-n-propyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, tripropylene glycol monoethyl ether, tripropylene glycol mono Methyl ether, ethylene glycol monobenzyl ether, diethylene glycol monobenzyl ether, etc.

Examples of saturated aliphatic monohydric alcohols include methanol, ethanol, n-propanol, isopropanol, 1-butanol, 2-butanol, isobutanol, tert-butanol, 2-pentanol, and tert-pentanol. Alcohol, and 1-hexanol, etc.

As unsaturated non-aromatic monohydric alcohol, aryl alcohol, propargyl alcohol, 2-butenyl alcohol, 3-butenyl alcohol, 4-penten-2-ol, etc. are mentioned, for example.

As a low molecular weight alcohol containing a ring structure, tetrahydrofurfuryl alcohol, furfuryl alcohol, 1, 3- cyclopentanediol, etc. are mentioned, for example.

As water-soluble ketones, for example, acetone (acetone), acetone (propanone), cyclobutanone, cyclopentanone, cyclohexanone, diacetone alcohol, 2-butanone, 5- Hexandione, 1,4-cyclohexanedione, 3-hydroxyacetophenone, 1,3-cyclohexanedione, and cyclohexanone, etc.

Examples of water-soluble esters include glycol monoesters such as ethyl acetate, ethylene glycol monoacetate, and diethylene glycol monoacetate, propylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether Diol monoether monoesters such as base ether acetate, propylene glycol monoethyl ether acetate, and ethylene glycol monoethyl ether acetate.

Among the water-soluble organic solvents, from the viewpoint of further enhancing the anti-corrosion effect, water-soluble alcohols are preferred, alkanediols, diols, or alkoxy alcohols are more preferred, alkoxy alcohols are more preferred, Particularly preferred is ethylene glycol monobutyl ether, tripropylene glycol monomethyl ether, or diethylene glycol monoethyl ether.

The water-soluble organic solvent may be used alone or in combination of two or more kinds as appropriate.

With respect to the total mass of the cleaning solution of the present invention, the content of the water-soluble organic solvent is preferably 0.1% by mass to 15% by mass, more preferably 1% by mass to 10% by mass.

<pH adjuster>

The pH of the cleaning solution of the present invention is not particularly limited, but is preferably not less than the pKa of the conjugate acid of hydroxylamine and hydroxylamine salt. When the pH of the treatment solution of the present invention is equal to or higher than the pKa of the conjugate acid of hydroxylamine and hydroxylamine salt, the residue removal performance is dramatically improved. In other words, the effect of the present invention can be significantly obtained when the ratio of hydroxylamine and hydroxylamine salt present in the molecular state in the cleaning solution is large. For example, the conjugate acid of hydroxylamine has a pKa of about 6.

Preferably, the pH of the cleaning solution of the present invention is set to 6-11. In order to bring the pH of the cleaning solution into the above-mentioned range, it is desirable to contain a pH adjuster in the cleaning solution.

If the pH of the cleaning solution is within the above range, both the corrosion rate and the residue removal performance will be more excellent.

From the viewpoint of detergency, the lower limit of the pH of the cleaning solution is preferably 6.5 or higher, more preferably 7 or higher, and still more preferably 7.5 or higher. On the other hand, from the viewpoint of corrosion suppression, the upper limit is preferably 10.5 or less, more preferably 10 or less, still more preferably 9.5 or less, particularly preferably 8.5 or less.

As a measuring method of pH, it can measure using a well-known pH meter.

Known ones can be used as the pH adjuster, but generally, it is preferable not to contain metal ions.

As a pH adjuster, for example, ammonium hydroxide, monoamines, imines (such as 1,8-diazabicyclo[5.4.0]undec-7-ene, and 1,5-diazabicyclo[5.4.0]undec-7-ene, Bicyclo[4.3.0]non-5-ene, etc.), 1,4-diazabicyclo[2.2.2]octane, and guanidine salts (such as guanidine carbonate), etc. Among them, ammonium hydroxide or imines (such as 1,8-diazabicyclo[5.4.0]undec-7-ene) are preferred from the viewpoint of significantly obtaining the desired effect of the present invention. , and 1,5-diazabicyclo[4.3.0]non-5-ene, etc.).

A pH adjuster may be used individually, and may be used in combination of 2 or more types suitably.

As long as the desired pH of the cleaning solution can be achieved, the amount of the pH adjuster is not particularly limited, but usually in the cleaning solution, it is ideal to be 0.1% by mass to 5% by mass relative to the total mass of the cleaning solution. % concentration, more preferably 0.1% by mass to 2% by mass.

<Quaternary ammonium hydroxide>

In addition, the cleaning solution of the present invention preferably contains quaternary ammonium hydroxides. by Tim Adding quaternary ammonium hydroxide can not only further improve the residue removal performance, but also function as a pH regulator.

As quaternary ammonium hydroxides, compounds represented by the following general formula (4) are preferable.

(In formula (4), R ^4A to R ^4D independently represent an alkyl group with 1 to 6 carbons, a hydroxyalkyl group with 1 to 6 carbons, a benzyl group, or an aryl group)

In formula (4), R ^4A ~ R ^4D independently represent an alkyl group with 1 to 6 carbons (such as methyl, ethyl, and butyl, etc.), a hydroxyalkyl group with 1 to 6 carbons (such as hydroxymethyl group, hydroxyethyl group, and hydroxybutyl group, etc.), benzyl group, or aryl group (such as phenyl, naphthyl group, and naphthalene group, etc.). Among them, an alkyl group, a hydroxyethyl group, or a benzyl group is preferable.

As the compound represented by formula (4), specifically, it is preferably selected from tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, trimethylhydroxyethylammonium hydroxide , methyltri(hydroxyethyl)ammonium hydroxide, tetra(hydroxyethyl)ammonium hydroxide, trimethylbenzylammonium hydroxide, and at least one quaternary ammonium hydroxide in the group consisting of choline , which, in the present invention, is more preferably selected from the group consisting of hydrogen oxidation At least one selected from the group consisting of tetramethylammonium, tetraethylammonium hydroxide, benzyltrimethylammonium hydroxide, and choline.

The quaternary ammonium hydroxides can be used alone or in combination of two or more.

In the cleaning liquid, relative to the total mass of the cleaning liquid of the present invention, the content of quaternary ammonium hydroxides is preferably 0.1% by mass to 15% by mass, more preferably 0.5% by mass to 10% by mass, and even more preferably It is 0.5% by mass to 5% by mass.

<Alkanolamines>

The cleaning solution preferably contains alkanolamines from the viewpoint of promoting the dissolution of additive components and organic residues and preventing corrosion.

The alkanolamines can be any of primary amines, secondary amines, and 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 cleaning solution of the present invention, a compound represented by the following formula (5) is preferable.

Formula (5): R ¹ R ² -N-CH ₂ CH ₂ -OR ³

(In formula (5), R ¹ and R ² independently represent a hydrogen atom, methyl, ethyl, or hydroxyethyl, and R ³ represents a hydrogen atom or a hydroxyethyl group. Wherein, at least one alkane is contained in the formula Alcohol)

Specific examples of alkanolamines include monoethanolamine, diethanolamine, triethanolamine, tert-butyldiethanolamine, isopropanolamine, 2-amino-1-propanol, 3-amino- 1-propanol, isobutanolamine, 2-amino-2-ethoxy-propanol, and 2-amino-2-ethoxy-ethanol, also known as diglycolamine.

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

In the cleaning liquid, relative to the total mass of the cleaning liquid of the present invention, the content of alkanolamines is preferably 0.1% by mass to 80% by mass, more preferably 0.5% by mass to 50% by mass, and even more preferably 0.5% by mass. Mass%~20 mass%.

<Other additives>

The cleaning solution of the present invention may contain other additives within the range in which the effects of the present invention are obtained. As other additives, a surfactant, an antifoamer, etc. are mentioned, for example.

<Appropriate form of cleaning solution>

As preferred forms of the cleaning solution of the present invention, the following forms are listed, but are not particularly limited thereto.

(1) A cleaning solution containing at least one hydroxylamine compound selected from hydroxylamine and hydroxylamine salts, water, an anti-corrosion agent, a chelating agent, and a water-soluble organic solvent.

(2) A cleaning solution containing at least one hydroxylamine compound selected from hydroxylamine and hydroxylamine salts, water, an anti-corrosion agent, and a water-soluble organic solvent and/or alkanolamines.

(3) A cleaning solution containing at least one hydroxylamine compound selected from hydroxylamine and hydroxylamine salts, water, quaternary ammonium hydroxides, an anti-corrosion agent, and a water-soluble organic solvent and/or alkanolamines.

(4) A cleaning solution containing at least one hydroxylamine compound selected from hydroxylamine and hydroxylamine salts, water, and a fluoride.

(5) Containing at least one hydroxylamine compound selected from hydroxylamine and hydroxylamine salts, water, and a compound selected from the following formula (A) to formula (C) (each definition in the formula is as above) , and any of substituted or unsubstituted tetrazoles Cleansing solution.

(6) In each of the cleaning solutions of (1) to (5), the content of Fe ions and Co ions is preferably the above content, and in addition, at least one ion species selected from Fe ions and Co ions The content ratio (mass ratio) of the content (the total amount when Fe ions and Co ions are contained at the same time) to the content of the hydroxylamine compound (the total amount when multiple hydroxylamine compounds are contained) is preferably the above-mentioned content ratio .

<Sets and Concentrates>

The cleaning solution of the present invention can also be used as a set in which the raw material is divided into a plurality. For example, a liquid composition containing at least one hydroxylamine compound selected from hydroxylamine and a hydroxylamine salt and water is prepared as the first liquid, and a liquid composition containing other components and water is prepared as the second liquid. As an example of its use, it is preferable to mix the two liquids to prepare a cleaning liquid, and then apply it to the above-mentioned treatment as appropriate. An organic solvent or the like may be contained in either the first liquid or the second liquid. Thereby, the degradation of the liquid performance due to the decomposition of the hydroxylamine compound or other components is not caused, and the desired function can be effectively exhibited. The content of each component in the 1st liquid and the 2nd liquid can be set suitably as content after mixing based on the content mentioned above.

In addition, the cleaning solution can also be prepared as a concentrated solution. In this case, it can be diluted with water and other organic solvents before use.

<container>

The cleaning solution of the present invention (regardless of whether it is a set or not) can be filled in any container, stored, transported, and used as long as corrosion or the like does not pose a problem. As a container, it is suitable for a semiconductor application, and it is preferable to have a high degree of cleanliness and little elution of impurities. Usable containers include the "Clean Bottle" series manufactured by Aicello Chemical Co., Ltd., and the "Pure Bottle" series manufactured by Kodama Plastics Co., Ltd. )", etc., but not limited to these containers. The inner wall of the container or its accommodating portion is preferably made of a resin different from the resin contained in the group consisting of polyethylene resin, polypropylene resin, and polyethylene-polypropylene resin, or is rust-resistant. Metal leaching prevents processed metal from forming.

As the different resin, a fluorine-based resin (perfluororesin) is preferable. By using a container whose inner wall of the housing part is made of fluororesin, compared with the case of using a container whose inner wall of the housing part is made of polyethylene resin, polypropylene resin, or polyethylene-polypropylene resin, it is possible to suppress ethylene or propylene The undesired situation of dissolution of oligomers occurs.

As a specific example of the container whose inner wall of the housing part is made of a fluorine-based resin, for example, a FluoroPure perfluoroalkoxy (PFA) composite tank manufactured by Entegris, etc. may be mentioned. In addition, pages 4, etc. of Japanese Patent Application Publication No. Hei 3-502677, pages 3, etc. of International Publication No. 2004/016526, and pages 9 and 9 of International Publication No. 99/46309 may also be used. Containers described on page 16 etc.

<filter>

The cleaning solution of the present invention is preferably filtered through a filter for the purpose of removing foreign substances, reducing defects, and the like.

As the material of the filter, as long as it is conventionally used for filtration purposes, etc., it can be used without particular limitation, for example: fluorine resins such as polytetrafluoroethylene (Polytetrafluoroethylene, PTFE), polyamide-based resins such as nylon, etc. , and polyolefin resins such as polyethylene and polypropylene (Polypropylene, PP) (including high density and ultra-high molecular weight), etc. Among these materials, polypropylene (including high-density polypropylene) or nylon is preferred.

The pore size of the filter is suitably about 0.001 μm to 1.0 μm, preferably about 0.02 μm to 0.5 μm, more preferably about 0.01 μm to 0.1 μm. By setting it as this range, clogging of a filter can be suppressed, and the fine foreign matter, such as the impurity contained in a liquid, and an aggregate, can be reliably removed.

When using filters, different filters can also be combined.

Filtration by each filter may be performed only once, or may be performed two or more times. The filtration more than two times refers to, for example, the case where the liquid is circulated and the same filter is used to perform the filtration two or more times.

As mentioned above, it is also possible to perform filtering by combining different filters. When performing two or more filtrations by combining different filters, it is preferable that the pore diameters of the second and subsequent filtrations are equal to or larger than those of the first filtration. In addition, the first type of filters having different pore diameters may be combined within the above-mentioned range. The pore size here can refer to the nominal value of the filter manufacturer. As filters are commercially available, for example from Japan Pall Co., Ltd., Advantec Toyo Co., Ltd., Nihon Entegris Co., Ltd. (formerly Mykrolis Co., Ltd.), and Kitazawa Choose from various filters offered by Kitz Microfilter Co., Ltd., etc.

As the second filter, a filter made of the same material as that of the first filter can be used. The pore diameter of the second filter is suitably about 0.01 μm to 1.0 μm, preferably about 0.1 μm to 0.5 μm. By setting it as this range, when the component particle|grains are contained in a liquid, the foreign material mixed in a liquid can be removed in the state which left the said component particle.

For example, by mixing only a part of the finally prepared cleaning solution in advance to prepare a mixed solution, after filtering the mixed solution with a first filter, to the mixed solution after filtering with the first filter, The rest of the ingredients to make up the cleaning solution were added to the solution, and the mixture was filtered a second time.

<Metal Concentration>

The cleaning solution of the present invention is preferably metals other than Fe and Co (metal elements of Na, K, Ca, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn) contained in the solution as impurities. ) ion concentrations are below 5ppm (preferably below 1ppm). In particular, in the manufacture of state-of-the-art semiconductor elements, since it is assumed that higher purity cleaning solutions are required, the metal concentration is preferably lower than the ppm level, that is, below the ppb level, and more preferably at the ppt level (The above-mentioned concentrations are all based on mass), especially preferably not containing substantially.

As a method of reducing the concentration of metals, for example, in the manufacture of cleaning solutions Distillation and/or filtration using an ion-exchange resin are sufficiently performed in at least one of the stages of the raw materials used during the process and the stage after preparation of the cleaning solution.

As another method of reducing the metal concentration, for the "container" containing the raw materials used in the production of the cleaning solution, use a container with little elution of impurities as shown in the above-mentioned <container>. In addition, a method such as lining the inner wall of the pipe with a fluorine-based resin so that the metal component does not elute from the "pipe" during preparation of the cleaning solution, etc. can also be mentioned.

<Impurities and Coarse Particles>

The cleaning solution of the present invention preferably has less impurities such as metal components in the solution in view of its intended use. In particular, it is preferable that the Na ion concentration, the K ion concentration, and the Ca ion concentration in the liquid are within a range of 5 ppm (mass basis) or less.

In addition, it is preferable that the cleaning liquid does not substantially contain coarse particles.

Furthermore, the coarse particles contained in the cleaning solution refer to particles such as dust, dust, organic solids, and inorganic solids contained in the raw materials as impurities, and particles mixed in as pollutants in the preparation of the cleaning solution. Particles such as dust, dust, organic solids, and inorganic solids are equivalent to those that do not dissolve in the cleaning solution and exist as particles. The amount of coarse particles present in the cleaning solution can be measured in the liquid phase using a commercially available measuring device in a light-scattering liquid particle measurement system using a laser as a light source.

[Substrate cleaning method]

The cleaning method of the substrate of the present invention comprises: cleaning solution preparation step A, preparing a solution containing at least one of hydroxylamine and hydroxylamine salts A cleaning solution of one hydroxylamine compound and water; and cleaning step B, using the cleaning solution to clean the equipment containing Cu, Co, W, AlOx, AlN, AlOxNy, WOx, Ti, TiN, ZrOx, HfO And any one or more metal hard mask substrates of TaOx. In addition, x and y are numbers represented by x=1~3 and y=1~2, respectively.

<Wash object>

As long as the object to be cleaned in the substrate cleaning method of the present invention is a material containing Cu, Co, W, WOx, AlOx, AlN, AlOxNy, Ti, TiN, ZrOx, HfOx, and TaOx (moreover, x and y are respectively represented by x = 1 to 3, and y = 1 to 2), the substrate of any one or more metal hard masks is not particularly limited.

Furthermore, the metal hard mask is formed in a pattern and has predetermined openings.

In addition, the object to be cleaned by the substrate cleaning method of the present invention includes, for example, a laminate including at least a metal film, an interlayer insulating film, and a metal hard mask in this order on a substrate. The laminate further has a hole formed from the surface (opening) of the metal hard mask toward the substrate by passing through a dry etching step or the like so that the metal film surface is exposed.

The manufacturing method of the above-mentioned layered product having holes is not particularly limited, and generally, the following method can be cited: a metal hard mask is used as a mask, and a substrate, a metal film, an interlayer insulating film, and a metal hard mask are sequentially formed. The dry etching step is performed on the pre-processed laminate of the mask, and the interlayer insulating film is etched so that the surface of the metal film is exposed, thereby providing holes penetrating through the metal hard mask and the interlayer insulating film.

Moreover, the manufacturing method of the metal hard mask is not particularly limited, for example, such as The following method is to form a metal film containing a predetermined composition, form a resist film of a predetermined pattern thereon, and use the resist film as a mask to etch the metal film to manufacture a metal hard mask.

Moreover, a laminate may have layers other than the said layer, For example, an etching stopper film, an antireflection layer, etc. are mentioned.

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

The laminate 10 shown in FIG. 1 is sequentially provided with a metal film 2, an etching stopper layer 3, an interlayer insulating film 4, and a metal hard mask 5 on a substrate 1, and is formed at a predetermined position by going through a dry etching step or the like. The hole 6 exposed by the metal film 2. That is, the object to be cleaned shown in FIG. The layered product is provided with holes 6 that penetrate from the surface to the surface of the metal film 2 at positions. The inner wall 11 of the hole 6 is composed of a cross-sectional wall 11a including the etch stop layer 3, the interlayer insulating film 4, and the metal hard mask 5, and a bottom wall 11b including the exposed metal film 2, and dry etching residue 12 is adhered thereto.

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 corrosion resistance to the inner wall 11 of the object to be cleaned (for example, the metal film 2 etc.) is also excellent.

In addition, the substrate cleaning method of the present invention can also be implemented on a laminate subjected to a dry ashing step after the dry etching step.

Hereinafter, the constituent materials of each layer of the laminate will be described.

(metal hard mask)

The metal hard mask is not particularly limited as long as it contains any one or more of Cu, Co, W, AlOx, AlN, AlOxNy, WOx, Ti, TiN, ZrOx, HfOx, and TaOx. Here, x and y are numbers represented by x=1~3 and y=1~2, respectively.

Examples of materials for the metal hard mask include TiN, WO ₂ , and ZrO ₂ .

(interlayer insulating film)

Although it does not specifically limit as an interlayer insulating film, For example, the dielectric constant k is preferably 3.0 or less, More preferably, it is 2.6 or less.

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

(etch stop layer)

It does not specifically limit as an etching stopper layer. Specific materials of the etching stop layer include silicon-based materials such as SiN, SiON, and SiOCN, and metal oxides such as AlOx.

(metal film)

Although it does not specifically limit as a wiring material which forms a metal film, A metal, a metal nitride, and an alloy are mentioned. Specifically, examples thereof include copper, titanium, titanium-tungsten, titanium nitride, tungsten, cobalt, tantalum, tantalum compounds, chromium, chromium oxide, and aluminum. From the viewpoint of enjoying the effect of the cleaning solution of the present invention, cobalt or tungsten is particularly preferable as the wiring material.

(substrate)

The "substrate" mentioned here includes, for example, a semiconductor substrate including a single layer and a semiconductor substrate including multiple layers.

The material constituting the single-layer semiconductor substrate is not particularly limited, and usually preferably includes III-V compounds such as silicon, silicon germanium, and GaAs, or any combination thereof.

In the case of a multi-layer semiconductor substrate, its composition is not particularly limited. For example, on the semiconductor substrate such as silicon, there may be exposed integrated circuits such as metal lines and dielectric materials such as interconnect structures (interconnect features). structure. As metals and alloys used in the interconnection structure, aluminum, aluminum alloyed with copper, copper, titanium, tantalum, cobalt and silicon, titanium nitride, tantalum nitride, and tungsten can be listed, but are not limited to These metals and alloys. In addition, an interlayer dielectric layer, a layer of silicon oxide, silicon nitride, silicon carbide, silicon oxide doped with carbon, or the like may be provided on the semiconductor substrate.

Hereinafter, the cleaning solution preparation step A and the cleaning step B will be described in detail respectively.

(Cleaning solution preparation step A)

The cleaning solution preparation step A is a step of preparing a cleaning solution containing at least one hydroxylamine compound selected from hydroxylamine and hydroxylamine salts and water.

The components used in this step are as described above.

The procedure of this step is not particularly limited. For example, the method of adding a hydroxylamine compound and other optional components to water and stirring and mixing is used to prepare a cleaning solution. In addition, when adding each component to water, it may add at once, and may divide and add in multiple times.

(washing step B)

Examples of the substrate with a mask to be cleaned in the cleaning step B include the above laminate, and as described above, a laminate in which a hole has been subjected to a dry etching step can be exemplified. Furthermore, in this laminate, dry etching residue adheres to the inside of the hole.

In addition, a laminate subjected to a dry ashing step after the dry etching step may also be used as an object to be cleaned.

The method of bringing the cleaning solution into contact with the masked substrate is not particularly limited, for example, a method of immersing the masked substrate in the cleaning solution added to the tank, spraying the cleaning solution onto the tape, etc. A method on a substrate with a mask, a method of pouring a cleaning solution on a substrate with a mask, and any combination thereof. From the viewpoint of residue removability, a method of immersing a substrate with a mask in a cleaning solution is preferable.

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

The cleaning time can be adjusted according to the cleaning method used and the temperature of the cleaning solution.

When washing is carried out by dipping batch method (batch method in which a plurality of pieces of objects to be cleaned are immersed in a treatment tank for treatment), for example, within 60 minutes, preferably 1 minute to 60 minutes, more preferably 3 minutes to 20 minutes, and more preferably 4 minutes to 15 minutes.

When the sheet-by-sheet method is used for cleaning, the cleaning time is, for example, 10 seconds to 5 minutes, preferably 15 seconds to 4 minutes, more preferably 15 seconds to 3 minutes, and even more preferably 20 seconds to 2 minutes.

Furthermore, in order to further increase the cleaning ability of the cleaning liquid, mechanical stirring means may also be used.

As the stirring method, for example, a method of circulating a cleaning solution on a masked substrate, a method of flowing or spraying a cleaning solution on a masked substrate, and a method of using ultrasonic waves or megasonic waves Stir and so on.

(Rinse step B2)

The substrate cleaning method of the present invention may further include a step of cleaning the substrate with a mask by using a solvent after the cleaning step B (rinsing step B2).

The rinsing step B2 is preferably carried out immediately after the washing step B, and is washed with a rinsing solvent for 5 seconds to 5 minutes. The rinsing step B2 can be performed using the mechanical stirring means.

Examples of eluting solvents include deionized (DI: De Ionize) water, methanol, ethanol, isopropanol, N-methylpyrrolidone, γ-butyrolactone, dimethylsulfoxide, ethyl lactate and Propylene glycol monomethyl ether acetate, but not limited to these rinse solvents. Alternatively, an aqueous eluent with pH>8 (diluted aqueous ammonium hydroxide, etc.) can also be used.

As a rinse solvent, it is preferably aqueous ammonium hydroxide, DI water, methanol, ethanol, or isopropanol, more preferably aqueous ammonium hydroxide, DI water, or isopropanol, and more preferably aqueous ammonium hydroxide or DI water.

As the method of bringing the rinsing solvent into contact with the masked substrate, the method of bringing the cleaning solution into contact with the masked substrate can be similarly applied.

The temperature of the rinsing solvent in the rinsing step B2 is preferably 16°C-27°C.

(drying step B3)

The substrate cleaning method of the present invention may include a drying step B3 of drying the masked substrate after the rinse step B2.

The drying method is not particularly limited. As a drying method, for example, spin drying, a method in which a dry gas is flowed over a substrate with a mask, a method in which a substrate is heated by heating means such as a hot plate or an infrared lamp, marangoni drying (marangoni drying) drying), rotagoni drying (rotagoni drying), isopropyl alcohol (Isopropyl Alcohol, IPA) drying, or any combination of these.

Although the drying time also depends on the drying method, it is usually preferably 30 seconds to several minutes.

(Metal ion removal step F, metal ion removal step G)

The method for cleaning the substrate of the present invention preferably includes removing at least one metal ion selected from Fe ions and Co ions from at least one of the hydroxylamine compound and water before the step A of preparing the cleaning solution. Removing step F, or after the cleaning solution preparation step A and before performing the cleaning step B, there is a metal ion removal method for removing at least one ion species selected from Fe ions and Co ions in the cleaning solution Step G.

Preferably, by implementing the metal ion removal step F or the metal ion removal step G, the content of Fe ions in the cleaning solution used in the cleaning step B is adjusted to 1 mass with respect to the total mass of the cleaning solution. ppt~10 mass ppm. Also, similarly, it is preferable to adjust the content of Co ions in the cleaning solution to 1 mass ppm to 10 mass ppm with respect to the total mass of the cleaning solution. Furthermore, the content of Fe ions in the cleaning solution and The appropriate range of the content of Co ions is as described above.

The specific method of the metal ion removal step F and the metal ion removal step G is not particularly limited, and examples thereof include distillation and/or purification with an ion exchange membrane.

By first adjusting the content of Fe ions and Co ions in the cleaning solution to the above-mentioned ranges, the cleaning performance of the cleaning solution can be maintained well over time, and the reusability is also excellent. In addition, by appropriately adjusting the content ratio of the total content of Fe ions and Co ions in the cleaning solution to the content of the hydroxylamine compound, the residue removal performance of the cleaning solution is further improved, and the reusability is also more excellent. .

(coarse particle removal step H)

The substrate cleaning method of the present invention preferably includes a coarse particle removal step H for removing coarse particles in the cleaning solution after the cleaning solution preparation step A and before performing the cleaning step B.

By reducing or removing the coarse particles in the cleaning solution, the amount of remaining coarse particles on the masked substrate after the cleaning step B can be reduced. As a result, damage to the pattern caused by the coarse particles on the masked substrate can be suppressed, and the influence on the drop in yield and reliability of the device can also be suppressed.

Specific methods for removing coarse particles include, for example, a method of filtering and purifying the cleaning solution that has passed through cleaning solution preparation step A using a particle removing membrane having a predetermined particle removing diameter.

In addition, the definition of a coarse particle is as above.

(Destaticization step I, destaticization step J)

The method for cleaning the substrate of the present invention is preferably performed in step A of preparing the cleaning solution. Before, there is a destaticizing step I for destaticizing water, or after the cleaning solution preparation step A and before performing the cleaning step B, there is a destaticizing step J for destaticizing the cleaning solution.

The cleaning solution of the present invention has the function of reducing metals because it contains a hydroxylamine compound. Therefore, the material of the liquid contact portion for supplying the cleaning liquid onto the masked substrate is preferably a resin that does not elute metal from the cleaning liquid. This kind of resin material has low electrical conductivity and is insulating, so for example, when the cleaning liquid is passed through the resin piping, and a resin particle removal membrane with a large contact area between the filter material and the liquid is used And when the ion exchange resin membrane made of resin is filtered and purified, the charging potential of the cleaning solution increases and there is a possibility of causing an electrostatic disaster.

Therefore, in the substrate cleaning method of the present invention, it is preferable to implement the deionizing step I or the deionizing step J to reduce the charged potential. In addition, by performing static elimination, the adhesion of foreign matter (coarse particles, etc.) to the substrate and damage (corrosion) to the substrate to be processed can be further suppressed.

As a static elimination method, the method of bringing water or a cleaning solution into contact with a conductive material is mentioned specifically,.

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

Specific examples of the resin material include: high-density polyethylene (High Density Polyethylene, HDPE), high-density polypropylene (PP), 6,6-nylon, tetrafluoroethylene (Polytetrafluoroethylene, PTFE), tetrafluoroethylene and all Fluoroalkyl vinyl ether copolymer (PFA), polychlorotrifluoroethylene (Polychlorotrifluoroethylene, PCTFE), Ethylene Chlorotrifluoroethylene (ECTFE), Ethylene Tetrafluoroethylene (ETFE), and Fluorinated Ethylene Propylene (FEP), etc. .

As the conductive material, stainless steel, gold, platinum, diamond, or glassy carbon is particularly preferable.

When the cleaning solution of the present invention has a reusable composition, the substrate cleaning method using the cleaning solution of the present invention can reuse the drain of the cleaning solution used in the cleaning step B, and then be used for other Cleaning of substrates with masks. In particular, it was found that when the cleaning solution contains a hydroxylamine compound and desired amounts of Fe ions and Co ions according to the present invention, the recyclability is more excellent.

When the substrate cleaning method of the present invention is in the form of reusing the drained cleaning solution, it preferably includes the following steps.

It includes: cleaning solution preparation step A, preparing a cleaning solution containing at least one hydroxylamine compound selected from hydroxylamine and hydroxylamine salts and water; cleaning step B, using the cleaning solution to clean the equipment containing Cu , Co, W, AlOx, AlN, AlOxNy, WOx, Ti, TiN, ZrOx, HfOx, and TaOx (moreover, x, y are numbers represented by x=1~3, y=1~2 respectively) The substrate of more than one metal hard mask; the drainage recovery step C, recovering the drainage of the cleaning solution used in the cleaning step B; the cleaning step D, using the drainage of the recovered cleaning solution, Cleaned and re-prepared It contains Cu, Co, W, AlOx, AlN, AlOxNy, WOx, Ti, TiN, ZrOx, HfOx, and TaOx (in addition, x, y are numbers represented by x=1~3, y=1~2, respectively. ) of any one or more metal hard mask substrates; and a drainage recovery step E, recovering the drainage of the cleaning solution used in the cleaning step D; and repeatedly implementing the cleaning step D and the Drain recovery step E.

In the form of reusing the drain, the cleaning solution preparation step A and cleaning step B have the same meaning as the cleaning solution preparation step A and cleaning step B described in the above form. In addition, the preferred The form is also the same. In addition, in the form of reusing the above-mentioned discharged liquid, it is preferable to also include the metal ion removal step F, the metal ion removal step G, the coarse particle removal step H, the static elimination step I, and the static removal step J described in the above-mentioned configuration. .

The cleaning step D of cleaning the substrate using the drain of the recovered cleaning solution is the same as the cleaning step B in the above-mentioned embodiment, and the preferred embodiment is also the same.

The drainage recovery means in the drainage recovery step C and the drainage recovery step E are not particularly limited. The collected effluent is preferably stored in the resin container in the destaticizing step J, and the same destaticizing step as the destaticizing step J may be performed at this time. In addition, it is also possible to provide a step of filtering the recovered effluent to remove impurities.

[Manufacturing method of semiconductor element]

The manufacturing method of the semiconductor device of the present invention includes using the cleaning solution of the present invention to clean the liquid containing any one or more of Cu, Co, W, AlOx, AlN, AlOxNy, WOx, Ti, TiN, ZrOx, HfOx, and TaOx. metal hard mask substrate cleaning steps. In addition, x and y are numbers represented by x=1~3 and y=1~2, respectively.

The manufacturing method of the semiconductor element of this invention should just include at least the said washing|cleaning process, The meaning of this washing|cleaning process is the same as the said washing|cleaning process B, and a preferable aspect is also the same. The manufacturing method of a semiconductor element may have a process other than a cleaning process, for example, may include the said rinsing process B2 and drying process B3.

Furthermore, usually after the cleaning step, after removing unnecessary metal hard masks, one or more additional circuits are formed on the substrate, or assembly (such as dicing and bonding) and packaging are performed, for example. (such as wafer sealing) to form semiconductor wafers, etc.

As a semiconductor element, a flash memory, a logic element, etc. are mentioned, for example.

[Example]

Hereinafter, the present invention will be described in more detail based on examples. Unless departing from the gist of this invention, the material, usage-amount, a ratio, process content, process procedure etc. which are shown in the following Example can be changed suitably. Therefore, the scope of the present invention should not be limitedly interpreted by the Examples shown below.

(1) Observation of plasma etching residues using a scanning electron microscope

(a) Fabrication of a laminate (sample 1) having a Co film

A laminate (corresponding to a pre-process laminate) is formed on a substrate (Si) sequentially comprising a Co film, a SiN film, a _SiO2 film, and a metal hard mask (TiN) having predetermined openings.

Using the obtained laminate, plasma etching was performed using the metal hard mask as a mask, and the SiN film and the _SiO2 film were etched until the surface of the Co film was exposed to form holes, and Sample 1 was produced (see FIG. 1 ). .

When the cross-section of the laminate was confirmed with a scanning electron microscope (SEM: Scanning Electron Microscope), plasma etching residues were seen on the hole wall surface.

(b) Fabrication of a laminate (sample 2) having a W (tungsten) film

A laminate comprising a W (tungsten) film, a SiN film, an SiO ₂ film, and a metal hard mask (TiN) having predetermined openings in this order is formed on a substrate (Si).

Using the obtained laminate, plasma etching was performed using the metal hard mask as a mask, and the SiN film and the _SiO2 film were etched until the surface of the W film was exposed to form holes, and Sample 2 was produced (see FIG. 1 ). .

Regarding the cross section of the obtained layered product, similarly to the above-mentioned layered product having the Co film, plasma etching residues were observed on the hole wall surface by SEM observation.

(2) Preparation of cleaning solution

<Refinement of water>

Water used for preparation of the following cleaning solution was prepared using the method described in paragraphs [0074] to [0084] of JP-A-2011-110515. Furthermore, the method includes a metal ion removal step.

The Fe ion content and the Co ion content of the obtained water were each 1 mass ppt or less. In addition, the content of Fe ions and the content of Co ions were measured by an inductively coupled plasma mass spectrometer (manufactured by Yokogawa Analytical Systems, Agilent (Agilent) 7500cs type).

Then, prepare respectively the cleaning solution shown in table 1～table 6 (embodiment 1A ~ Example 20A, Example 1B ~ Example 11B, Example 1C ~ Example 29C, Example 1D ~ Example 16D, Example 1E ~ Example 12E, Example 1F ~ Example 10F, Example 1G ~ Implementation Example 12G, Example 1H ~ Example 12H, Comparative Example 1A). In addition, in each cleaning solution, the concentration (mass %) of each component used was as described in the table|surface, and the remainder was the water obtained by the said method. In addition, pH was adjusted to 7-11.

Furthermore, the content of Fe ions and the content of Co ions are refined by refining the hydroxylamine compound and solvent contained in the cleaning solution (metal ion removal step F), and/or refining the prepared cleaning solution ( Metal ion removal step G) to prepare the desired amount. Specifically, an ion exchange resin membrane (IonKleen SL product No.DFA1SRPESW44 manufactured by Japan Pall Co., Ltd., with a flow rate of 0.3L/min to 0.6L/min, the surface area of the membrane is 1100cm ² , The number of filters: 1~2) is prepared by passing through the liquid.

The content of Fe ions and the content of Co ions in the cleaning solution relative to the total mass of the cleaning solution were measured by an inductively coupled plasma mass spectrometer (manufactured by Yokogawa Analytical Systems, Agilent 7500cs).

The various ingredients used in the cleaning solution are shown below.

<reducing agent>

HA: hydroxylamine (manufactured by BASF)

HAS: Hydroxyammonium sulfate (manufactured by BASF)

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

<Fluoride>

HF: Hydrogen fluoride (manufactured by Kanto Chemical Co., Ltd.)

NH ₄ F: Ammonium fluoride (manufactured by Wako Pure Chemical Industries, Ltd.)

H ₂ SiF ₆ : Fluorosilicic acid (manufactured by Wako Pure Chemical Industries, Ltd.)

<Anticorrosion agent>

1-Thioglycerol (equivalent to formula (A), manufactured by Wako Pure Chemical Industries, Ltd.)

L-cysteine (equivalent to formula (A), manufactured by Wako Pure Chemical Industries, Ltd.)

Thiomalic acid (equivalent to formula (A), manufactured by Wako Pure Chemical Industries, Ltd.)

Catechol (equivalent to formula (B), manufactured by Kanto Chemical Co., Ltd.)

4-tertiary butylcatechol (equivalent to formula (B), manufactured by Kanto Chemical Co., Ltd. (in the table, equivalent to tBu-catechol))

1H-1,2,3-triazole (corresponds to formula (C), manufactured by Tokyo Chemical Industry Co., Ltd. (in the table, corresponds to 1,2,3-triazole))

Benzotriazole (equivalent to formula (C), manufactured by Tokyo Chemical Industry Co., Ltd.)

5-Methyl-1H-benzotriazole (corresponds to formula (C), manufactured by Tokyo Chemical Industry Co., Ltd. (in the table, corresponds to 5-methylbenzotriazole))

Tetrazole (manufactured by Tokyo Chemical Industry Co., Ltd.)

<chelating agent>

DPTA: Diethylenetriaminepentaacetic acid (manufactured by Chubu Chelest)

EDTA: Ethylenediaminetetraacetic acid (manufactured by Chubu Gillisd Corporation)

<Water-soluble organic solvent>

EGBE: Ethylene glycol butyl ether (manufactured by Wako Pure Chemical Industries, Ltd.)

TPGME: Tripropylene glycol methyl ether (manufactured by Wako Pure Chemical Industries, Ltd.)

DEGEE: Diethylene glycol monoethyl ether (manufactured by Wako Pure Chemical Industries, Ltd.)

<pH adjuster>

DBU: 1,8-diazabicyclo[5.4.0]undec-7-ene (manufactured by San-Apro)

<Quaternary ammonium hydroxide>

TMAH: tetramethylammonium hydroxide (manufactured by Sachem)

Choline: Manufactured by Sankai

<Alkanolamines>

Monoethanolamine (manufactured by Tokyo Chemical Industry Co., Ltd.)

Diethylene glycol amine (manufactured by Tokyo Chemical Industry Co., Ltd.)

(3) Evaluation

Various evaluations shown below were performed on each of the cleaning solutions prepared above.

(a) Evaluation of detergency when the cleaning solution is freshly prepared (within 1 hour immediately after the cleaning solution is formed)

The detergency of the cleaning solution immediately after preparation (within 1 hour immediately after the cleaning solution was composed) was evaluated by the following procedure.

First, immerse the prepared slices (approximately 2.0 cm x 2.0 cm) of sample 1 and sample 2 in each cleaning solution whose temperature was adjusted to 60° C., and take out sample 1 and sample 2 after 10 minutes. The slices were immediately washed with ultrapure water and dried under N ₂ .

Thereafter, the sliced surfaces of sample 1 and sample 2 after immersion were observed by SEM, and the removal properties of plasma etching residues ("residue removal performance") were determined according to the following criteria, Co, W, SiO ₂ The corrosion resistance (respectively "Co corrosion resistance", "W corrosion resistance", "SiO ₂ corrosion resistance") was evaluated. In addition, the results of using Sample 1 are shown regarding the residue removal performance and the SiO ₂ corrosion protection performance.

<Residue removal performance>

"AA": Plasma etching residues were completely removed within 0.5 minutes.

"A": The plasma etching residue was completely removed within 0.5 minutes and within 1 minute.

"B": Plasma etching residues were not completely removed within 2 minutes and remained slightly, but met practically required performance.

"C": The plasma etching residue was hardly removed within 2 minutes.

<Co corrosion resistance>

"A": Almost no corrosion was observed in the Co film (corrosion of 0.5% or less).

"B": Corrosion was slightly observed in the Co film (more than 0.5% and less than 1% corrosion).

"C": Slight corrosion (more than 1% and less than 5% corrosion) was observed in the Co film.

"D": Large corrosion (more than 5% corrosion) was seen in the Co film.

In addition, for example, "corrosion of 0.5% or less" means that when the initial film thickness is taken as 100%, the amount of film reduction after chemical solution treatment is 0.5% or less. It also has the same meaning in each evaluation of the following <W anticorrosion ability> and <SiO ₂ anticorrosion ability>.

<W corrosion resistance>

"A": Almost no corrosion (corrosion of 0.5% or less) was observed in the W film.

"B": Slight corrosion was observed in the W film (more than 0.5% and less than 1% corrosion).

"C": Slight corrosion (more than 1% and less than 5% corrosion) was observed in the W film.

"D": Large corrosion (more than 5% corrosion) was seen in the W film.

<SiO ₂ Corrosion Resistance>

"A": Almost no corrosion (0.5% or less corrosion) was observed in the SiO ₂ film.

"B": Slight corrosion was seen in the SiO ₂ film (more than 0.5%, less than 1% corrosion).

"C": Large corrosion (more than 1% corrosion) was seen in the SiO ₂ film.

(b) Detergency evaluation after repeated use of the cleaning solution (after 25 tablets were treated)

With respect to each cleaning solution, the evaluation of detergency after 25 samples 1 were processed was performed using the sample 1 prepared above.

Specifically, the sample 1 was cleaned one by one without changing the cleaning solution according to the cleaning procedure and conditions carried out in the evaluation of the detergency immediately after preparation of the cleaning solution (a), The 25th sliced surface of sample 1 after immersion was observed by SEM to evaluate the residue removal performance, Co corrosion protection ability, W corrosion protection ability, and SiO ₂ corrosion protection ability.

The detergency after repeated use of the detergency solution (after 25 tablets were treated) was evaluated according to the following criteria.

"A": In various evaluations of residue removal performance, Co corrosion resistance, W corrosion protection, and SiO ₂ corrosion resistance, the same results as those immediately after production were obtained.

"B": In any evaluation of residue removal performance, Co corrosion resistance, W corrosion resistance, and SiO ₂ corrosion protection, the result was slightly inferior to that of the initial production.

"C": In any evaluation of residue removal performance, Co corrosion protection performance, W corrosion protection performance, and SiO ₂ corrosion protection performance, the result is far worse than that of the initial production, but satisfies practically required performance.

"D": In any evaluation of residue removal performance, Co corrosion protection performance, W corrosion protection performance, and SiO ₂ corrosion protection performance, it is far worse than when it was just produced, and does not meet the performance required for practical use.

(c) Evaluation of detergency after 24 hours of the detergent

The evaluation of the detergency after 24 hours elapsed was performed for each cleaning liquid using the sample 1 prepared above.

Specifically, after putting the cleaning solution into a storage bottle and storing it in a sealed container at 60°C for 24 hours, use the cleaning procedure performed in (a) the cleaning performance evaluation of the cleaning solution immediately after preparation. and conditions, sample 1 was cleaned.

Thereafter, the sliced surface of Sample 1 after immersion was observed by SEM to evaluate the residue removal performance, Co corrosion protection performance, W corrosion protection performance, and SiO ₂ corrosion protection performance.

The detergency after 24 hours of the cleaning solution was evaluated based on the following criteria.

"A": In various evaluations of residue removal performance, Co corrosion resistance, W corrosion protection, and SiO ₂ corrosion resistance, the same results as those immediately after production were obtained.

"B": In any evaluation of residue removal performance, Co corrosion resistance, W corrosion resistance, and SiO ₂ corrosion protection, the result was slightly inferior to that of the initial production.

"C": In any evaluation of residue removal performance, Co corrosion protection performance, W corrosion protection performance, and SiO ₂ corrosion protection performance, the result is far worse than that of the initial production, but satisfies practically required performance.

"D": In any evaluation of residue removal performance, Co corrosion protection performance, W corrosion protection performance, and SiO ₂ corrosion protection performance, it is far worse than when it was just produced, and does not meet the performance required for practical use.

In the following tables, each unit of the cleaning solution is based on mass.

In addition, for example, "5×10^9" in the column of "HA/Fe(Co)ion" means "5×10 ⁹ ".

In addition, "-" in the performance evaluation column shows "not measured".

In addition, in Tables 1 to 6, blanks in the column of Fe ions and Co ions in the formula column indicate that the detection limit was not met. Also, other blanks in the recipe column mean unmixed.

From the results shown in Tables 1 to 6, it was confirmed that the cleaning solution of the present invention using hydroxylamine as a reducing agent and/or its salt as a reducing agent has excellent residue removal performance and corrosion resistance.

On the other hand, as shown in Comparative Example 1A, when HF was used, it was confirmed that SiO ₂ was corroded even at a low concentration. In addition, corrosion of the metal film (Co, W) was confirmed.

In addition, as is clear from Table 1, the Fe ions in the solution are reduced to 1 ppt by mass by refining the components contained in the cleaning solution (solvent, hydroxylamine compound, etc.) and/or the cleaning solution itself. 1 mass ppm, it can maintain good cleaning performance even after 24 hours. In addition, similarly to Fe ions, by making Co ions 1 mass ppm to 1 mass ppm, good cleaning performance can be maintained even after 24 hours.

Furthermore, it was confirmed that when at least one of Fe ions and Co ions in the liquid is changed to 10 mass ppt to 5 mass ppb, the residue removal performance is improved, and further, when at least one of Fe ions and Co ions in the liquid is changed to 1 mass ppb At ~5 mass ppb, in addition to the residue removal performance, the Co corrosion protection performance is also improved. In addition, at this time, it was confirmed that when the concentrations of Fe ions and Co ions were both adjusted to the above-mentioned ranges, the residue removal performance was more excellent.

Furthermore, it was confirmed that when the total content of the hydroxylamine compound is 5×10 ⁴ to 5×10 ¹⁰ relative to the total content (mass % ratio) of at least one selected from Fe ions and Co ions, even after time passes The cleaning performance of the cleaning solution is maintained well. In particular, when the total content of hydroxylamine compounds is 1×10 ⁷ ~5×10 ⁹ (preferably 1×10 ⁷ ~ 5×10 ⁷ ), further improvement was also confirmed regarding the residue removal performance of the cleaning solution, the corrosion resistance to the object to be cleaned, and the like.

In addition, as is clear from Table 1, it was confirmed that the cleaning solution to which Fe ions or Co ions were added was excellent in reusability.

In addition, if Example 1C, Example 3C～Example 5C of Table 3, Example 1F～Example 9F of Table 5 are compared, it is confirmed that it is different from other examples (Example 1C of Table 3, Example 5 of Table 5) 1F～Example 9F), compared with Example 3C～Example 5C of Table 3 has significantly excellent performance.

Specifically, it was confirmed that the cleaning solution of Example 3C and Example 4C containing 1 mass ppb to 5 mass ppb of Fe ions maintained good residue removal performance even when 100 or more sheets were treated, and further, Corrosion resistance to objects to be cleaned is also well maintained. In addition, it was confirmed that the cleaning solution of Example 5C containing Fe ions and Co ions at 1 mass ppb to 5 mass ppb respectively maintained good residue removal performance even when 100 or more sheets were treated, and furthermore, Co corrosion prevention In addition to the performance, the corrosion resistance to the object to be cleaned is also well maintained.

In addition, as is clear from the comparison of the results of Examples 1A to 3A and Table 2, it was confirmed that the corrosion resistance of Co was further improved by adding the anticorrosion agent.

In addition, from the comparison of the results of Example 9B in Table 2 and Example 8C and Example 9C in Table 3, it is clear that the inclusion of a chelating agent reduces the change in performance over time and is excellent in reusability.

In addition, according to the comparison with Example 8C, Example 10C~Example 12C in Table 3, it was confirmed that by containing a water-soluble organic solvent, the residue removal performance was further improved. Lift.

In addition, as is clear from the comparison of the results of Examples 1A to 3A and Table 4, it was confirmed that the residue removal performance was further improved by formulating quaternary ammonium hydroxides, fluorides, or alkanolamines.

In addition, according to the comparison of the results of Example 1A~Example 3A and Table 5 and Table 6, it can be seen that water, at least one selected from hydroxylamine and its salts, 10 mass ppt~5 mass ppb (preferably 1 mass ppb ~ 5 mass ppb) of Fe ions and other additive components combined at least any one of the residue removal performance, corrosion resistance, reusability, and good cleaning performance after 24 hours are more excellent.

In addition, regarding water, at least one selected from hydroxylamine and its salts, Co ions in the range of 10 mass ppt to 5 mass ppb (preferably 1 mass ppb to 5 mass ppb), and other additives. The net liquid also sees the same result.

(3) Static elimination evaluation

For medicinal liquid A (embodiment 7B), medicinal liquid B (embodiment 8B), medicinal liquid C (embodiment 13C), medicinal liquid D (embodiment 1D), medicinal liquid E (embodiment 2D), medicinal liquid F ( Example 8D), using the grounded material SUS316 for static elimination, and setting the immersion time to 20 minutes, except that, in the same way, carry out the residue removal performance, Co corrosion resistance, W corrosion resistance, _SiO2 corrosion resistance. evaluate.

As a result of the evaluation, the residue removal performance of any of the chemical solutions was the same as when it was just made, and in various evaluations of Co corrosion resistance, W corrosion resistance, and _SiO2 corrosion resistance, it was possible to obtain a product that was superior in corrosion resistance than when it was just made. result.

From this result, it turns out that corrosion resistance becomes more excellent by passing through a static elimination process.

Regarding the drug solution of Example 14C, the pH was adjusted by adjusting the amount of TMAH. In addition, when setting it as acidic pH, oxalic acid dihydrate (made by Wako Pure Chemical Industries, Ltd.) was added and adjusted. In this way, medical solutions I1 to I6 having pHs of 5.0, 6.0, 7.0, 7.5, 9.0, and 11.0 were produced. Each prepared cleaning solution was evaluated by the same method as in Example 14C. As a result of the evaluation, regarding the residue removal performance, the cleaning solution I1 became B, the cleaning solution I2 became B, and the cleaning solutions I3 to I6 became A. In addition, with regard to the anti-corrosion ability of Co, the cleaning solution I1 becomes B, and the cleaning solutions I2 to I6 change to A. In addition, with regard to the anticorrosion ability of W, the cleaning solution I1 and the cleaning solution I2 become B, and the cleaning solutions I3 to I6 become A. With regard to other evaluations, poorness was not observed.

Regarding the liquid medicine of Example 4D, the pH was adjusted by adjusting the amount of choline. In addition, when setting it as acidic pH, oxalic acid dihydrate (made by Wako Pure Chemical Industries, Ltd.) was added and adjusted. In this way, chemical solutions J1 to J6 having pHs of 5.0, 6.0, 7.0, 7.5, 9.0, and 11.0 were produced. Each prepared cleaning solution was evaluated by the same method as in Example 4D. As a result of the evaluation, regarding the residue removal performance, cleaning liquid J1 and cleaning liquid J2 became B, and cleaning liquid J3 to cleaning liquid J6 became A. In addition, with regard to the Co corrosion prevention ability, the cleaning solution J1 becomes B, and the cleaning solutions J2 to J6 become A. In addition, with regard to the anticorrosion ability of W, cleaning liquid J1 and cleaning liquid J2 become B, and cleaning liquid J3 to cleaning liquid J6 become A. With regard to other evaluations, poorness was not observed.

1‧‧‧substrate

2‧‧‧Metal film

3‧‧‧Etch stop layer

4‧‧‧Interlayer insulating film

5‧‧‧Metal Hard Mask

6‧‧‧hole

10‧‧‧Laminates

11‧‧‧inner wall

11a‧‧‧section wall

11b‧‧‧bottom wall

12‧‧‧Dry etching residue

Claims (51)

A cleaning solution, which is a cleaning solution for a substrate with a metal hard mask containing any one or more of Cu, Co, W, AlOx, AlN, AlOxNy, WOx, Ti, TiN, ZrOx, HfOx, and TaOx, comprising : At least one hydroxylamine compound selected from hydroxylamine and hydroxylamine salts, water, and Fe ions of 1 mass ppm to 10 mass ppm, the content of the hydroxylamine compound being 0.01% by mass relative to the total mass of the cleaning solution ~30% by mass. Furthermore, x and y are numbers represented by x=1~3 and y=1~2, respectively. The cleaning solution described in item 1 of the scope of the patent application further includes 1 mass ppm to 10 mass ppm of Co ions. The cleaning solution as described in item 1 of the scope of the patent application further includes an anti-corrosion agent. The cleaning solution as described in item 3 of the scope of the patent application, wherein the anti-corrosion agent is selected from the compounds represented by the following formula (A) ~ formula (C), and substituted or unsubstituted tetrazole any kind,

In formula (A), R ^1A ~ R ^5A independently represent a hydrogen atom, a hydrocarbon group, a hydroxyl group, a carboxyl group or an amino group; wherein, the structure contains at least one group selected from a hydroxyl group, a carboxyl group and an amino group; the formula ( In B), R ^1B ~ R ^4B independently represent a hydrogen atom or a hydrocarbon group; in formula (C), R ^1C , R ^2C and R ^N independently represent a hydrogen atom or a hydrocarbon group; in addition, R ^1C and R ^2C can be bonded Knot to form a ring. The cleaning solution as described in Item 1 of the patent application, which further includes a chelating agent. The cleaning solution described in claim 1 of the patent application further includes a water-soluble organic solvent. The cleaning solution described in claim 1 of the patent application further includes a pH adjusting agent. The cleaning solution as described in item 1 of the scope of the patent application further includes quaternary ammonium hydroxides. The cleaning solution described in item 1 of the patent application further includes fluoride. The cleaning solution described in item 1 of the scope of the patent application has a pH of 6-11. A cleaning solution, which is a cleaning solution for a substrate with a metal hard mask containing any one or more of Cu, Co, W, AlOx, AlN, AlOxNy, WOx, Ti, TiN, ZrOx, HfOx, and TaOx, comprising : At least one hydroxylamine compound selected from hydroxylamine and hydroxylamine salts, water, Fe ions from 1 mass ppm to 10 mass ppm, and selected from 1,8-diazabicyclo[5.4.0]undec-7 -ene and 1,5-diazabicyclo [4.3.0] One or more of the group consisting of non-5-ene, the content of the hydroxylamine compound is 0.01% by mass to 30% by mass relative to the total mass of the cleaning solution, and x, y are the numbers represented by x=1~3 and y=1~2 respectively. The cleaning solution described in item 11 of the scope of the patent application further includes 1 mass ppm to 10 mass ppm of Co ions. The cleaning solution as described in item 11 of the scope of the patent application further includes an anti-corrosion agent. The cleaning solution as described in item 13 of the scope of the patent application, wherein the anti-corrosion agent is selected from the compounds represented by the following formula (A) ~ formula (C), and substituted or unsubstituted tetrazole any kind,

In formula (A), R ^1A ~ R ^5A independently represent a hydrogen atom, a hydrocarbon group, a hydroxyl group, a carboxyl group or an amino group; wherein, the structure contains at least one group selected from a hydroxyl group, a carboxyl group and an amino group; the formula ( In B), R ^1B ~ R ^4B independently represent a hydrogen atom or a hydrocarbon group; in formula (C), R ^1C , R ^2C and R ^N independently represent a hydrogen atom or a hydrocarbon group; in addition, R ^1C and R ^2C may be bonded Knot to form a ring. The cleaning solution as described in item 11 of the scope of the patent application further includes a chelating agent. The cleaning solution described in claim 11 of the patent application further includes a water-soluble organic solvent. The cleaning liquid as described in item 11 of the scope of the patent application further includes quaternary ammonium hydroxides. The cleaning solution as described in claim 11 of the patent application further includes fluoride. The pH of the cleaning solution as described in item 11 of the patent application is 6-11. A cleaning solution, which is a cleaning solution for a substrate with a metal hard mask containing any one or more of Cu, Co, W, AlOx, AlN, AlOxNy, WOx, Ti, TiN, ZrOx, HfOx, and TaOx, comprising : At least one hydroxylamine compound selected from hydroxylamine and hydroxylamine salts, water, Fe ions of 1 mass ppm to 10 mass ppm, and quaternary ammonium hydroxides, the content of the hydroxylamine compound relative to the cleaning solution The total mass of is 0.01% by mass to 30% by mass, and x and y are numbers represented by x=1~3 and y=1~2, respectively. The cleaning solution described in claim 20 of the patent application further includes 1 mass ppm to 10 mass ppm of Co ions. The cleaning solution as described in item 20 of the scope of the patent application further includes an anti-corrosion agent. The cleaning solution as described in item 22 of the scope of the patent application, wherein the anti-corrosion agent is selected from the compounds represented by the following formula (A) ~ formula (C), and substituted or unsubstituted tetrazole any kind,

In formula (A), R ^1A ~ R ^5A independently represent a hydrogen atom, a hydrocarbon group, a hydroxyl group, a carboxyl group or an amino group; wherein, the structure contains at least one group selected from a hydroxyl group, a carboxyl group and an amino group; the formula ( In B), R ^1B ~ R ^4B independently represent a hydrogen atom or a hydrocarbon group; in formula (C), R ^1C , R ^2C and R ^N independently represent a hydrogen atom or a hydrocarbon group; in addition, R ^1C and R ^2C may be bonded Knot to form a ring. The cleaning solution as described in claim 20 of the patent application further includes a chelating agent. The cleaning solution described in claim 20 of the patent application further includes a water-soluble organic solvent. The cleaning solution described in claim 20 of the patent application further includes a pH adjusting agent. The cleaning solution as described in claim 20 of the patent application further includes fluoride. The pH of the cleaning solution described in item 20 of the patent application is 6-11. A cleaning solution, which is a cleaning solution for a substrate with a metal hard mask containing any one or more of Cu, Co, W, AlOx, AlN, AlOxNy, WOx, Ti, TiN, ZrOx, HfOx, and TaOx, comprising : At least one hydroxylamine compound selected from hydroxylamine and hydroxylamine salts, water, 1 mass ppm to 10 mass ppm of Fe ions, and ammonium hydroxide, 1,8-diazabicyclo[5.4.0] One or more pH regulators in the group consisting of undec-7-ene and 1,5-diazabicyclo[4.3.0]non-5-ene, the content of the hydroxylamine compound relative to the washing The total mass of the net liquid is 0.01% by mass to 30% by mass, and the amount of the pH adjuster is 0.1% by mass to 5% by mass relative to the total mass of the cleaning liquid. Furthermore, x and y are represented by x= 1~3, the number represented by y=1~2. The cleaning solution described in item 29 of the scope of the patent application further includes 1 mass ppm to 10 mass ppm of Co ions. The cleaning solution as described in item 29 of the scope of the patent application further includes an anti-corrosion agent. The cleaning solution as described in item 31 of the scope of the patent application, wherein the anti-corrosion agent is selected from the compounds represented by the following formula (A) ~ formula (C), and substituted or unsubstituted tetrazole any kind,

In formula (A), R ^1A ~ R ^5A independently represent a hydrogen atom, a hydrocarbon group, a hydroxyl group, a carboxyl group or an amino group; wherein, the structure contains at least one group selected from a hydroxyl group, a carboxyl group and an amino group; the formula ( In B), R ^1B ~ R ^4B independently represent a hydrogen atom or a hydrocarbon group; in formula (C), R ^1C , R ^2C and R ^N independently represent a hydrogen atom or a hydrocarbon group; in addition, R ^1C and R ^2C may be bonded Knot to form a ring. The cleaning liquid as described in claim 29 of the patent application further includes a chelating agent. The cleaning solution as described in claim 29 of the patent application further includes a water-soluble organic solvent. The cleaning solution as described in item 29 of the scope of the patent application further includes quaternary ammonium hydroxides. The cleaning solution described in item 29 of the patent application further includes fluoride. The pH of the cleaning solution described in item 29 of the patent application is 6-11. A cleaning solution, which is a cleaning solution for a substrate with a metal hard mask containing any one or more of Cu, Co, W, AlOx, AlN, AlOxNy, WOx, Ti, TiN, ZrOx, HfOx, and TaOx, comprising : At least one hydroxylamine compound selected from hydroxylamine and hydroxylamine salts, water, Fe ions of 1 mass ppm to 10 mass ppm, corrosion inhibitors, and at least one of water-soluble organic solvents and alkanolamines, the The content of the hydroxylamine compound is 20% by mass to 30% by mass relative to the total mass of the cleaning solution, and x and y are numbers represented by x=1~3 and y=1~2, respectively. The cleaning solution described in claim 38 of the patent application further includes Co ions in the range of 1 mass ppm to 10 mass ppm. The cleaning solution as described in item 38 of the scope of the patent application, wherein the anti-corrosion agent is selected from the compounds represented by the following formula (A) ~ formula (C), and substituted or unsubstituted tetrazole any kind,

In formula (A), R ^1A ~ R ^5A independently represent a hydrogen atom, a hydrocarbon group, a hydroxyl group, a carboxyl group or an amino group; wherein, the structure contains at least one group selected from a hydroxyl group, a carboxyl group and an amino group; the formula ( In B), R ^1B ~ R ^4B independently represent a hydrogen atom or a hydrocarbon group; in formula (C), R ^1C , R ^2C and R ^N independently represent a hydrogen atom or a hydrocarbon group; in addition, R ^1C and R ^2C may be bonded Knot to form a ring. The cleaning solution as described in item 38 of the patent application, which further includes a chelating agent. The cleaning solution as described in claim 38 of the patent application, which includes a water-soluble organic solvent. The cleaning solution described in claim 38 of the patent application further includes a pH adjusting agent. The cleaning liquid as described in item 38 of the scope of the patent application further includes quaternary ammonium hydroxides. The cleaning solution as described in item 38 of the patent application, which further includes fluoride. As the cleaning solution described in item 38 of the patent application, its pH is 6-11. A method for cleaning a substrate, comprising: cleaning solution preparation step A, preparing the cleaning solution described in any one of items 1 to 46 of the patent application; and cleaning step B, using the cleaning solution Liquid, cleaning with Cu, Co, W, AlOx, AlN, AlOxNy, WOx, Ti, TiN, ZrOx, HfOx and TaOx Any one or more metal hard mask substrates; moreover, x and y are numbers represented by x=1~3 and y=1~2, respectively. The substrate cleaning method described in item 47 of the scope of patent application, which includes: cleaning solution preparation step A, preparing the cleaning solution described in any one of items 1 to 46 of the scope of application for patents; cleaning Step B, using the cleaning solution to clean the substrate with a metal hard mask containing any one or more of Cu, Co, W, AlOx, AlN, AlOxNy, WOx, Ti, TiN, ZrOx, HfOx and TaOx; Liquid recovery step C, recovering the drain of the cleaning solution used in the cleaning step B; washing step D, using the recovered drain of the cleaning solution, washing the re-prepared equipment containing Cu, Co, W, AlOx, AlN, AlOxNy, WOx, Ti, TiN, ZrOx, HfOx and TaOx any one or more metal hard mask substrates; and the drainage recovery step E, recovery in the cleaning step D Drainage of the cleaning solution used; and repeatedly implementing the cleaning step D and the drainage recovery step E to reuse the drainage of the cleaning solution. The substrate cleaning method described in item 47 or item 48 of the scope of the patent application, before the cleaning solution preparation step A, has the function of removing from at least one of the hydroxylamine compound and the water selected from Metal ion removal step F of at least one ion species of Fe ions and Co ions, or after the cleaning solution preparation step A and before performing the cleaning step B Before, there is a metal ion removal step G of removing at least one ion species selected from Fe ions and Co ions in the cleaning solution. The substrate cleaning method described in item 47 or item 48 of the patent scope of the application, before the cleaning solution preparation step A, has a destaticizing step I for destaticizing the water, or in the cleaning solution After the preparation step A and before performing the cleaning step B, there is a static removal step J of removing static electricity from the cleaning solution. A method for manufacturing a semiconductor element, which includes using the cleaning solution described in any one of items 1 to 46 of the scope of the patent application to clean the equipment containing Cu, Co, W, AlOx, AlN, AlOxNy, WOx, The step of using any one or more metal hard mask substrates of Ti, TiN, ZrOx, HfOx, and TaOx, and x, y are numbers represented by x=1~3, y=1~2, respectively.

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