TWI896555B - Treatment solution and treatment method - Google Patents

Abstract

The present invention provides a treatment liquid and treatment method that are excellent in removing target objects while suppressing etching of a first metal-containing substance comprising one or more first metals selected from the group consisting of Co and Cu. The treatment liquid of the present invention is used when treating a treatment object containing a first metal-containing substance comprising one or more first metals selected from the group consisting of Co and Cu. The treatment liquid contains an etchant, an organic solvent, and an anticorrosive agent. The organic solvent content is 80% by mass or greater relative to the total mass of the treatment liquid. The anticorrosive agent is one or more compounds selected from the group consisting of Compound X, Compound Y, and Compound Z.

Description

Treatment fluid, treatment method

The present invention relates to a treatment liquid and a treatment method.

Photolithography is used to form fine electronic circuit patterns on substrates to manufacture semiconductor devices such as CCDs (charge-coupled devices) and memories. Specifically, an example involves forming a laminate comprising a substrate, a metal layer serving as a wiring material formed on the substrate, an etch-stop layer formed on the metal layer, an interlayer insulating film formed on the etch-stop layer, and a metal hard mask formed on the interlayer insulating film. A dry etching step is performed using the metal hard mask as a mask, and each component is etched to expose the surface of each metal layer, thereby creating holes penetrating the metal hard mask, the interlayer insulating film, and the etch-stop layer.

A process is performed to further remove unnecessary parts (target removal) from the laminate.

For example, in a laminate that has undergone a dry etching step, residues from various components (dry etching residues) adhere to at least one of the metal layer forming the holes and the interlayer insulating film. Therefore, a treatment liquid is used to remove the residues from various components.

As such a treatment liquid, Patent Document 1 discloses an "aqueous cleaning composition comprising at least one anticorrosive agent, water, and optionally at least one etchant, etc. (Claim 1)." Hydrofluoric acid, etc., is proposed as the etchant in the aqueous cleaning composition (treatment liquid) (Claim 4).

[Patent Document 1] Japanese Patent Publication No. 2013-533631

When the laminate that has undergone the dry etching step contains cobalt (Co) or copper (Cu) inclusions as a metal layer, when the treatment liquid is used to remove the target material, the Co (or Cu) inclusions that were not intended to be removed may also be etched (removed).

Therefore, the present invention aims to provide a treatment solution and treatment method that can effectively remove target materials (such as dry etching residues and/or metal hard masks) while suppressing the etching of a first metal-containing material including one or more first metals selected from the group consisting of Co and Cu.

The inventors have conducted in-depth research on the above-mentioned issues and have discovered that the above-mentioned issues can be solved by the following structure.

[1]

A treatment solution for use in treating a treatment object containing a first metal-containing material comprising at least one first metal selected from the group consisting of Co and Cu. The treatment solution comprises: an etchant; an organic solvent; and an anti-corrosion agent. The organic solvent is present in an amount of 80% by mass or greater relative to the total mass of the treatment solution. The anti-corrosion agent is one or more compounds selected from the group consisting of compound X, compound Y, and compound Z. Compound X is one or more compounds selected from the group consisting of compounds containing one substituent XA represented by any one of the general formulae (XA1) to (XA3) and one or more substituents XB represented by any one of the general formulae (XB1) to (XB7), and compounds containing two or more of the substituents XA.

In general formulas (XA1) to (XA3) and (XB1) to (XB7), * represents a bonding position. R each independently represents a hydrogen atom or an alkyl group.

Compound Y: A compound represented by the general formula (Y).

Y ^Q -COOH (Y)

In the general formula (Y), Y ^Q represents an aromatic cyclic group having a phosphonooxy group, an aromatic cyclic group having a boronic acid group, or a phosphono-alkylene group.

Compound Z: One or more compounds selected from the group consisting of mellitic acid and oxalic acid.

[2]

The processing liquid as described in [1], wherein the above-mentioned etchant is a fluorine-containing compound.

[3]

The processing liquid as described in [1] or [2], wherein the above-mentioned etchant is one or more compounds selected from the group consisting of hydrogen fluoride, ammonium fluoride, tetramethylammonium fluoride, tetraethylammonium fluoride, tetrabutylammonium fluoride, hexafluorosilicic acid, hexafluorophosphoric acid and tetrafluoroboric acid.

[4]

The treatment solution as described in any one of [1] to [3], wherein the organic solvent contains an alcohol solvent.

[5]

The treatment liquid as described in any one of items [1] to [4], wherein the organic solvent is one or more compounds selected from the group consisting of ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, hexanol, 1-octanol, 2-octanol and 2-ethylhexanol.

[6]

The treatment solution as described in any one of [1] to [5], wherein the compound X is a compound containing only one partial structure represented by -COOH.

[7]

The treatment solution as described in any one of items [1] to [5], wherein the preservative is one or more compounds selected from the group consisting of L-cysteine, gluconic acid, homoarginine, L-citrulline, DL-alanine glycine, o-carboxyphenylboronic acid, mellitic acid, and oxalic acid.

[8]

The treatment liquid as described in any one of [1] to [7], wherein, relative to the total mass of the treatment liquid, it contains 0.1-3 mass% of the etchant, 80-99 mass% of the organic solvent, 0.05-3.0 mass% of the preservative, and 0.05-14 mass% of water.

[9]

The treatment solution as described in any one of [1] to [8], wherein the pH is 4.0 or less.

[10]

A treatment method, wherein the object to be treated further contains a second metal inclusion comprising one or more second metals selected from the group consisting of Zr, Ti, Hf, and Ta, and the treatment method comprises the step of bringing the treatment liquid described in any one of items [1] to [9] into contact with the object to be treated to remove the second metal inclusion.

[11]

A processing method, wherein the object to be processed further contains dry etching residue, and the processing method comprises the step of bringing the processing liquid described in any one of items [1] to [9] into contact with the object to be processed to remove the dry etching residue.

[12]

The treatment method as described in [10] or [11], wherein the first metal inclusion contains Co.

[13]

The treatment method as described in any one of [10] to [12], wherein the removal rate of the first metal inclusion when the treatment liquid is brought into contact with the object to be treated is 10 Å/min or less.

[14]

The treatment method as described in any one of [10] to [13], wherein the above-mentioned treated object further contains Al or _{Al2O3 ,} i.e., aluminum-based materials.

[15]

The treatment method as described in [14], wherein the removal rate of the aluminum-based material when the treatment liquid is in contact with the object to be treated is less than 10Å/min.

[16]

The treatment method as described in any one of [10] to [15], wherein the treatment solution is used at 25-60°C.

[Invention Effect]

According to the present invention, a treatment solution and treatment method can be provided that are excellent in removing target objects while suppressing etching of a first metal-containing substance including one or more first metals selected from the group consisting of Co and Cu.

1:Substrate

2: Metal layer

3: Etch stop layer

4: Interlayer insulation film

5: Metal Hard Mask

6: Hole

10: Layered body

11: Inner wall

11a: Section wall

11b: Bottom wall

12: Dry etching residue

Figure 1 is a schematic cross-sectional view showing an example of an object to be treated using the treatment solution of the present invention.

The present invention is described below.

Furthermore, in the present invention, a numerical range represented by “~” refers to a range that includes the numerical values before and after the “~” as the lower limit and the upper limit.

Furthermore, the term "preparation" in the present invention includes not only synthesizing and blending predetermined materials, but also acquiring predetermined materials through purchase, etc.

In addition, in the present invention, 1Å (angstrom) is equivalent to 0.1nm.

Furthermore, in the notation of groups (atomic groups) in the present invention, unsubstituted and unsubstituted groups include groups with substituents, as well as groups without substituents, to the extent that the effects of the present invention are not impaired. For example, "alkyl" includes not only alkyl groups without substituents (unsubstituted alkyl groups) but also alkyl groups with substituents (substituted alkyl groups). The same applies to all compounds.

In the present invention, "pH" refers to the value measured at 23°C using a pH meter (product name: "pH Meter F-51", manufactured by HORIBA, Ltd.). The pH value is the value read after the measurement starts and the displayed value stabilizes.

[Treatment fluid]

The treatment liquid of the present invention is used to treat a workpiece containing a first metal-containing material including one or more first metals selected from the group consisting of Co and Cu. The treatment liquid contains an etchant, an organic solvent, and an anti-corrosion agent.

The content of organic solvent is greater than 80% by mass relative to the total mass of the treatment solution.

The preservative is one or more compounds selected from the group consisting of Compound X, Compound Y, and Compound Z.

The treatment liquid of the present invention has the structure described above. While the mechanism by which the present invention solves the problem is not yet clear, the inventors make the following assumptions.

Specifically, the treatment solution of the present invention contains an etchant, or a predetermined corrosion inhibitor, in a high-concentration organic solvent. While the treatment solution primarily removes the target material with the etchant, the predetermined corrosion inhibitor also inhibits (prevents) etching of the first metal component. The corrosion inhibitor exhibits particularly good corrosion protection in high-concentration organic solvents, and it is speculated that this characteristic contributes to the effectiveness of the present invention.

Furthermore, the treatment solution of the present invention also has good corrosion resistance against Al or Al ₂ O ₃ , i.e., aluminum-based materials.

Furthermore, in the present invention, as removal targets, for example, metal hard masks and etching residues can be cited.

If one or more of the corrosion resistance against the first metal inclusion (e.g., corrosion resistance against Co inclusion and corrosion resistance against Cu inclusion), corrosion resistance against aluminum-based materials, and removal performance of the target removal object are superior, the effect of the present invention can be considered superior.

<Etchant>

The processing liquid of the present invention contains an etchant.

Etching agents have the function of removing (dissolving) the target object (metal hard mask and etching residue, etc.).

The etchant is preferably a halogen-containing compound (a compound containing a halogen atom), and more preferably a fluorine-containing compound.

The fluorine-containing compound is not particularly limited as long as it contains fluorine atoms, and known fluorine-containing compounds can be used. Among them, compounds that dissociate in the treatment solution to release fluoride ions are also preferred.

Examples of fluorine-containing compounds include hydrogen fluoride (HF), ammonium fluoride, tetramethylammonium fluoride, tetraethylammonium fluoride, tetrabutylammonium fluoride, hexafluorosilicic acid, hexafluorophosphoric acid, tetrafluoroboric acid, ammonium hexafluorophosphate, and ammonium hexafluorosilicate.

From the perspective of achieving the better effects of the present invention, the fluorine-containing compound is preferably hydrogen fluoride (HF), ammonium fluoride, tetramethylammonium fluoride, tetraethylammonium fluoride, tetrabutylammonium fluoride, hexafluorosilicic acid, hexafluorophosphoric acid, or tetrafluoroboric acid, with hydrogen fluoride being even more preferred.

To achieve the best results of the present invention, the content of the etchant (preferably a fluorine-containing compound) in the treatment liquid is preferably 0.01% by mass or greater, more preferably 0.05% by mass or greater, and even more preferably 0.1% by mass or greater, relative to the total mass of the treatment liquid. As an upper limit, it is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 3% by mass or less.

The etchant (preferably a fluorine-containing compound) may be used alone or in combination of two or more.

When using two or more etchants (preferably fluorine-containing compounds), the total content is preferably within the above range.

<Organic solvent>

The treatment solution of the present invention contains an organic solvent.

In the treatment solution of the present invention, the content of the organic solvent (preferably an alcoholic solvent) is 80% by mass or greater, preferably 80-99.9% by mass, more preferably 80-99% by mass, and even more preferably 90-98% by mass, relative to the total mass of the treatment solution.

Organic solvents may be used alone or in combination of two or more.

When using two or more organic solvents, it is best if the total content is within the above range.

Any known organic solvent can be used as the organic solvent, but hydrophilic organic solvents are preferred. A hydrophilic organic solvent is one that can be uniformly mixed with water in any ratio.

Examples of organic solvents include alcohol solvents, ketone solvents, ester solvents, ether solvents (e.g., glycol diether), sulfonium solvents, sulfide solvents, nitrile solvents, and amide solvents. These organic solvents are preferably hydrophilic.

Alcohol-based organic solvents are preferred.

Examples of alcoholic solvents include alkane diols (e.g., including alkylene glycols), alkoxy alcohols (e.g., including ethylene glycol monoethers), saturated aliphatic monohydric alcohols, unsaturated and non-aromatic monohydric alcohols, and low-molecular-weight alcohols containing a ring structure.

Among them, the alcohol solvent is preferably ethylene glycol monoether or saturated aliphatic monohydric alcohol.

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

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

Examples of alkoxy alcohols include 3-methoxy-3-methyl-1-butanol, 3-methoxy-1-butanol, 1-methoxy-2-butanol, and glycol monoethers.

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

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

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

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

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

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

Among them, ethylene glycol monobutyl ether, tripropylene glycol methyl ether, and diethylene glycol monoethyl ether are preferred.

Examples of sulfonium-based solvents include cyclobutane sulfonium, 3-methylcyclobutane sulfonium, and 2,4-dimethylcyclobutane sulfonium.

Examples of sulfoxide-based solvents include dimethyl sulfoxide.

Examples of nitrile-based solvents include acetonitrile.

Examples of amide solvents include N,N-dimethylformamide, 1-methyl-2-pyrrolidone, 2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 2-pyrrolidone, ε-caprolactam, formamide, N-methylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpropionamide, and hexamethylphosphotriamide.

Among them, one or more compounds selected from the group consisting of ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, hexanol, 1-octanol, 2-octanol, and 2-ethylhexanol are preferred.

It is also preferred to use a high-purity organic solvent with a reduced metal ion content, and it can also be further purified for use.

The purification method is not particularly limited, but known methods such as filtration, ion exchange, distillation, adsorption purification, recrystallization, reprecipitation, sublimation, and purification using a column can be used, and combinations of these methods may also be used.

<Preservatives>

The treatment fluid of the present invention contains a preservative.

The preservative is one or more compounds selected from the group consisting of Compound X, Compound Y, and Compound Z.

The above-mentioned preservatives may be used singly or in combination. When two or more preservatives are used, the two or more preservatives may be solely compound X, solely compound Y, solely compound Z, or two or three of compound X, compound Y, and compound Z.

Below, Compound X, Compound Y, and Compound Z are described in detail.

(Compound X)

Compound X is one or more compounds selected from the group consisting of a compound containing one substituent XA represented by any one of the general formulae (XA1) to (XA3) and one or more substituents XB represented by any one of the general formulae (XB1) to (XB7) (compound X1), and a compound containing two or more of the above substituents XA (compound X2).

In general formulas (XA1) to (XA3) and (XB1) to (XB7), * indicates the bonding position.

Furthermore, R in general formulas (XA1), (XA2), (XB4), and (XB5) each independently represents a hydrogen atom or an alkyl group. The alkyl group may be linear or branched, and may be entirely or partially cyclic. The alkyl group preferably has 1 to 6 carbon atoms, more preferably 1. The alkyl group is preferably unsubstituted.

From the perspective of further suppressing etching of the first metal inclusion, it is preferred that R in the group represented by general formula (XA2) is a hydrogen atom.

From the perspective of further suppressing etching of the first metal inclusion, the substituent XA is preferably a group represented by the general formula (XA1), a group represented by the general formula (XA2), a group in which R is a hydrogen atom, or a group represented by the general formula (XA3).

Furthermore, the substituent XB is not a group contained in the substituent XA.

That is, when examining whether a partial structure in a compound contains either substituent XA or substituent XB, first examine whether substituent XA is present. If substituent XA is not present, then examine whether substituent XB is present.

In other words, the substituent XB can only be present in the partial structure where the group corresponding to the substituent XA in the compound does not exist.

For example, when a carboxyhydroxymethyl group (-CH(OH)-COOH) is present in a compound, the carboxyhydroxymethyl group corresponds to the substituent XA (the group represented by the general formula (XA3)), while the -OH group that is part of the carboxyhydroxymethyl group does not correspond to the substituent XB (the group represented by the general formula (XB1)).

Furthermore, the group represented by general formula (XB1) is not a group contained in the group represented by general formula (XB2), nor is it a group contained in the group represented by general formula (XB6).

Furthermore, when a -COOH group other than "-COOH as part of the substituent XA" is present, the -OH group, which is a part of the -COOH group, corresponds to the group represented by the general formula (XB1). It is preferred that the group represented by the general formula (XB1) be other than the -OH group, which is a part of the -COOH group.

The group represented by the general formula (XB1) is preferably bonded to a carbon atom (preferably a carbon atom other than the carbonyl carbon atom, more preferably an sp3 carbon atom).

From the perspective of achieving a more superior effect of the present invention, the substituent XB is preferably a group represented by any of the general formulae (XB1), (XB3) to (XB7).

Compound X1, which is one form of compound X, is a compound containing one substituent XA represented by any one of the general formulae (XA1) to (XA3) and one or more substituents XB represented by any one of the general formulae (XB1) to (XB7).

The number of substituents XA contained in compound X1 is 1.

The number of substituents XB contained in compound X1 is preferably 1 to 10. When there are multiple substituents XB, the multiple substituents XB may be the same or different.

Compound X2, which is one form of compound X, is a compound containing two or more substituents XA represented by any one of the general formulas (XA1) to (XA3).

The number of substituents XA contained in compound X2 is preferably 2 to 10, and more preferably 2. Multiple substituents XA may be the same or different.

Compound X2 may contain a substituent XB. When compound X2 contains a substituent XB, the number of substituents XB contained in compound X2 is preferably 1 to 10. When there are multiple substituents XB, the multiple substituents XB may be the same or different.

Compound X is preferably a compound represented by the following general formula (X).

X ^A -X ^C -X ^AB (X)

In the general formula (X), ^XA represents a substituent XA (a group represented by any one of the general formulae (XA1) to (XA3)).

In general formula (X), X ^AB represents a substituent XA (a group represented by any one of general formulas (XA1) to (XA3)) or a substituent XB (a group represented by any one of general formulas (XB1) to (XB7)). Preferably, X ^AB represents substituent XB.

In the general formula (X), ^XC represents a single bond or an alkylene group. In the alkylene group, one or more (preferably 1 to 5) _-CH2- groups constituting the alkylene chain may be substituted with -CO- and/or -S-. The -CO- groups are not continuously bonded to each other.

The alkylene group may be linear or branched. Furthermore, a portion or the entire alkylene group may be cyclic. Preferably, the alkylene group is linear. The alkylene group may contain a substituent, preferably a hydroxyl group. Preferably, the alkylene group does not contain any substituent other than a hydroxyl group.

The carbon number of the aforementioned alkylene group is preferably 1 to 10. The aforementioned carbon number includes the number of carbon atoms in -CH ₂ - substituted by -S-.

Among them, X ^C is preferably a group represented by "-(L ^X ) _mx -".

In "-(L ^X ) _mx -", mx represents an integer from 0 to 10. When mx is 0, "-(L ^X ) _mx -" is a single key.

In "-(L ^X ) _mx -", L ^X represents -CR ^X ₂ -, -CO-, or -S-. However, -CO- are not continuously bonded to each other.

The two _RXs in ^-CRX2- independently represent a hydrogen atom or a substituent (preferably a hydroxyl group). Preferably, one or both ^of the two ^RXs in _one ^-CRX2- are hydrogen _atoms . When there are multiple ^-CRX2- in ^LX , the _multiple ^-CRX2- may be the same or different.

Specific combinations of ^XA and ^XAB in the general formula (X) include, for example, "XA1/XB2,""XA1/XB3,""XA1/XB6,""XA1/XB7,""XA1/XA1,""XA2/XB3,""XA2/XB4,""XA2/XB5," or "XA3/XB1," and more preferably, "XA1/XB3,""XA1/XB6,""XA1/XB7,""XA2/XB4," or "XA2/XB5."

In the above description, "XA1/XB2" means a combination in which ^XA is a group represented by the general formula (XA1) and ^XAB is a group represented by the general formula (XB2). The same applies to other similar descriptions.

When ^XA is a group represented by the general formula (XA1) and ^XAB is a combination of groups represented by the general formula (XB7), ^XC is preferably a single bond or an alkylene group having 1 to 3 carbon atoms.

Compound X preferably contains 1 to 5 partial structures represented by -COOH, and more preferably contains only 1 partial structure.

The partial structure represented by -COOH refers to all -COOH groups present in the compound. For example, the -COOH groups present as part of the substituent XA are also included in the partial structure represented by -COOH.

Compound X may be used singly or in combination. When two or more compounds X are used, the two or more compounds X may be solely compound X1, solely compound X2, or both compound X1 and compound X2.

(Compound Y)

Compound Y is a compound represented by the general formula (Y).

Y ^Q -COOH (Y)

Y ^Q represents an aromatic cyclic group having a phosphonooxy group (—OPO(OH) ₂ ), an aromatic cyclic group having a boronic acid group (—B(OH) ₂ ), or a phosphono-alkylene group.

The aromatic ring groups in the aromatic ring groups having a phosphonooxy group and the aromatic ring groups having a boronic acid group can each independently be an aromatic alkyl ring group or an aromatic heterocyclic group, with aromatic alkyl ring groups being preferred. These aromatic ring groups can be monocyclic or polycyclic, with monocyclic groups being preferred. The number of rings in these aromatic ring groups is preferably 5 to 15, and more preferably 6.

The COOH group shown in general formula (Y) is directly bonded to a ring member atom of the aforementioned aromatic ring group.

Furthermore, in the aromatic cyclic group having a phosphonooxy group, the phosphonooxy group and the COOH group shown in general formula (Y) are directly bonded to a ring member atom of the aromatic cyclic group. The aromatic cyclic group having a phosphonooxy group may or may not contain substituents other than those listed above, but preferably does not contain such substituents.

In the aromatic ring group having a boronic acid group, the boronic acid group and the COOH group shown in general formula (Y) are directly bonded to a ring member atom of the aromatic ring group. The aromatic ring group having a boronic acid group may or may not contain substituents other than those listed above, but preferably, it does not contain such substituents.

The alkylene group in "phosphono-alkylene-" can be linear or branched, and preferably has 1 to 10 carbon atoms.

In a "phosphono-alkylene-" group, the phosphonic acid group and the COOH group shown in general formula (Y) are directly bonded to a carbon atom of the alkylene chain constituting the alkylene group. A "phosphono-alkylene-" group may or may not contain substituents other than those listed above, but preferably does not contain any substituents.

(Compound Z)

Compound Z is one or more compounds selected from the group consisting of mellitic acid (mellitate) and oxalic acid (HOOC-COOH).

Compound Z may be used alone or in combination.

Among them, the preservative in the present invention is preferably one or more compounds selected from the group consisting of L-cysteine, o-carboxyphenylboronic acid, creatine, N-acetylglycine (acetamidoacetic acid), homoarginine, N ⁶ -(aminocarbonyl)-L-ricin (homocitrulline), L-o-phosphorylserine, 2-phosphonobenzoic acid, mellitic acid, oxalic acid, gluconic acid, L-citrulline, DL-alanylglycine, d-cystine, and dl-galactosamine. More preferably, it is one or more compounds selected from the group consisting of L-cysteine, gluconic acid, homoarginine, L-citrulline, DL-alanylglycine, o-carboxyphenylboronic acid, mellitic acid, and oxalic acid.

The preservative content in the treatment solution (the total content when two or more preservatives are used) is preferably 0.01-7 mass %, more preferably 0.01-5 mass %, even more preferably 0.05-3 mass %, and particularly preferably 0.07-3 mass % relative to the total mass of the treatment solution.

The content of compound Y is particularly preferably 0.07% by mass or more and less than 1% by mass relative to the total mass of the treatment solution.

<Water>

The treatment liquid of the present invention may also contain water.

The water used is not particularly limited, but ultrapure water used in semiconductor manufacturing is preferred. Ultrapure water that has been further purified to reduce inorganic anions and metal ions is even more preferred. The purification method is not particularly limited, but purification using a filtration membrane or ion exchange membrane, or purification by distillation, is preferred. For example, purification using the method described in Japanese Patent Application Laid-Open No. 2007-254168 is preferred.

The water content in the treatment solution is preferably 0.01-18 mass %, more preferably 0.05-14 mass %, and even more preferably 0.1-9 mass %, relative to the total mass of the treatment solution.

<pH Adjuster>

The treatment solution of the present invention may contain a pH adjuster.

pH adjusters are ingredients other than the above ingredients.

As pH adjusters, quaternary ammonium salts such as choline, alkali hydroxides such as potassium hydroxide or alkaline earth salts, and amino compounds such as 2-aminoethanol and guanidine can be used to increase the pH. Although not limited to the above, it is generally preferred that the compound does not contain metal ions. Examples of the compound include ammonium hydroxide, choline compounds, monoamines, imines (e.g., 1,8-diazabicyclo[5.4.0]undec-7-ene (diazabicycloundecene), 1,5-diazabicyclo[4.3.0]non-5-ene), 1,4-diazabicyclo[2.2.2]octane, guanidine salts (e.g., guanidine carbonate), hydroxylamines, and hydroxylamine salts. Any of these compounds can be used to enhance the desired effect of the present application. Among them, ammonium hydroxide, imines (such as 1,8-diazabicyclo[5.4.0]undec-7-ene and 1,5-diazabicyclo[4.3.0]non-5-ene), hydroxylamines, or hydroxylamine salts are preferred from the perspective of significantly achieving the desired effects of the present application.

To lower the pH, inorganic acids and organic acids such as carboxylic acids and organic sulfuric acids can be used. Specific examples of inorganic acids include hydrochloric acid, sulfuric acid, carbonic acid, hypophosphorous acid, phosphorous acid, and phosphoric acid. Specific examples of carboxylic acids include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, 2-methylbutyric acid, n-hexanoic acid, 3,3-dimethylbutyric acid, 2-ethylbutyric acid, 4-methylvaleric acid, n-heptanoic acid, 2-methylhexanoic acid, n-octanoic acid, 2-ethylhexanoic acid, benzoic acid, glycolic acid, salicylic acid, glycerol, glutaric acid, oxalic acid, pimelic acid, maleic acid, phthalic acid, malic acid, tartaric acid, lactic acid, diglycolic acid, 2-furancarboxylic acid, 2,5-furancarboxylic acid, 3-furancarboxylic acid, 2-tetrahydrofurancarboxylic acid, methoxyacetic acid, methoxyphenylacetic acid, and phenoxyacetic acid. Specific examples of organic sulfuric acids include methanesulfonic acid, ethanesulfonic acid, and hydroxyethanesulfonic acid.

pH adjusters can be used alone or in combination of two or more.

The content of the pH adjuster is not particularly limited. For example, the pH of the treatment solution can be appropriately determined so as to fall within a predetermined range.

The pH of the treatment solution is preferably below 5.0, more preferably below 4.0, even more preferably between 0.00 and 4.0, and particularly preferably above 0.05 and below 3.5.

<Coarse particles>

It is also preferred that the treatment solution of the present invention contain substantially no coarse particles.

Coarse particles refer to particles with a diameter of 0.2 μm or larger, for example, when the particles are considered spherical. Furthermore, "substantially free of coarse particles" means that, when the treatment liquid is measured using a commercially available light-scattering liquid particle measurement device, there are 10 or fewer particles of 0.2 μm or larger per 1 mL of the treatment liquid.

Furthermore, the coarse particles contained in the treatment fluid are particles of dust, ash, organic solids, and inorganic solids contained in the raw materials as impurities, as well as particles of dust, ash, organic solids, and inorganic solids introduced as contaminants during the preparation of the treatment fluid. They also correspond to components that do not dissolve in the treatment fluid and ultimately exist as particles.

The amount of coarse particles present in the treatment solution can be measured in the liquid phase using a commercially available measuring device that uses a laser as a light source for light scattering liquid particle measurement.

As a method for removing coarse particles, for example, filtration and other treatments described below can be cited.

<Other ingredients>

The treatment solution of the present invention may contain other components in addition to the above-mentioned components.

Examples of other ingredients include preservatives other than those listed above (preservatives that do not correspond to any of compounds X, Y, and Z), surfactants, oxidants, chelating agents, defoaming agents, rust inhibitors, and preservatives.

<Combination Example>

The treatment liquid of the present invention preferably contains, for example, 0.01-10 mass% (preferably 0.05-5 mass%, and even more preferably 0.1-3 mass%) of an etchant, 80-99.9 mass% (preferably 80-99 mass%, and even more preferably 90-99 mass%) of an organic solvent, 0.01-5 mass% (preferably 0.05-3 mass%, and even more preferably 0.07-3 mass%) of a preservative, and 0.01-18 mass% (preferably 0.05-14 mass%, and even more preferably 0.1-9 mass%) of water, relative to the total mass of the treatment liquid.

Furthermore, the above-mentioned treatment solution may contain ingredients (such as pH adjusters) in addition to the listed ingredients (etchant, organic solvent, preservative, and water) as desired.

<Purpose>

The processing liquid of the present invention is typically used as a semiconductor device processing liquid for semiconductor devices. In the present invention, "semiconductor device processing liquid" refers to a liquid used in the manufacture of semiconductor devices. In addition to being used to remove metal hard masks and etching residues, the processing liquid of the present invention can also be used in any step of the semiconductor device manufacturing process.

For example, processing fluids can also be used as pre-wetting solutions, solutions (such as removal and stripping solutions) for removing permanent films (e.g., color filters, transparent insulating films, and resin lenses) from semiconductor substrates, and post-chemical mechanical polishing (PCMP) cleaning solutions. Furthermore, semiconductor substrates after permanent film removal are sometimes reused in semiconductor devices, so permanent film removal is also included in the semiconductor device manufacturing process.

The specific application method of the treatment solution of the present invention will be described later.

<Reagent Kit and Concentrate>

The processing solution of the present invention can also be used as a reagent kit to divide the raw material into multiple parts.

Alternatively, the treatment solution can be prepared as a concentrated solution. In this case, it can be diluted with water and/or an organic solvent before use.

<Container (Storage Container)>

The treatment solution of the present invention can be stored, transported, and/or used in any container, regardless of whether it is a reagent kit or a concentrated solution, as long as it presents no issues with corrosiveness. For semiconductor applications, containers with high internal cleanliness and minimal impurity release are preferred. Examples of suitable containers include, but are not limited to, the "Clean-Bottle" series manufactured by AICELLO CHEMICAL CO., LTD. and the "PureBottle" manufactured by KODAMA PASTICS Co., Ltd. The inner wall of the container is preferably formed of one or more resins selected from the group consisting of polyethylene resin, polypropylene resin, and polyethylene-polypropylene resin, or a different resin, or a metal treated to prevent rust and metal dissolution, such as stainless steel, Hoechst alloy, Inconel, and Monel.

Fluorine-based resins (perfluororesins) are preferably used as the different resins mentioned above. As mentioned above, using a container with an inner wall made of polyethylene resin, polypropylene resin, or polyethylene-polypropylene resin can suppress the occurrence of adverse effects such as the elution of ethylene or propylene oligomers.

Specific examples of such containers with fluororesin inner walls include FluoroPure PFA composite columns manufactured by Entegris, Inc. Containers described in Japanese Patent Publication No. 3-502677, page 4 et seq., International Publication No. 2004/016526, page 3 et seq., and International Publication No. 99/046309, pages 9 and 16 et seq., can also be used.

Furthermore, as materials for the inner wall of the container, in addition to the above-mentioned fluorine-based resins, examples include quartz and electrolytically polished metal materials (i.e., metal materials that have been electrolytically polished).

The metal material used to produce the electrolytically polished metal material described above preferably contains at least one selected from the group consisting of chromium and nickel, with the total content of chromium and nickel exceeding 25% by mass relative to the total mass of the metal material. Examples of such metal materials include stainless steel and nickel-chromium alloys.

The total content of chromium and nickel in the metal material is preferably 25% by mass or more, and more preferably 30% by mass or more, relative to the total mass of the metal material.

There is no particular upper limit on the total content of chromium and nickel in the metal material, but it is generally preferably 90% by mass or less.

There are no particular limitations on the stainless steel; any known stainless steel can be used. Among them, alloys containing 8% by mass or more nickel are preferred, and austenitic stainless steel containing 8% by mass or more nickel is even more preferred. Examples of austenitic stainless steel include SUS (Steel Use Stainless Steel) 304 (8% Ni, 18% Cr), SUS304L (9% Ni, 18% Cr), SUS316 (10% Ni, 16% Cr), and SUS316L (12% Ni, 16% Cr).

The nickel-chromium alloy is not particularly limited, and any known nickel-chromium alloy can be used. Preferred nickel-chromium alloys include those having a nickel content of 40-75% by mass and a chromium content of 1-30% by mass.

Examples of nickel-chromium alloys include Herschel alloy (hereinafter referred to as the same product name), Monel alloy (hereinafter referred to as the same product name), and Inconel alloy (hereinafter referred to as the same product name). More specifically, Herschel alloy C-276 (Ni content 63% by mass, Cr content 16% by mass), Herschel alloy-C (Ni content 60% by mass, Cr content 17% by mass), and Herschel alloy C-22 (Ni content 61% by mass, Cr content 22% by mass) are examples.

Furthermore, nickel-chromium alloys may contain boron, silicon, tungsten, molybdenum, copper, and cobalt, in addition to the above alloys, as needed.

The method for electrolytic polishing of metal materials is not particularly limited, and known methods can be used. For example, the methods described in paragraphs [0011] to [0014] of Japanese Patent Application Laid-Open No. 2015-227501 and paragraphs [0036] to [0042] of Japanese Patent Application Laid-Open No. 2008-264929 can be used.

It is speculated that electrolytic polishing of metal materials causes the chromium content in the passivation layer on the surface to become greater than that in the matrix. This is thought to reduce the release of metallic elements from the inner wall of the electrolytically polished metal coating into the treatment solution, resulting in a semiconductor chemical solution low in specific metallic elements such as Ca, Fe, and Na atoms.

Furthermore, polishing of metal materials is preferred. The polishing method is not particularly limited, and known methods can be used. The abrasive grain size used for fine polishing is not particularly limited, but from the perspective of more easily reducing surface irregularities on the metal material, grains of #400 or less are preferred.

Furthermore, polishing is preferably performed before electrolytic polishing.

Furthermore, metal materials can also be processed by combining one or more processes such as polishing, acid cleaning, and magnetic fluid polishing to achieve multiple stages of treatment by varying the size and coarseness of the abrasive grains.

In the present invention, the container containing the above-mentioned container and the above-mentioned treatment liquid contained therein is sometimes referred to as a treatment liquid container.

It is best to clean the interior of these containers with a liquid before filling. The liquid can be selected appropriately depending on the intended use, but the effects of the present invention are most effectively achieved when it is the treatment liquid of the present invention itself, a liquid diluted with the treatment liquid of the present invention, or a liquid containing at least one of the components added to the treatment liquid of the present invention. After production, the treatment liquid of the present invention can also be transported and stored in containers such as gallons or coating bottles.

To prevent changes in the composition of the treatment liquid during storage, the atmosphere in the container can be replaced with an inert gas (such as nitrogen or argon) with a purity of 99.99995% by volume or higher. Gases with low water content are particularly preferred. During transportation and storage, the temperature can be kept at room temperature, but to prevent deterioration, it is also advisable to maintain the temperature within the range of -20°C to 20°C.

<Cleanroom>

All operations, including the preparation of the treatment solution of the present invention, the opening and/or cleaning of the storage container, the filling of the treatment solution, and the processing, analysis, and measurement, are preferably performed in a cleanroom. Preferably, the cleanroom meets ISO (International Organization for Standardization) 14644-1 cleanroom standards. Meeting any of ISO Class 1, ISO Class 2, ISO Class 3, and ISO Class 4 is preferred, with ISO Class 1 or ISO Class 2 being more preferred, and ISO Class 1 being even more preferred.

<Filter>

In order to remove foreign matter and coarse particles, the treatment liquid of the present invention is preferably filtered.

The filter used for filtration can be used without particular limitation, as long as it has been used for filtration purposes. Examples of materials used to construct the filter include fluororesins such as PTFE (polytetrafluoroethylene), polyamide resins such as nylon, and polyolefin resins (including high-density and ultra-high molecular weight resins) such as polyethylene and polypropylene (PP). Among these, polyamide resins, PTFE, or polypropylene (including high-density polypropylene) are preferred. Using filters made from these materials allows for more effective removal of highly polar foreign matter that can easily cause residue and particle defects.

The critical surface tension of the filter is preferably 70 mN/m or higher as the lower limit, and 95 mN/m or lower as the upper limit. In particular, the critical surface tension of the filter is preferably 75-85 mN/m.

The critical surface tension value is the manufacturer's nominal value. Using a filter with a critical surface tension within the above range effectively removes highly polar foreign matter that can cause slag and particle defects.

The filter pore size is preferably between 0.001 and 1.0 μm, more preferably between 0.02 and 0.5 μm, and even more preferably between 0.01 and 0.1 μm. By setting the filter pore size within this range, clogging can be suppressed while reliably removing fine foreign matter contained in the treatment solution.

When using filters, different filters can be combined. In this case, filtering with the first filter can be performed only once or twice or more. When filtering with different filters twice or more, the filters can be of the same type or different types, with different types being preferred. Generally, the first and second filters preferably differ in at least one of pore size and constituent material.

The pore size of the second and subsequent filtration passes is preferably the same as or smaller than that of the first filtration pass. Furthermore, first filters with different pore sizes within the above range can be combined. The pore size can be determined by referring to the nominal value specified by the filter manufacturer. Commercially available filters include those offered by NIHONPALL LTD., Advantec Toyo Kaisha, Ltd., Nihon Entegris K.K. (formerly Nippon Mykroli Corporation), or KITZ MICROFILTER CORPORATION. Alternatively, the polyamide "P-nylon filter (pore size 0.02 μm, critical surface tension 77 mN/m)" (manufactured by NIHONPALL LTD.), the high-density polyethylene "PE Clean Filter (pore size 0.02 μm)" (manufactured by NIHONPALL LTD.), and the high-density polyethylene "PE Clean Filter (pore size 0.01 μm)" (manufactured by NIHONPALL LTD.) can also be used.

The second filter can be made of the same material as the first filter. It can also have the same pore size as the first filter. When using a second filter with a smaller pore size than the first filter, the ratio of the pore size of the second filter to the pore size of the first filter (pore size of the second filter / pore size of the first filter) is preferably 0.01-0.99, more preferably 0.1-0.9, and even more preferably 0.3-0.9. By setting the pore size of the second filter within this range, fine foreign matter mixed in with the treatment liquid can be more reliably removed.

For example, filtration under the first filter can be performed using a mixed solution containing some of the components of the treatment solution, and after the residual components are mixed in to prepare the treatment solution, filtration under the second filter can be performed.

Furthermore, it is preferred that the filter used be treated before filtering the treatment liquid. The liquid used in this treatment is not particularly limited, but the desired effects of this application are significantly achieved when it is the treatment liquid of the present invention itself, a liquid diluted with the treatment liquid of the present invention, or a liquid containing some of the components of the treatment liquid.

During filtration, the upper limit of the filtration temperature is preferably room temperature (25°C) or lower, more preferably 23°C or lower, and even more preferably 20°C or lower. Furthermore, the lower limit of the filtration temperature is preferably 0°C or higher, more preferably 5°C or higher, and even more preferably 10°C or higher.

While filtration can remove particulate matter and impurities, the amount of particulate matter and impurities dissolved in the treatment solution decreases when performed at the above temperature, allowing for more efficient filtration.

[Handling Method]

The treatment solution of the present invention is used to treat a treatment object containing a first metal-containing material including one or more first metals selected from the group consisting of Co and Cu.

<Objects to be processed>

The treatment liquid of the present invention is applicable to any material without limitation as long as it contains a first metal-containing material comprising one or more first metals selected from the group consisting of Co and Cu.

The object to be processed may further contain a second metal containing one or more second metals selected from the group consisting of Zr, Ti, Hf, and Ta and/or an aluminum-based material such as Al or Al ₂ O ₃ .

Furthermore, the processed material may also contain dry etching residue.

Furthermore, the first metal-containing material, which includes one or more first metals selected from the group consisting of Co (cobalt) and Cu (copper), contained in the treatment object to which the treatment solution of the present invention is applied, may be, for example, a single first metal, an alloy of first metals, an alloy of one or more first metals and a metal other than the first metal, an oxide (complex oxide), nitride (complex nitride), or oxynitride (complex oxynitride) of one or more first metals, a composite oxide, composite nitride, or composite oxynitride of one or more first metals and a metal other than the first metal, or a mixture thereof.

The first metal inclusion may be a Co inclusion where the first metal is Co, or a Cu inclusion where the first metal is Cu.

Furthermore, in a Co-containing material, the first metal is only Co, and Cu is used as a metal other than the first metal. This is the same as a first metal-containing material, except that the first metal is only Cu, and Co is used as a metal other than the first metal.

The first metal content relative to the total mass of the metal components contained in the first metal inclusion is preferably 50-100 mass%, more preferably 75-100 mass%, and even more preferably 99-100 mass%.

It is preferred that the first metal content contains at least Co, and it is also preferred that the first metal content is Co.

Examples of the first metal inclusion include Co and Cu, with Co being preferred.

When the treatment liquid contacts the object to be treated (such as the laminate described below), the removal rate of the first metal inclusion (preferably Co inclusion) is preferably 10 Å/min or less, more preferably 5 Å/min or less, and even more preferably 1 Å/min or less. The lower limit is not particularly limited, but may be, for example, 0.001 Å/min or greater.

The second metal-containing material that can be contained in the treatment liquid to which the present invention is applied, and that includes one or more second metals selected from the group consisting of Zr (zirconium), Ti (titanium), Hf (arsenic), and Ta (tantalum), can be, for example, a single second metal, an alloy of two second metals, an alloy of one or more second metals and a metal other than the second metal, an oxide (complex oxide), nitride (complex nitride), or oxynitride (complex oxynitride) of one or more second metals, a composite oxide, composite nitride, or composite oxynitride of one or more second metals and a metal other than the second metal, or a mixture thereof.

The second metal inclusion may be a Zr inclusion where the second metal is Zr, a Ti inclusion where the second metal is Ti, an Hf inclusion where the second metal is Hf, or a Ta inclusion where the second metal is Ta.

The second metal content relative to the total mass of the metal components contained in the second metal inclusion is preferably 50-100 mass%, more preferably 75-100 mass%, and even more preferably 99-100 mass%.

Examples of the second metal inclusion include ZrOx ( _ZrO2 , etc.), Ti, TiN, HfOx, and TaOx. x is a number represented by x = 1 to 3.

Furthermore, the second metal inclusion may be dry etching residue. When the second metal inclusion having such dry etching residue is used as a metal hard mask, for example, the residue of the metal hard mask generated by dry etching can be raised.

The aluminum-based material that can be contained in the treatment solution of the present invention is Al (single element) or _Al2O3 (aluminum oxide), and can be _both Al _{and Al2O3. When both Al and Al2O3 are present ,} Al _{and Al2O3} can exist in contact with each other or separately.

When the treatment liquid contacts an aluminum-containing object (such as a laminate described below), the aluminum removal rate is preferably 10 Å/min or less, more preferably 5 Å/min or less, and even more preferably 3 Å/min or less. The lower limit is not critical, but may be 0.001 Å/min or more, for example.

When the removal rate of the second metal inclusion in the treatment solution of the present invention is ER1, and the removal rate of the first metal inclusion or aluminum-based material in the treatment solution of the present invention is ER2, the removal rate ratio ER1/ER2 is preferably 0.5-1000, more preferably 0.8-800, and even more preferably 1-500.

When the removal rate ratio ER1/ER2 is within the above range, the effect of the present invention is more excellent.

Among them, it is preferred that the processed material be a semiconductor device using a multilayer body.

The above-mentioned multilayer body, for example, includes a substrate, a third layer formed on the substrate, a second layer formed on the third layer, and a first layer formed on the second layer.

The third layer is preferably made of a material containing the first metal component. Furthermore, the third layer is preferably made of an aluminum-based material (preferably Al).

The third layer is preferably a metal layer (wiring).

The second layer is preferably formed of a Si-containing material (e.g., SiOx, SiOC, SiN, and/or SiON). Furthermore, the first and second layers are preferably formed of different materials.

The second layer is preferably an interlayer insulating film.

It is preferred that the first layer contains a second metal inclusion.

A metal hard mask is preferred as the first layer.

Furthermore, the second layer and/or the first layer may be omitted.

Furthermore, the laminate may contain layers other than the aforementioned layers, such as an etch stop layer and an anti-reflection layer. The etch stop layer preferably contains an aluminum-based material (preferably Al ₂ O ₃ ) and/or a first metal component (preferably a Co component, more preferably a single body of Co). The metal layer may also function as the etch stop layer.

The above-mentioned laminate may further contain dry etching residues. The dry etching residues exist, for example, adhering to the surface portions of the first layer, the second layer, and/or the third layer of the laminate.

Let’s explain the above-mentioned layered structure in more detail.

Specifically, the aforementioned multilayer structure can be exemplified by a multilayer structure for semiconductor devices that sequentially comprises a substrate, a metal layer (equivalent to the aforementioned third layer), an interlayer insulating film (equivalent to the second layer), and a metal hard mask (equivalent to the first layer).

The laminate may also preferably include holes formed from the surface (opening) of the metal hard mask toward the substrate, exposing the surface of the metal layer, by undergoing a dry etching step or the like.

The method for manufacturing the aforementioned multilayer structure containing holes is not particularly limited, but a typical method is to perform a dry etching step on the pre-processed multilayer structure comprising, in order, a substrate, a metal layer, an interlayer insulating film, and the metal hard mask, using a metal hard mask as a mask. The interlayer insulating film is then etched to expose the surface of the metal layer, thereby creating holes penetrating the metal hard mask and the interlayer insulating film.

Furthermore, there are no particular limitations on the method for manufacturing a metal hard mask. For example, a method may be used in which a metal hard mask front layer containing a predetermined composition is first formed on an interlayer insulating film, and a resist film having a predetermined pattern is then formed on the metal hard mask front layer. Subsequently, the resist film is used as a mask to etch the metal hard mask front layer, thereby manufacturing a metal hard mask (i.e., a film having a patterned metal hard mask front layer).

Furthermore, the laminate may contain layers other than the above-mentioned layers, for example, an etch stop layer and an anti-reflection layer.

Figure 1 is a schematic cross-sectional view showing an example of a multilayer structure for a semiconductor device as a processed object.

The laminate 10 shown in FIG1 comprises a metal layer 2, an etch stop layer 3, an interlayer insulating film 4, and a metal hard mask 5, in this order, on a substrate 1. A hole 6 is formed at a predetermined location, exposing a portion of the metal layer 2, through a dry etching step or the like. Specifically, the laminate 10 shown in FIG1 comprises a substrate 1, a metal layer 2, an etch stop layer 3, an interlayer insulating film 4, and a metal hard mask 5, in this order. At the opening of the metal hard mask 5, a hole 6 is formed, penetrating from the surface thereof to the surface of the metal layer 2. The inner wall 11 of the hole 6 is composed of a cross-sectional wall 11a formed by the etch stop layer 3, the interlayer insulating film 4, and the metal hard mask 5, and a bottom wall 11b formed by the exposed metal layer 2, and is attached with dry etching residue 12.

The processing method of the present invention is preferably used for cleaning to remove dry etching residues 12 and/or removing the metal hard mask 5. Specifically, while achieving excellent removal of dry etching residues 12 and/or the metal hard mask 5, it can also suppress etching of the inner wall 11 of the laminate (e.g., the metal layer 2).

(Metal Hard Mask)

The metal hard mask contains a second metal inclusion. The metal hard mask can be the second metal inclusion itself.

(Interlayer insulation film)

Regarding the interlayer insulating film (sometimes referred to as "insulating film" in this specification), materials with a dielectric constant k of 3.0 or less are preferred, and materials with a dielectric constant k of 2.6 or less are even more preferred.

Specific examples of interlayer insulating film materials include Si-containing materials (such as SiOx, SiOC, SiN, and/or SiON). Here, x is a number from 1 to 3.

(Etch stop layer)

The material of the etch stop layer is not particularly limited. Specific examples of etch stop layer materials include aluminum-based materials, first metal-containing materials (preferably Co-containing materials, more preferably Co monomers), TEOS (tetraethoxysilane), SiN, SiOC, poly-Si (polycrystalline silicon), and a-Si (amorphous silicon).

The aluminum-based material constituting the etch stop layer is preferably Al ₂ O ₃ .

(Metal layer)

The wiring material forming the metal layer contains a first metal component. The metal layer may be the first metal component itself.

Furthermore, it is also preferred that the metal layer contain an aluminum-based material. The aluminum-based material constituting the metal layer is preferably Al.

(Substrate)

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

The material constituting the semiconductor substrate composed of a single layer is not particularly limited, but is preferably composed of silicon, silicon germanium, a Group III-V compound such as GaAs, or any combination thereof.

In the case of a multi-layered semiconductor substrate, its structure is not particularly limited. For example, a semiconductor substrate made of silicon or other materials may include exposed integrated circuit structures such as metal wires and dielectric interconnect features. Examples of metals and alloys used for interconnect structures include, but are not limited to, aluminum, aluminum alloyed with copper, copper, titanium, tantalum, cobalt, silicon, titanium nitride, tantalum nitride, and tungsten. Furthermore, a semiconductor substrate may include layers such as interlayer dielectric layers, silicon oxide, silicon nitride, silicon carbide, and carbon-doped silicon oxide.

<Steps>

The specific sequence of the treatment method of the present invention is explained.

The first aspect of the processing method of the present invention includes a step (step Ba) of bringing a processing liquid into contact with a workpiece containing a first metal component (such as the aforementioned third layer (metal layer)) and a second metal component (such as the aforementioned first layer (metal hard mask)) other than dry etching residue, thereby removing the second metal component other than the dry etching residue.

The second aspect of the treatment method of the present invention includes a step (step Bb) of bringing a treatment liquid into contact with a treatment object containing a first metal component (such as the third layer (metal layer)) and dry etching residue to remove the dry etching residue.

The dry etching residue may include dry etching residue from a metal hard mask. When the metal hard mask is composed of a second metal inclusion, the dry etching residue from the metal hard mask can be considered a form of the second metal inclusion. As described above, in the second aspect of the processing method of the present invention, some or all of the dry etching residue may or may not be the second metal inclusion.

In the treatment method of the present invention, both the first and second treatment methods can be applied to a single object, or the step Ba and the step Bb can be applied simultaneously. For example, when the object to be processed is a laminate having the above-described morphology, including a first metal component, a second metal component other than dry etching residue, and dry etching residue (dry etching residue as the second metal component and/or other dry etching residue), a step (step Bc) can be performed in which the second metal component other than the dry etching residue and the dry etching residue (dry etching residue as the second metal component and/or other dry etching residue) are simultaneously removed by bringing the processing liquid into contact with the object to be processed.

The above steps Ba, Bb, and Bc are also collectively referred to as processing steps B.

The treatment method of the present invention may include step A of preparing the above-mentioned treatment solution before step B.

In the following description of the treatment method of the present invention, the case where the treatment solution preparation step A is performed before the treatment step B is shown as an example. However, the present invention is not limited to this. The treatment method of the present invention can also be performed using the above-mentioned treatment solution prepared in advance.

In treatment step B, at least one of the removal of the second metal inclusions other than the dry etching slag and the removal of the dry etching slag (the dry etching slag as the second metal inclusions and/or the dry etching slag other than these) is performed.

Because the treatment method of the present invention utilizes the aforementioned treatment solution, it excels in removing the target object and can suppress etching of the first metal-containing material (preferably the metal layer). Furthermore, when the treated object (preferably in the metal layer and/or etch-stop layer) contains an aluminum-based material, etching of the aluminum-based material can be suppressed.

First, the treatment solution preparation step A and treatment step B are described in detail.

(Treatment Solution Preparation Step A)

Treatment solution preparation step A is the step for preparing the treatment solution described above. The components used in this step are as described above.

The order of these steps is not particularly limited. For example, a method can be used in which an etchant, preservative, and other optional ingredients are added to a solvent such as water and/or an organic solvent and stirred to prepare a treatment solution.

Furthermore, it is preferred that the raw materials used in preparing the treatment solution be classified as semiconductor grade or of an equivalent high-purity grade. Furthermore, raw materials with high impurities should preferably be filtered to remove foreign matter and/or their ionic content reduced using ion exchange resins, etc. before use.

(Processing Step B)

In treatment step B, the treatment liquid is brought into contact with the object to be treated. This allows for at least one of cleaning for the purpose of removing dry etching residues and removal of the metal hard mask (wet etching).

The method for bringing the treatment liquid into contact with the treatment object is not particularly limited, but examples thereof include immersing the treatment object in the treatment liquid placed in a tank, spraying the treatment liquid onto the treatment object, flowing the treatment liquid over the treatment object, or any combination thereof.

The temperature of the treatment liquid when it comes into contact with the treated object is preferably below 90°C, and more preferably between 25°C and 60°C.

The treatment time can be adjusted according to the contact method and temperature of the treatment solution.

When using a batch immersion method (a batch method in which multiple pieces of material are immersed in a treatment tank for treatment), the treatment time is, for example, within 60 minutes, with 1-60 minutes being preferred, 3-20 minutes being more preferred, and 4-15 minutes being even more preferred.

When processing using a single chip method, the processing 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.

In addition, mechanical stirring can also be used to further improve the handling capacity of the treatment fluid.

Examples of mechanical agitation methods include circulating the treatment liquid over the treated material, flowing or spraying the treatment liquid over the treated material, and using ultrasonic or mega-frequency agitation to agitate the treatment liquid.

(Rinse Step B2)

The treatment method of the present invention may further include a step of cleaning the treated material with a solvent (rinsing step B2) after treatment step B.

Rinsing step B2 is performed continuously with treatment step B. Preferably, the rinsing step is performed for 5 seconds to 5 minutes using a rinsing solvent (rinsing liquid). Rinsing step B2 can also be performed using the mechanical agitation method described above.

Examples of rinsing solvents include, but are not limited to, deionized water, methanol, ethanol, isopropyl alcohol, N-methylpyrrolidone, γ-butyrolactone, dimethyl sulfoxide, ethyl lactate, and propylene glycol monomethyl ether acetate. Aqueous rinsing solutions with a pH greater than 8 (such as diluted aqueous ammonium hydroxide) can also be used.

The rinsing solvent is preferably an aqueous ammonium hydroxide solution, deionized water, methanol, ethanol, or isopropyl alcohol, more preferably an aqueous ammonium hydroxide solution, deionized water, or isopropyl alcohol, and even more preferably an aqueous ammonium hydroxide solution or deionized water.

As a method for bringing the rinsing solvent into contact with the workpiece, the same method as bringing the above-mentioned treatment liquid into contact with the workpiece can also be applied.

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

The above-mentioned treatment solution can be used as the rinsing solvent in rinsing step B2.

(Drying Step B3)

The treatment method of the present invention may include a drying step B3 for drying the treated material after the rinsing step B2.

The drying method is not particularly limited. Examples of drying methods include rotary drying, methods in which a dry gas is passed over the substrate, methods in which the substrate is heated using a heating mechanism such as a hot plate or infrared lamp, Marangoni drying, Notagni drying, IPA (isopropyl alcohol) drying, and any combination thereof.

Drying time depends on the specific method used, but 30 seconds to a few minutes is generally ideal.

(Coarse Particle Removal Step H)

The treatment method of the present invention may include a coarse particle removal step H for removing coarse particles from the treatment solution before performing the above-mentioned treatment step B.

By reducing or removing coarse particles from the treatment solution, the amount of coarse particles remaining on the substrate after treatment step B can be reduced. Consequently, pattern damage caused by coarse particles on the substrate can be suppressed, and the resulting reduction in device yield and reliability can be minimized.

As a specific method for removing coarse particles, for example, a method of filtering and purifying the treatment liquid after the treatment liquid preparation step A using a particle removal membrane of a predetermined particle removal size can be cited.

Furthermore, the definition of coarse particles is as described above.

(De-electrification steps I and J)

The treatment method of the present invention may include: a charge removal step I, wherein water is used to prepare the treatment solution in the treatment solution preparation step A, and the water is subjected to charge removal prior to the treatment solution preparation step A; and/or a charge removal step J, wherein the treatment solution is subjected to charge removal after the treatment solution preparation step A and before the treatment step B.

The material of the liquid contact part used to supply the treatment liquid to the treated object can be a resin that does not dissolve metals in the treatment liquid.

In the treatment method of the present invention, it is also preferred to perform at least one of the aforementioned de-electrification steps I and J to reduce the charge potential of the treatment solution. Furthermore, de-electrification can further suppress the adhesion of foreign matter (coarse particles, etc.) to the substrate and damage (corrosion) to the treated object.

As a specific method for removing static electricity, one method that can be cited is to bring water and/or treatment liquid into contact with a conductive material.

The contact time between water and/or treatment liquid and the conductive material is preferably 0.001 to 1 second, more preferably 0.01 to 0.1 second.

Specific examples of resins include high-density polyethylene (HDPE), high-density polypropylene (PP), 6,6-nylon, tetrafluoroethylene (PTFE), copolymers of tetrafluoroethylene and perfluoroalkyl vinyl ether (PFA), polychlorotrifluoroethylene (PCTFE), ethylene-chlorotrifluoroethylene copolymer (ECTFE), ethylene-tetrafluoroethylene copolymer (ETFE), and tetrafluoroethylene-hexafluoropropylene copolymer (FEP).

Examples of conductive materials include stainless steel, gold, platinum, diamond, and glassy carbon.

The treatment method of the present invention can reuse the drainage of the treatment liquid used in treatment step B for cleaning other treated objects.

When the treatment method of the present invention reuses the effluent from the treatment liquid, it preferably comprises the following steps. This treatment method comprises: the treatment step B; a effluent recovery step C of recovering the effluent from the treatment liquid used in the treatment step B; a treatment step D of using the recovered effluent from the treatment liquid to treat a newly prepared material to be treated; and a effluent recovery step E of recovering the effluent from the treatment liquid used in the treatment step D, the method comprising repeating the treatment steps D and E.

In the embodiment where the wastewater is reused, treatment step B has the same meaning as treatment step B described in the above embodiment, and the preferred embodiment is also the same. Furthermore, in the embodiment where the wastewater is reused, a coarse particle removal step H and charge removal steps I and J may also be included. Furthermore, prior to treatment step B, the treatment solution preparation step A described in the above embodiment may be included.

Processing step D has the same meaning as processing step B in the above-mentioned embodiment, and the preferred embodiment is also the same.

The wastewater recovery mechanism in wastewater recovery steps C and E is not particularly limited. The recovered wastewater can be stored in the resin container described above in the destaticization step J, and the same destaticization steps as in the destaticization step J can be performed at this time. Furthermore, a step of filtering the recovered wastewater to remove impurities, etc., can be provided.

[Example]

The present invention is described in detail below using examples. However, the present invention is not limited thereto. Furthermore, unless otherwise specified, "%" refers to mass standards.

<<Experiment X>>

[Preparation of treatment solution]

<Composition of treatment fluid>

The following raw materials were used to prepare the treatment solutions for the Examples and Comparative Examples.

(Etchant (fluorine-containing compound))

HF: Hydrogen fluoride (manufactured by KANTOCHEMICAL CO., INC.)

(Organic solvent)

DEGBE: Diethylene glycol monobutyl ether

(water)

Water: Ultrapure water

(Preservative)

‧Preservatives corresponding to any one of Compound X, Compound Y, and Compound Z

L-Cysteine

o-Carboxyphenylboronic acid

Creatine

N-acetylglycine (acetamidoacetic acid)

Homoarginine

N ⁶ -(aminocarbonyl)-L-ricin (homocitrulline)

L-phospho-serine

2-Phosphonoyloxybenzoic acid

Mellitic acid

Oxalic acid

Gluconic acid

L-Citrulline

DL-Alanylglycine

d-Cystine

dl-Amine

‧Comparison of preservatives

Benzotriazole

Triazole

Acetic acid

Lauric acid

2-Hydroxyoctanoic acid

Glycolic acid

(pH adjuster)

MSA: Methanesulfonic acid

DBU: Diazabicycloundecene

Furthermore, add an appropriate amount (less than 1% by mass relative to the total mass of the treatment solution) of either MSA or DBU as a pH adjuster to adjust the pH of the treatment solution to the values listed in the table.

Furthermore, DBU was used only in the treatment solution of Comparative Example 2; MSA was used in all other treatment solutions.

<Preparation of treatment solution>

The above raw materials were mixed and stirred as shown in Table 1 below to obtain the treatment solutions of Examples and Comparative Examples.

Furthermore, hydrogen fluoride was introduced into the treatment liquid in the form of an aqueous hydrogen fluoride solution. However, the HF content shown in Table 1 does not represent the amount of the aqueous hydrogen fluoride solution, but rather the amount (mass %) of the hydrogen fluoride compound contained in the treatment liquid.

[Trial]

The following tests were carried out using the obtained treated liquid.

<Etching performance (corrosion resistance)>

Model films (Co or Al ₂ O ₃ films) containing each material listed in Table 1 were prepared, and their etching properties were evaluated based on their etching rates. The film thickness of each model film was 1000 Å.

Each model film was etched using the treatment solutions of the Examples and Comparative Examples. Specifically, each model film was immersed in the treatment solution at 25°C for 10 minutes, and the etching rate (Å/min) was calculated based on the difference in film thickness before and after immersion.

Furthermore, for the model film C, the film thickness of the model film before and after treatment was calculated by resistivity measurement. The resistivity measurement was performed using Loresta GP (manufactured by Mitsubishi Chemical Corporation), which uses the four-probe method as its measurement principle.

When the model film was Al ₂ O ₃ , the film thickness of the model film before and after treatment was measured using elliptical polarization (spectroscopic elliptical polarimeter, product name "Vase", manufactured by JA Woollam Japan Co., Inc.) with a measurement range of 250-1000 nm and measurement angles of 70 and 75 degrees.

The corrosion resistance relative to Co and _Al2O3 (Co corrosion resistance and _Al2O3 corrosion resistance) was evaluated based on the calculated etching rates according to the following divisions. _It can be judged that the lower the etching rate relative _to Co or _Al2O3 , the better _the corrosion resistance of _the treatment solution relative to Co or _Al2O3 .

(When the model film is Co)

A: Etching speed is less than 1Å/min

B: Etching speed is greater than 1Å/min and less than 5Å/min

C: Etching speed is greater than 5Å/min and less than 10Å/min

D: Etching speed exceeds 10Å/min

(When the model film is Al ₂ O ₃ )

A: Etching speed is less than 3Å/minute

B: Etching speed is greater than 3Å/min and less than 5Å/min

C: Etching speed is greater than 5Å/min and less than 10Å/min

D: Etching speed exceeds 10Å/min

<PER (Post Etching Residue) Removal Performance>

On a Si substrate, a laminate (corresponding to the pre-processed laminate) was formed in this order, comprising a _third layer (Co), other layers (etch stop layer: _Al2O3 ), a second layer (insulating film: _SiO2 ), and a first layer (metal hard mask: _ZrO2 ) containing a predetermined opening. Using the resulting laminate and the first layer as a mask, plasma etching was performed using an etching gas containing nitrogen and halogen gases. The second layer was then etched until the surface of the third layer was exposed, forming a hole to produce Sample 1 (see Figure 1). When a cross-section of the laminate was examined using a SEM/EDX (scanning electron microscope with energy dispersive X-ray analyzer), dry etching residue containing Zr was observed on the surface of the laminate.

Furthermore, cleaning performance (removal performance) was evaluated using the following procedure. First, each treatment solution was heated to 50°C, and the laminate was immersed in the treatment solution for 10 minutes. After confirming the residual residue after immersion in the laminate using SEM/EDX, cleaning performance was evaluated using the following criteria.

A: Completely clean (100%) (SEM confirmed residues before immersion were 100% removed after immersion)

B: Cleaned more than 80% and less than 100% (residue confirmed by SEM before immersion).

More than 80% and less than 100% removed after immersion)

C: Cleaned by more than 50% and less than 80% (the residue confirmed by SEM before immersion was removed by more than 50% and less than 80% after immersion)

D: Cleaning less than 50% (residues confirmed by SEM before immersion were removed by less than 50% after immersion)

[result]

Table 1 shows the formulation of the treatment solution and the test results.

In Table 1, the "Amount" column indicates the content (mass %) of each component.

The "XA" column under the "Compound X" column indicates the type of substituent XA contained in the preservative used, when the preservative corresponds to Compound X. If "×2" is indicated in the formula, it means that the preservative contains two instances of the substituent XA shown in the formula.

The "XB" column under the "Compound X" column indicates the type of substituent XB contained in the preservative used when it corresponds to Compound X.

The "COOH Number" column under the "Compound X" column indicates the number of COOH structures contained in the preservative used when it corresponds to Compound X.

The "YQ" column under the "Compound Y" column indicates the type of group represented by ^YQ contained in the preservative used, when the preservative corresponds to Compound Y. "Phosphine-O-Ar-" refers to an aromatic ring group having a phosphonooxy group, and "boron-Ar-" refers to an aromatic ring group having a boronic acid group.

The "Amount of Organic Solvent (DEGBE) + pH Adjuster (MSA or DBU)" column indicates the total content (mass %) of the organic solvent and pH adjuster in the treatment solution relative to the total mass of the treatment solution. The pH adjuster content is adjusted to the value indicated in the "pH" column of the treatment solution. Specifically, the content in any treatment solution should be less than 1 mass % relative to the total mass of the treatment solution.

The results shown in the table indicate that the treatment solution of the present invention exhibits excellent corrosion resistance against the first metal component (Co-containing component). Furthermore, the treatment solution of the present invention exhibits excellent removal performance against the target material. Furthermore, the treatment solution of the present invention exhibits excellent corrosion resistance against aluminum-based materials.

When the water content in the treatment liquid is 14% by mass or less (more preferably 9% by mass or less), it is confirmed that the effect of the present invention is more excellent (see the comparison of Examples 2, 4, 5, and 6, etc.).

When the preservative is compound X, the present invention demonstrates superior effects when the preservative content is 0.07% by mass or greater relative to the total mass of the treatment solution (see the comparison of Examples 1, 7, and 8, etc.).

When the preservative is compound Y, the present invention demonstrates superior effects when the preservative content is greater than 0.07 mass% and less than 1 mass% relative to the total mass of the treatment liquid (see the comparison of Examples 12, 14, and 15, etc.).

When the preservative is compound X, if compound X contains only one partial structure represented by -COOH, it was confirmed that the anticorrosive property is superior to that of a compound containing Co (see the results of Examples 35-36, etc.).

When the pH is less than 3.0, it is confirmed that the effect of the present invention is more excellent (see the comparison of Examples 1, 9, and 10, etc.).

(Additional test)

Additional experiments were conducted.

In the following descriptions of additional tests, unless otherwise specified, the content of each component is expressed relative to the total mass of the treatment solution. Furthermore, when the content of a component is changed in the following additional tests, the total content of the organic solvent and pH adjuster is changed, and the total content of all components in the treatment solution is adjusted to 100 mass%, unless otherwise specified.

In Example 6, a treatment solution was prepared and evaluated in the same manner except that the water content was changed from 15.0 mass % to 18.0 mass %. The same results as in Example 6 were obtained.

In Comparative Example 10, a treatment solution was prepared and evaluated in the same manner, except that the water content was changed from 25.0 mass % to 19.2 mass %. The same results as in Comparative Example 10 were obtained.

In Example 10, a treatment solution was prepared and evaluated in the same manner except that the pH was changed from 3.5 to 3.8, resulting in the same results as in Example 10.

In Example 10, a treatment solution was prepared and evaluated in the same manner except that the pH was changed from 3.5 to 4.2. The same results as in Example 10 were obtained except that the removal performance was rated C.

In Example 8, a treatment solution was prepared and evaluated in the same manner except that HF was replaced with ammonium fluoride. The same results as in Example 8 were obtained, except that the removal performance was rated C.

In Example 8, a treatment solution was prepared and evaluated in the same manner, except that the L-cysteine content (1.0 mass %) was changed to a total content of L-cysteine and o-carboxyphenylboronic acid (L-cysteine/o-carboxyphenylboronic acid = 8/2 (mass ratio)). The same results as in Example 8 were obtained.

In Example 8, except for changing the L-cysteine content from 1.0 mass % to 2.7 mass %, a treatment solution was prepared and evaluated in the same manner, resulting in the same results as in Example 8.

In Example 8, a treatment solution was prepared and evaluated in the same manner except that the L-cysteine content was changed from 1.0 mass % to 3.5 mass %. The same results as in Example 8 were obtained, except that the removal performance was rated B.

In Example 8, a treatment solution was prepared and evaluated in the same manner except that the L-cysteine content was changed from 1.0 mass % to 4.2 mass %. The same results as in Example 8 were obtained, except that the removal performance was rated B.

In Example 8, a treatment solution was prepared and evaluated in the same manner except that the L-cysteine content was changed from 1.0 mass % to 5.2 mass %. The same results as in Example 8 were obtained, except that the removal performance was rated C.

<<Test Y>>

The aforementioned "Etching Performance (Corrosion Resistance)" test was conducted using a Cu film as a model film. The treatment solutions of Examples 1 to 36 were used. The results showed that all treatment solutions demonstrated excellent corrosion resistance, similar to the results obtained using Co as the model film.

<<Test Z>>

The tests described in the above "PER (Post Etching Residue) Removal Performance" were conducted in the same manner except that the first layer (metal hard mask) was changed from _ZrO2 to TiN or TaO.

(In this case, dry etching residue containing Ti or Ta, not Zr, was observed on the surface of the laminate before immersion in the treatment solution.)

The test results using the treatment solutions of Examples 1 to 36 showed that even when the metal hard mask was TiN or TaO, each treatment solution showed good cleaning properties (removal performance), and confirmed results close to the same as when _ZrO2 was used as the metal hard mask.

1:Substrate

2: Metal layer

3: Etch stop layer

4: Interlayer insulation film

5: Metal Hard Mask

6: Hole

10: Layered body

11: Inner wall

11a: Section wall

11b: Bottom wall

12: Dry etching residue

Claims (16)

A treatment solution is used when treating a treatment object containing a first metal-containing substance including at least one first metal selected from the group consisting of Co and Cu. The treatment solution contains: an etchant; an organic solvent; and an anti-corrosion agent. Relative to the total mass of the treatment solution, the etchant content is 0.01% by mass to 10% by mass, the organic solvent content is 80% by mass or more, the anti-corrosion content is 0.01% by mass to 7% by mass, and the water content is 0.01% by mass to 18% by mass. The anti-corrosion agent is a compound represented by the following general formula (X): ^XA - ^XC - ^XAB (X) In general formula (X), ^XA represents a substituent XA; ^XAB represents a substituent XA or a substituent XB; X ^C represents a single bond or an alkylene group, the substituent XA is a group represented by the general formula (XA1) or (XA2), and the substituent XB is a group represented by any one of the general formulas (XB3), (XB5) and (XB6), In general formulas (XA1), (XA2), (XB3), (XB5), and (XB6), * represents a bonding position, and R independently represents a hydrogen atom or an alkyl group. When the substituent XA is of general formula (XA1), the substituent XB is of general formula (XB3) or (XB6); when the substituent XA is of general formula (XA2), the substituent XB is of general formula (XB5). The processing liquid as described in claim 1, wherein the aforementioned etchant is a fluorine-containing compound. The processing liquid as described in claim 1 or claim 2, wherein the etchant is one or more compounds selected from the group consisting of hydrogen fluoride, ammonium fluoride, tetramethylammonium fluoride, tetraethylammonium fluoride, tetrabutylammonium fluoride, hexafluorosilicic acid, hexafluorophosphoric acid, and tetrafluoroboric acid. The treatment solution as described in claim 1 or claim 2, wherein the organic solvent contains an alcohol-based solvent. The treatment solution of claim 1 or claim 2, wherein: the organic solvent is one or more compounds selected from the group consisting of ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, hexanol, 1-octanol, 2-octanol, and 2-ethylhexanol. The treatment solution as described in claim 1 or claim 2, wherein the compound X is a compound containing only one partial structure represented by -COOH. The treatment liquid as described in claim 1 or claim 2, wherein the preservative is one or more compounds selected from the group consisting of L-cysteine, homoarginine, L-citrulline, DL-alanine glycine, and o-carboxyphenylboronic acid. The treatment liquid as described in claim 1 or claim 2, wherein, relative to the total mass of the treatment liquid, it contains 0.1% to 3% by mass of the etchant, 80% to 99% by mass of the organic solvent, 0.05% to 3.0% by mass of the preservative, and 0.05% to 14% by mass of water. The treatment solution as described in claim 1 or claim 2, wherein the pH is 4.0 or less. A treatment method comprising the step of contacting the treatment solution according to any one of claims 1 to 9 with the treated object to remove the second metal inclusion, wherein the treated object further contains at least one second metal selected from the group consisting of Zr, Ti, Hf, and Ta. A processing method, wherein: The processing method includes the step of contacting the processing liquid described in any one of claims 1 to 9 with the object to be processed to remove dry etching residue, wherein the object to be processed further contains the dry etching residue. The treatment method as described in claim 10 or claim 11, wherein the first metal inclusion includes Co. The treatment method according to claim 10 or claim 11, wherein the removal rate of the first metal inclusion when the treatment liquid contacts the object to be treated is 10 Å/min or less. The treatment method as described in claim 10 or claim 11, wherein the treated material further contains an aluminum-based material, wherein the aluminum-based material is Al or Al ₂ O ₃ . The treatment method as described in claim 14, wherein the removal rate of the aluminum-based material when the treatment liquid contacts the treated object is less than 10 Å/min. The treatment method as described in claim 10 or claim 11, wherein the treatment solution is used at a temperature between 25°C and 60°C.