TW202124691A - Semiconductor processing composition and processing method composition is excellent in storage stability, and can suppress corrosion of metal wiring of the processed object and prevent corrosion from the processed object - Google Patents

Abstract

The subject of the present invention is to provide a semiconductor processing composition and a processing method using the same. The semiconductor processing composition is excellent in storage stability, and can suppress corrosion of metal wiring of the processed object and prevent corrosion from the processed object. The surface effectively removes pollution. The semiconductor processing composition of the present invention contains (A) at least one selected from the group consisting of cyclodextrin and cyclodextrin derivatives, (B) a compound having a zwitterionic structure, and (C) a liquid medium, When the content of the (A) component is MA [mass%] and the content of the (B) component is MB [mass%], MA/MB=3-15.

Description

Semiconductor processing composition and processing method

The present invention relates to a composition for semiconductor processing and a processing method using the same.

The CMP slurry for chemical mechanical polishing used in chemical mechanical polishing (CMP), which is effective for manufacturing semiconductor devices, contains not only abrasive particles (abrasive grains), but also an etchant. When abrasive particles aggregate to produce coarse particles, it becomes a cause of abrasive damage. Therefore, a method has been proposed to effectively use a containment compound such as cyclodextrin to improve the stability of the CMP slurry (for example, refer to Patent Document 1).

In addition, in the manufacture of a semiconductor device, after the CMP step, etc., a cleaning step is required to remove contaminations such as polishing debris or organic residues from the surface of the semiconductor substrate. Metal wiring materials such as tungsten and cobalt are exposed on the surface of the semiconductor substrate. Therefore, in the cleaning step, it is necessary to suppress the corrosion of the polished surface where the metal wiring material is exposed. As a technique for suppressing corrosion of the surface of a semiconductor substrate, a method of effectively using a containment compound such as cyclodextrin has been proposed (for example, refer to Patent Document 2). [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2009-302255 [Patent Document 2] Japanese Patent Publication No. 2019-507207

[The problem to be solved by the invention] However, with the further miniaturization of circuit structures in recent years, a processing technique that can further suppress corrosion of metal wiring of the object to be processed and the like and effectively remove contamination from the surface of the object to be processed is required. In addition, in order to further improve the production stability of semiconductor devices, it is also necessary to improve the storage stability of the processing agent.

Therefore, some aspects of the present invention provide a semiconductor processing composition and a processing method using the same by solving at least a part of the problem. The semiconductor processing composition has excellent storage stability and can suppress damage to the processed Corrosion caused by the metal wiring of the body and the like effectively removes contamination from the surface of the body to be processed.

[Means to solve the problem] The present invention is made to solve at least a part of the above-mentioned problems, and can be implemented as any of the following aspects.

One aspect of the semiconductor processing composition of the present invention contains: (A) at least one selected from the group consisting of cyclodextrin and cyclodextrin derivatives, (B) a compound having a zwitterionic structure, and (C ) Liquid medium, when the content of the (A) component is M _A [mass %] and the content of the (B) component is M _B [mass %], M _A /M _B =3 ~15.

The semiconductor processing composition of the above aspect can be used after being diluted from 1 to 100 times.

In any aspect of the semiconductor processing composition, The (B) component may be a compound having at least one functional group selected from the group consisting of a carboxyl group and a sulfonic acid group and an alkyl group having 12 or more and 18 or less carbon atoms.

In any aspect of the semiconductor processing composition, The cyclodextrin derivative may be at least one selected from 2-hydroxypropyl-β-cyclodextrin and 2-hydroxyethyl-β-cyclodextrin.

In any aspect of the semiconductor processing composition, It can also contain organic acids.

In any aspect of the semiconductor processing composition, It can also contain water-soluble polymers.

One aspect of the processing method of the present invention includes the following steps: The semiconductor processing composition of any one of the above aspects is used to process a wiring board containing tungsten as a wiring material.

One aspect of the processing method of the present invention includes the following steps: After chemical mechanical polishing is performed on the wiring substrate containing tungsten as the wiring material of the wiring substrate, the semiconductor processing composition of any one of the aspects is used for processing.

[Effects of the invention] According to the semiconductor processing composition of the present invention, even if it is stored for a long period of time, deterioration in polishing characteristics or cleaning characteristics is small, and semiconductor manufacturing can be performed stably. In addition, according to the semiconductor processing composition of the present invention, it is possible to suppress corrosion of the metal wiring of the object to be processed, etc., and to effectively remove contamination from the surface of the object to be processed. The semiconductor processing composition of the present invention is particularly effective when processing a wiring board containing tungsten or cobalt as a wiring material.

Hereinafter, a suitable embodiment of the present invention will be described in detail. In addition, the present invention is not limited to the following embodiments, and includes various modifications implemented within a range that does not change the gist of the present invention.

1. Semiconductor processing composition The semiconductor processing composition of one embodiment of the present invention contains (A) at least one selected from the group consisting of cyclodextrin and cyclodextrin derivatives (in this specification, also Referred to as "(A) component"), (B) a compound having a zwitterionic structure (in this specification, also referred to as "(B) component") and (C) a liquid medium, when the (A) When the content of the component is M _A [mass %], and the content of the (B) component is M _B [mass %], M _A /M _B =3-15. The semiconductor processing composition of the present embodiment may be a concentrated type intended to be used after being diluted with a liquid medium such as pure water or an organic solvent if necessary, or may be a non-diluted type intended to be used directly without dilution. In this specification, when it is not specified as a concentrated type or a non-diluted type, the term "semiconductor processing composition" can be interpreted as including both the concentrated type and the non-diluted type.

In addition, the semiconductor processing composition of this embodiment can be used as a CMP slurry for chemical mechanical polishing, a cleaning agent for removing particles or metal impurities on the surface of a processed object after CMP, etc. A resist stripper for peeling a resist from a semiconductor substrate processed with a resist, and a processing agent such as an etchant for lightly etching the surface of metal wiring and the like to remove surface contamination.

That is, the "treatment agent" in the present invention refers to a treatment agent prepared by adding a liquid medium to the concentrated semiconductor processing composition for dilution, or the non-diluted semiconductor processing composition It is the liquid used when actually processing the surface to be processed. The concentrated semiconductor processing composition generally exists in a concentrated state of each component. Therefore, each user dilutes the concentrated semiconductor processing composition with a liquid medium to prepare a processing agent, or uses the non-diluted semiconductor processing composition directly as a processing agent, and the processing agent can be used as a chemical treatment agent. CMP slurry for mechanical polishing, cleaning agent for cleaning the surface of semiconductor, resist stripper, and etchant are used. Hereinafter, each component contained in the semiconductor processing composition of this embodiment will be described in detail.

1.1. (A) Cyclodextrin and cyclodextrin derivatives The semiconductor processing composition of this embodiment contains (A) at least one selected from the group consisting of cyclodextrin and cyclodextrin derivatives. Here, cyclodextrin is a type of cyclic oligosaccharides with several molecules of D-glucose bonded by glucosidic bonds to obtain a cyclic structure. It is known that cyclodextrins are bound to 5 or more glucoses, and the usual cyclodextrins are cyclodextrins to which 6 to 8 glucoses are bound. As the cyclodextrin, α-cyclodextrin to which 6 glucose is bonded, β-cyclodextrin to which 7 glucose is bonded, and γ-cyclodextrin to which 8 glucose is bonded can be preferably used.

The cyclodextrin derivative is obtained by modifying the hydroxyl group possessed by the cyclodextrin as described above. As the cyclodextrin derivative, for example, 2-hydroxypropyl-β-cyclodextrin, 2-hydroxyethyl-β-cyclodextrin, etc. can be preferably used.

In the concentrated CMP slurry, when the total mass of the semiconductor processing composition is 100% by mass, the lower limit of the content of the component (A) is preferably 0.01% by mass, more preferably 0.03% by mass, Especially preferably, it is 0.05% by mass. On the other hand, when the total mass of the semiconductor processing composition is 100% by mass, the upper limit of the content of the component (A) is preferably 0.5% by mass, more preferably 0.3% by mass, and particularly preferably 0.2% by mass %. In the undiluted CMP slurry, when the total mass of the semiconductor processing composition is 100% by mass, the lower limit of the content of the component (A) is preferably 0.005% by mass, more preferably 0.01% by mass , Particularly preferably 0.02% by mass. On the other hand, when the total mass of the semiconductor processing composition is 100% by mass, the upper limit of the content of the component (A) is preferably 1% by mass, more preferably 0.5% by mass, and particularly preferably 0.1% by mass %. If the content of the (A) component is within the above-mentioned range, the (B) component can be effectively contained in the hydrophobic cavity inside the ring structure of the (A) component, and therefore the storage stability can be improved without generating precipitation.

In other concentrated processing agents (such as cleaning agents), when the total mass of the semiconductor processing composition is 100% by mass, the lower limit of the content of component (A) is preferably 0.1% by mass, more preferably It is 0.2% by mass, particularly preferably 0.3% by mass. On the other hand, when the total mass of the semiconductor processing composition is 100% by mass, the upper limit of the content of the component (A) is preferably 10% by mass, more preferably 7% by mass, and particularly preferably 5% by mass %. In other undiluted processing agents (such as cleaning agents), when the total mass of the semiconductor processing composition is 100% by mass, the lower limit of the content of component (A) is preferably 0.005% by mass, and more Preferably, it is 0.01% by mass, and particularly preferably is 0.02% by mass. On the other hand, when the total mass of the semiconductor processing composition is 100% by mass, the upper limit of the content of the component (A) is preferably 1% by mass, more preferably 0.5% by mass, and particularly preferably 0.1% by mass %. If the content of (A) component is within the above-mentioned range, particles or metal impurities present on the surface of the object to be processed after completion of CMP can be contained in the hydrophobic cavity inside the ring structure of (A) component Therefore, it is possible to reduce the residue contamination on the object to be processed, and suppress the generation of residue contamination from the semiconductor processing composition.

1.2. (B) Compounds with zwitterionic structure The semiconductor processing composition of this embodiment contains (B) a compound having a zwitterionic structure. Here, the compound having a zwitterionic structure refers to a compound having one or more functional groups that may have a positive charge in the composition and one or more functional groups that may have a negative charge in the composition in the same molecule. . As such a compound having a zwitterionic structure, for example, in the same molecule, a functional group for generating positive charges such as ammonium cations and a functional group for generating negative charges such as carboxylate anions in the same molecule can be cited. Salt compound.

The component (B) is not particularly limited as long as it is a compound having such a zwitterionic structure, but it preferably has at least one functional group selected from the group consisting of a carboxyl group and a sulfonic acid group and a carbon number of 12 The zwitterionic structure of the above and 18 or less alkyl groups is more preferably a compound represented by the following general formula (1).

[化1]

In the formula (1), R ¹ and R ² each independently represent a substituted or unsubstituted alkanediyl group having 1 to 6 carbon atoms, but preferably an alkanediyl group having 1 to 4 carbon atoms, more preferably It is an alkanediyl group having 1 to 2 carbons. In the formula (1), R ³ represents an alkyl group having 12 or more and 18 or less carbon atoms.

In particular, the compound represented by the general formula (1) has carboxyl groups at both ends of the molecule. The (B) component having such a structure has a high coordination ability with respect to metal ions, and therefore can effectively suppress corrosion of metal wiring materials and the like.

(B) Specific examples of the component include, for example, alanine, arginine, aspartic acid, aspartic acid, cysteine, glutamic acid, glutamic acid, glycine, and isobaric acid. Amino acid, leucine, lysine, methionine, phenylalanine, serine, threonine, tyrosine, valine, tryptophan, histidine, 2-amino- 3-aminopropionic acid, N-[2-[(2-aminoethyl)dodecylamino]ethyl]glycine and other amino acids; lysine betaine, ornithine betaine , Lobster inosine (Homarine), trigonelline (trigonelline), alanine betaine, taurobetaine, phenylpropanine betaine carnitine, homoserine betaine, valine betaine, trimethyl Glycine (glycine betaine), stachydrine (stachydrine), γ-butyrobetaine (γ-butyrobetaine), lauryl dimethylaminoacetate betaine, lauryl hydroxysultaine, hard Fatty dimethyl amino acetate betaine, lauryl amidopropyl betaine, coco amidopropyl betaine, glutamate betaine, sodium lauryl amido diacetate, sodium lauryl amido dipropionate Etc., one or more selected from these can be used.

In the concentrated CMP slurry, when the total mass of the semiconductor processing composition is 100% by mass, the lower limit of the content of the component (B) is preferably 0.002% by mass, more preferably 0.005% by mass, Especially preferably, it is 0.01% by mass. On the other hand, when the total mass of the semiconductor processing composition is 100% by mass, the upper limit of the content of the component (B) is preferably 0.2% by mass, more preferably 0.1% by mass, and particularly preferably 0.05% by mass %. In the undiluted CMP slurry, when the total mass of the semiconductor processing composition is 100% by mass, the lower limit of the content of the component (B) is preferably 0.001% by mass, more preferably 0.002% by mass , Particularly preferably 0.005 mass%. On the other hand, when the total mass of the semiconductor processing composition is 100% by mass, the upper limit of the content of the component (B) is preferably 0.2% by mass, more preferably 0.1% by mass, and particularly preferably 0.05% by mass %. If the content of the (B) component is within the above range, the (B) component can be effectively contained in the hydrophobic cavity inside the ring structure of the (A) component, and therefore the storage stability can be improved without generating precipitation.

In other concentrated processing agents (such as cleaning agents), when the total mass of the semiconductor processing composition is 100% by mass, the lower limit of the content of component (B) is preferably 0.01% by mass, more preferably It is 0.03% by mass, particularly preferably 0.06% by mass. On the other hand, when the total mass of the semiconductor processing composition is 100% by mass, the upper limit of the content of the component (B) is preferably 5% by mass, more preferably 3% by mass, and particularly preferably 1% by mass %. In other undiluted treatment agents (for example, cleaning agents), when the total mass of the semiconductor processing composition is 100% by mass, the lower limit of the content of component (B) is preferably 0.005% by mass, and more Preferably, it is 0.01% by mass, and particularly preferably is 0.02% by mass. On the other hand, when the total mass of the semiconductor processing composition is 100% by mass, the upper limit of the content of the component (B) is preferably 0.2% by mass, more preferably 0.1% by mass, and particularly preferably 0.05% by mass %. If the content of component (B) is within the above range, particles or metal impurities present on the surface of the object to be processed after the completion of CMP can be effectively reduced or removed, and metals such as metal wiring materials can be less likely to be corroded .

1.3. The content ratio of (A) component and (B) component Regarding the content ratio of (A) component and (B) component in the semiconductor processing composition of this embodiment, when the content of (A) component is M _A [mass %], and when the content of the component (B) is M _B [mass %], _{the lower limit of the value of M A} /M _B is preferably 3.0, more preferably 3.5. The upper limit of the value of M _A /M _B is preferably 15.0, more preferably 14.5.

In the semiconductor processing composition of the present embodiment, it is estimated that the inclusion compound is formed by taking the component (B) into the hydrophobic cavity inside the ring structure of the component (A). _{If the value of M A} /M _B , which is the content ratio of (A) component and (B) component, is within the above range, the content of (A) component or (B) component that does not form a containment compound can be suppressed, so it is estimated Even when the (B) component is present in the semiconductor processing composition in a high concentration, the precipitation of the (B) component is suppressed, and the characteristics of the concentrated semiconductor processing composition are not deteriorated, and the long-term growth can be achieved. Period of storage. In addition, if _{the value of M A} /M _B is within the above-mentioned range, the content of the component (B) that does not form the inclusion compound can be suppressed. Therefore, it is considered that the exposure of the surface to be processed can be suppressed in the semiconductor processing step. The generation of residues of the condensation products of metal materials such as copper or tungsten with (B) as the nucleus.

On the other hand, when _{the value of M A} /M _B exceeds the above-mentioned range, the component (A) adheres to and remains on the processed body after the treatment and becomes a defect, which induces the electrical characteristics of the semiconductor circuit as the processed body The yield reduction caused by the deterioration of the product is unsatisfactory. On the other hand, when _{the value of M A} /M _B is less than the above-mentioned range, the metal material such as copper or tungsten exposed on the surface to be processed and the non-contained compound existing in the semiconductor processing composition The (B) component and the (B) component adhere to or remain on metal materials such as copper or tungsten and become defects, and it is considered that the flatness or electrical properties of the processed surface will be degraded. In addition, since the content of the (A) component is too small relative to the content of the (B) component, there are cases where the (B) component becomes excessive, thereby causing precipitation and impairing storage stability.

In addition, in the CMP of the to-be-processed body which has tungsten as a wiring material, the CMP slurry containing iron ion and peroxide (hydrogen peroxide, potassium iodate, etc.) may be used. The iron ions contained in the CMP slurry are easily adsorbed on the surface of the object to be processed, and therefore the polished surface is easily contaminated by iron. In this case, by using the semiconductor processing composition of this embodiment to clean the surface to be polished, the production of easily soluble salts such as potassium tungstate or sodium tungstate is promoted in the cleaning step. Thereby, it is considered that the metal contamination on the wiring board can be reduced, the corrosion of the object to be processed can be reduced, and the polishing residue can be efficiently removed.

1.4. Liquid medium (C) The semiconductor processing composition of this embodiment contains a liquid medium (C) as a main component. The type of the liquid medium (C) can be appropriately selected according to the purpose of use of the treatment agent such as polishing, cleaning, etching, and resist peeling of the object to be processed.

When the semiconductor processing composition of this embodiment is used as a CMP slurry or a cleaning agent, the liquid medium (C) is preferably an aqueous medium containing water as a main component. Examples of such an aqueous medium include a mixed medium of water, water, and alcohol, and a mixed medium containing water and an organic solvent compatible with water. Among these water-based media, it is preferable to use a mixed medium of water, water, and alcohol, and it is more preferable to use water.

When the semiconductor processing composition of this embodiment is used as an etchant or a resist stripper, the liquid medium (C) is preferably a non-aqueous medium containing an organic solvent as a main component. Examples of such non-aqueous media include polar solvents such as ketone-based solvents, ester-based solvents, ether-based solvents, and amide-based solvents, or hydrocarbon-based solvents equal to known organic solvents that can be used in the semiconductor processing step.

Examples of ketone solvents include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone, 4-heptanone, 1-hexanone, and 2-hexanone , Diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetone, acetonyl acetone, ionone, diacetone alcohol , Acetyl methanol, acetophenone, methyl naphthyl ketone, isophorone, propylene carbonate, γ-butyrolactone, etc.

As ester solvents, for example, chain ester solvents include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, ethyl methoxyacetate, and ethoxy. Ethyl ethyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether Acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monophenyl ether acetate, diethylene two Alcohol monobutyl ether acetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 3-methyl-3-methoxy Butyl butyl acetate, 3-ethyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, 2-ethoxy Butyl acetate, 4-ethoxybutyl acetate, 4-propoxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate , 4-methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate, 3-methyl-3-methoxypentyl acetate, 3-methyl-4 -Methoxypentyl acetate, 4-methyl-4-methoxypentyl acetate, propylene glycol diacetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl carbonate Ester, propyl carbonate, butyl carbonate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, butyl pyruvate, methyl acetylacetate, ethyl acetylacetate, methyl propionate, ethyl propionate Ester, propyl propionate, isopropyl propionate, methyl-3-methoxypropionate, ethyl-3-methoxypropionate, ethyl-3-ethoxypropionate, propyl Group -3-methoxy propionate and so on. In addition, examples of the cyclic ester solvent include lactones such as γ-butyrolactone.

Examples of ether-based solvents include glycols such as ethylene glycol dibutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol dibutyl ether. Ether solvents; diisoamyl ether, diisobutyl ether, dioxane, tetrahydrofuran, anisole, perfluoro-2-butyltetrahydrofuran, perfluorotetrahydrofuran, 1,4-dioxane, etc.

Examples of amide-based solvents include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, and hexamethylphosphatidylamine , 1,3-Dimethyl-2-imidazolidinone, etc. Examples of the other polar solvents include dimethyl sulfene and the like.

Examples of hydrocarbon solvents include pentane, hexane, octane, decane, 2,2,4-trimethylpentane, 2,2,3-trimethylhexane, perfluorohexane, Aliphatic hydrocarbon solvents such as perfluoroheptane, limonene and pinene; toluene, xylene, ethylbenzene, propylbenzene, 1-methylpropylbenzene, 2-methylpropylbenzene, dimethylbenzene, Aromatic hydrocarbon solvents such as diethylbenzene, ethylmethylbenzene, trimethylbenzene, ethyldimethylbenzene, and dipropylbenzene.

1.5. Other ingredients In addition to the above-mentioned components, the semiconductor processing composition of the present embodiment may appropriately contain required components according to the purpose of use of the processing agent such as polishing, cleaning, etching, and resist stripping. Examples of such components include abrasive grains, water-soluble polymers, organic acids, amines, pH adjusters, surfactants, and the like.

1.5.1. Abrasive particles When using the semiconductor processing composition of this embodiment as a CMP slurry, it is preferable to contain abrasive grains. Examples of abrasive particles include inorganic particles such as silica, cerium oxide, alumina, zirconia, and titanium oxide. Among these, silicon dioxide particles are preferred.

Examples of the silica particles include colloidal silica, fumed silica, and the like. Among these, colloidal silica is preferred. From the viewpoint of reducing grinding defects such as scratches, colloidal silica may be preferably used. As the colloidal silica, for example, one produced by the method described in JP 2003-109921 A, etc. can be used. In addition, you can also use, for example, Japanese Patent Laid-Open No. 2010-269985 or Journal of Industrial and Engineering Chemistry (JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY, J. Ind. Eng. Chem.), Vol. 12, No. 6, (2006). ) Colloidal silica prepared by surface modification as described in 911-917, etc.

When the total mass of the CMP slurry used for the object to be processed is set to 100% by mass, the content of abrasive grains is preferably 0.01% by mass or more and 4% by mass or less, more preferably 0.1% by mass or more and 1.5% by mass % Or less, particularly preferably 0.5% by mass or more and 1% by mass or less. When the content ratio of the abrasive grains is in the above range, a practical polishing rate for the object to be processed can be obtained.

1.5.2. Water-soluble polymer The semiconductor processing composition of this embodiment may contain a water-soluble polymer even if it is a processing agent for any purpose of use. Since the water-soluble polymer is contained and adsorbed on the surface of the object to be processed, a film is formed. Therefore, it may be possible to further reduce the corrosion of the object to be processed. Furthermore, in the present invention, the term "water-soluble" means that the mass dissolved in 100 g of water at 20°C is 0.1 g or more.

Examples of water-soluble polymers include polyacrylic acid, polymethacrylic acid, polymaleic acid, polyvinylsulfonic acid, polyallylsulfonic acid, polystyrenesulfonic acid, and their salts; styrene, α -Copolymers of monomers such as methylstyrene and 4-methylstyrene with acid monomers such as (meth)acrylic acid and maleic acid, or the use of formalin to condense benzenesulfonic acid, naphthalenesulfonic acid, etc. Polymers containing repeating units with aromatic hydrocarbon groups and their salts; polyvinyl alcohol, polyoxyethylene, polyvinylpyrrolidone, polyvinylpyridine, polypropyleneamide, polyvinylmethamide, Polyethyleneimine, polyvinyloxazoline, polyvinylimidazole, polyallylamine and other synthetic vinyl polymers; modified products of natural polysaccharides such as hydroxyethylcellulose, carboxymethylcellulose, processed starch, etc. Etc., but not limited to these. These water-soluble polymers can be used individually by 1 type or in combination of 2 or more types.

The weight average molecular weight (Mw) of the water-soluble polymer that can be used in this embodiment is preferably 1,000 or more and 1.5 million or less, and more preferably 3,000 or more and 1.2 million or less. In addition, the "weight average molecular weight" in this specification refers to the weight average molecular weight in terms of polyethylene glycol measured by Gel Permeation Chromatography (GPC).

The content ratio of the water-soluble polymer can be adjusted so that the viscosity of the semiconductor processing composition at room temperature becomes 2 mPa·s or less. If the viscosity of the semiconductor processing composition at room temperature exceeds 2 mPa·s, there are cases where the viscosity becomes too high, and the semiconductor processing composition cannot be stably supplied to the object to be processed. The viscosity of the semiconductor processing composition is affected by the weight average molecular weight or content of the water-soluble polymer added, so it can be adjusted while considering these balances.

When the semiconductor processing composition of this embodiment is used as a cleaning agent, the content of the water-soluble polymer can be determined by metal wiring materials such as copper or tungsten exposed on the surface of the processed body after CMP, and oxidation The materials of insulating materials such as silicon, barrier metal materials such as tantalum nitride or titanium nitride, and the composition of the CMP slurry used are appropriately changed.

In addition, when the semiconductor processing composition of the present embodiment is used as a cleaning agent, the content ratio of the water-soluble polymer may be appropriately changed according to the degree of dilution of the concentrated semiconductor processing composition. When the total mass of the processing agent prepared by diluting the concentrated semiconductor processing composition or the non-diluting semiconductor processing composition (processing agent) is set to 100% by mass, the content ratio of the water-soluble polymer is preferably 0.001% by mass or more and 1% by mass or less, more preferably 0.01% by mass or more and 0.1% by mass or less. If the content of the water-soluble polymer is within the above-mentioned range, the inhibition of corrosion promotion and the effect of removing particles or metal impurities contained in the CMP slurry from the wiring board coexist, making it easy to obtain a better processed body .

1.5.3. Organic acids The semiconductor processing composition of this embodiment may contain organic acids other than the (B) component even if it is a processing agent for any purpose of use. In addition, the "organic acid" in this specification does not include the above-mentioned water-soluble polymer.

As an organic acid, it is preferable to have one or more acidic functional groups, such as a carboxyl group and a sulfo group. Specific examples of organic acids include: citric acid, maleic acid, malic acid, tartaric acid, oxalic acid, malonic acid, succinic acid, ethylenediaminetetraacetic acid, acrylic acid, methacrylic acid, benzoic acid, phenyllactic acid, Hydroxyphenyllactic acid, hydroxymalonic acid, phenylsuccinic acid, naphthalenesulfonic acid and their salts. These organic acids may be used individually by 1 type, and may mix and use 2 or more types.

Among the organic acids, a compound represented by the following general formula (2) can be preferably used.

（所述通式（2）中，R⁴ 表示碳數1～20的有機基）[化2]

(In the general formula (2), R ⁴ represents an organic group having 1 to 20 carbons)

^{As the organic group having 1 to 20 carbons in R 4} in the general formula (2), for example, a saturated aliphatic hydrocarbon group having 1 to 20 carbons, an unsaturated aliphatic hydrocarbon group having 1 to 20 carbons, and a ring C6-C20 organic group with saturated hydrocarbon group, C6-C20 organic group with unsaturated cyclic hydrocarbon group, C1-C20 hydrocarbon group with carboxyl group, C1-C20 hydrocarbon group with hydroxyl group , A hydrocarbon group with 1 to 20 carbons having both a carboxyl group and a hydroxyl group, a hydrocarbon group with 1 to 20 carbons having an amine group, a hydrocarbon group with 1 to 20 carbons having both an amine group and a carboxyl group, and a heterocyclic group Among them, an organic group having 1 to 20 carbons having a saturated aliphatic hydrocarbon group, an organic group having 1 to 20 carbons having an unsaturated aliphatic hydrocarbon group, or an organic group having 1 to 20 carbons is preferred. The hydrocarbon group having 1 to 20 carbon atoms of the carboxyl group is particularly preferably an organic group having 6 to 20 carbon atoms or a carboxymethyl group having an aryl group.

Specific examples of the compound represented by the general formula (2) include: citric acid, malonic acid, maleic acid, tartaric acid, malic acid, succinic acid, phthalic acid, glutamic acid, and aspartic acid Acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, iminodiacetic acid, etc. Among these, it is preferably at least one selected from the group consisting of citric acid, malonic acid, maleic acid, tartaric acid, malic acid and succinic acid, and more preferably selected from citric acid, malonic acid and apple At least one of the group consisting of acids, particularly preferably citric acid and malonic acid. If it is such a component (B), there are cases where pollution can be particularly reduced or removed. The exemplified compounds may be used singly, or two or more of them may be used in combination.

When the semiconductor processing composition of this embodiment is used as a cleaning agent, the content of organic acid can be determined based on the metal wiring materials such as copper or tungsten, silicon oxide, etc., which are exposed on the surface of the processed body after CMP. The materials of the insulating material, barrier metal materials such as tantalum nitride or titanium nitride, and the composition of the CMP slurry used are appropriately changed.

Furthermore, the content ratio of the organic acid may be appropriately changed according to the degree of dilution of the concentrated semiconductor processing composition of the present embodiment. When the total mass of the processing agent prepared by diluting the concentrated semiconductor processing composition or the non-diluting semiconductor processing composition (processing agent) is set to 100% by mass, the content of the organic acid is preferably 0.0001 mass% % Or more and 1 mass% or less, more preferably 0.0005 mass% or more and 0.5 mass% or less. If the content ratio of the organic acid is within the above-mentioned range, there are cases in which impurities adhering to the surface of the wiring material can be removed more effectively. In addition, there are cases where the progress of excessive etching is more effectively suppressed, and a good object to be processed may be obtained.

1.5.4. Amine When the semiconductor processing composition of this embodiment is used as a cleaning agent, it is preferable to contain an amine. Amine has a function as an etchant. Therefore, it is believed that by adding amine, the metal oxide film (for example, CuO, Cu ₂ O, and Cu(OH) ₂ layers) or organic residues (for example, benzotriazine) on the wiring substrate can be removed in the cleaning step after CMP. Azole (Benzotriazole, BTA) layer) is etched and removed.

The amine used in the cleaning agent is preferably a water-soluble amine. Regarding the definition of "water solubility", as described above, it means that the mass dissolved in 100 g of water at 20°C is 0.1 g or more. Examples of amines include alkanolamines, primary amines, secondary amines, and tertiary amines.

Examples of alkanolamines include monoethanolamine, diethanolamine, triethanolamine, N-methylethanolamine, N-methyl-N,N-diethanolamine, N,N-dimethylethanolamine, and N,N-diethyl Ethanolamine, N,N-dibutylethanolamine, N-(β-aminoethyl)ethanolamine, N-ethylethanolamine, monopropanolamine, dipropanolamine, tripropanolamine, monoisopropanolamine , Diisopropanolamine, Triisopropanolamine, etc. Examples of the primary amine include methylamine, ethylamine, propylamine, butylamine, pentylamine, 1,3-propanediamine, and the like. Examples of secondary amines include piperidine and piperazine. Examples of tertiary amines include trimethylamine, triethylamine, and the like. These amines may be used individually by 1 type, and may mix and use 2 or more types.

Among these amines, monoethanolamine and monoisopropanolamine are preferable, and monoethanolamine is more preferable in terms of the high effect of etching the metal oxide film or organic residue on the wiring board.

When the semiconductor processing composition of the present embodiment is used as a cleaning agent, the content of amine can be determined based on the metal wiring materials such as copper or tungsten, and insulating materials such as silicon oxide that are exposed on the surface of the processed body after CMP. The materials, barrier metal materials such as tantalum nitride or titanium nitride, and the composition of the CMP slurry used are appropriately changed.

Furthermore, the amine content ratio may be appropriately changed according to the degree of dilution of the concentrated semiconductor processing composition of the present embodiment. When the total mass of the processing agent prepared by diluting the concentrated semiconductor processing composition or the non-diluting semiconductor processing composition (processing agent) is set to 100% by mass, the content of the amine is preferably 0.0001% by mass Above and 1% by mass or less, more preferably 0.0005% by mass or more and 0.5% by mass or less. If the content ratio of the amine is within the above range, the metal oxide film or organic residue on the wiring substrate can be more effectively etched away in the cleaning step after the CMP.

1.5.5. pH adjuster In the case of a semiconductor processing composition for processing a surface to be processed containing copper as a wiring material, the lower limit of the pH is preferably 9, more preferably 10, and the upper limit of the pH is preferably 14. In the case of a semiconductor processing composition for processing a surface to be processed containing tungsten as a wiring material, the lower limit of the pH is preferably 2, and the upper limit of the pH is preferably 7, and more preferably 6.

In the semiconductor processing composition of the present embodiment, when the desired pH value cannot be obtained by adding the above-mentioned components, in order to adjust the pH value within the above range, it may be added separately pH adjuster. Examples of pH adjusters include inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid, and phosphoric acid; alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, rubidium hydroxide, and cesium hydroxide; organic compounds such as tetramethylammonium hydroxide. Ammonium salt; basic compounds such as ammonia. These pH adjusters may be used individually by 1 type, and may mix and use 2 or more types.

In the present invention, the so-called pH value refers to the hydrogen ion index, and its value can be measured using a commercially available pH meter (for example, a desktop pH meter manufactured by Horiba Manufacturing Co., Ltd.) under the conditions of 25°C and 1 atmosphere. Determination.

1.5.6. Surfactant The semiconductor processing composition of this embodiment may contain a surfactant (except for the (A) component and (B) component) even if it is a processing agent for any purpose of use. As the surfactant, a nonionic surfactant or an anionic surfactant can be preferably used. By adding a surfactant, there are cases where the effect of removing particles or metal impurities contained in the CMP slurry from the wiring substrate is improved, and a better processed surface can be obtained.

Examples of nonionic surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; Polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether and other polyoxyethylene aryl ethers; sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, etc. Sorbitan fatty acid esters; polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate and other polyoxyethylene sorbitan fatty acid esters Wait. The exemplified nonionic surfactants may be used singly, or two or more of them may be mixed and used.

Examples of the anionic surfactant include: alkylbenzenesulfonic acids such as dodecylbenzenesulfonic acid; alkylnaphthalenesulfonic acid; alkylsulfuric acid esters such as laurylsulfuric acid; polyoxyethylene such as polyoxyethylene laurylsulfuric acid Sulfate ester of alkyl ether; naphthalenesulfonic acid condensate; alkyl imino dicarboxylic acid; lignin sulfonic acid, etc. These anionic surfactants can also be used in the form of salts. In this case, as a counter cation, sodium ion, potassium ion, ammonium ion, etc. are mentioned, for example, From a viewpoint of preventing potassium or sodium from being contained excessively, ammonium ion is preferable.

In the CMP of the to-be-processed body which has tungsten as a wiring material, the CMP slurry containing iron ion and peroxide (hydrogen peroxide, potassium iodate, etc.) may be used. The iron ions contained in the CMP slurry are easily adsorbed on the surface of the object to be processed, and therefore the surface of the object to be processed is easily contaminated by iron. In this case, iron ions are positively charged, so there are cases where the addition of an anionic surfactant to the semiconductor processing composition can effectively remove iron contamination on the surface of the object to be processed.

The content of the surfactant can be based on the materials of metal wiring materials such as copper or tungsten, insulating materials such as silicon oxide, and barrier metal materials such as tantalum nitride or titanium nitride that are exposed on the surface of the processed body after CMP. Or the composition of the CMP slurry used is appropriately changed.

Furthermore, the content ratio of the surfactant may be appropriately changed according to the degree of dilution of the concentrated semiconductor processing composition of the present embodiment. When the total mass of the processing agent prepared by diluting the concentrated semiconductor processing composition or the undiluted semiconductor processing composition (processing agent) is set to 100% by mass, the content ratio of the surfactant is preferably 0.001 Mass% or more and 1 mass% or less, more preferably 0.005 mass% or more and 0.5 mass% or less. If the content ratio of the surfactant is within the above-mentioned range, there are cases where the effect of removing particles or metal impurities contained in the CMP slurry from the wiring substrate is improved, and a better surface to be processed can be obtained.

1.6. Preparation method of semiconductor processing composition The semiconductor processing composition of this embodiment is not particularly limited, and can be prepared by using a known method. Specifically, it can be prepared by dissolving each component described above in a liquid medium such as water or an organic solvent and filtering it. The mixing order or mixing method of the above-mentioned components is not particularly limited.

In the preparation method of the semiconductor processing composition of the present embodiment, it is preferable to perform filtration with a depth filter or a pleated filter as necessary to control the amount of particles. Here, the deep-type filter is a high-precision filter which is also called a deep-layer filter or a volume filter type filter. Such a deep filter includes a filter having a layered structure in which a filter membrane having a plurality of pores is laminated, a filter in which a fiber bundle is wound, and the like. As a deep filter, specific examples include: Profile II, Nexis NXA, Nexis NXT, Polyfine XLD, Okipuri Ultipleat Profile, etc. (all manufactured by Pall Japan); depth cartridge filter, wynd cartridge filter, etc. (all Advantec) Company manufacturing); CP filters, BM filters, etc. (all manufactured by Chisso); Slope-Pure, Dia, Microsyria, etc. ( All are manufactured by Roki Techno company) and so on.

As a pleated filter, a microfiltration membrane sheet including non-woven fabric, filter paper, wire mesh, etc., is folded and processed, and then formed into a cylindrical shape, and the seams of the folds of the sheet are liquid-tightly sealed, and Both ends of the cylinder are liquid-tightly sealed to obtain a cylindrical high-precision filter filter. Specifically, it can include: HDCII, Polyfine II, etc. (all manufactured by Pall Japan); PP pleated cartridge filter (Advantec) (Manufactured by the company); Porous Fine (manufactured by Chisso); Sarton Pore, Micropure, etc. (all manufactured by Roki Techno), etc. .

2. Treatment agent As described above, each user may dilute the concentrated semiconductor processing composition with a liquid medium to prepare a processing agent, or use the undiluted semiconductor processing composition as it is as the processing agent. Moreover, the treatment agent can be used as a CMP slurry for chemical mechanical polishing, a cleaning agent for cleaning the surface of a semiconductor, a resist stripper or an etchant.

Here, the liquid medium used for dilution has the same meaning as the liquid medium contained in the semiconductor processing composition, and can be appropriately selected from the exemplified liquid mediums according to the type of processing agent.

As a method of adding a liquid medium to the concentrated semiconductor processing composition for dilution, there is the following method: the pipe for supplying the concentrated semiconductor processing composition and the pipe for supplying the liquid medium are merged and mixed in the middle, The mixed treatment agent is supplied to the surface to be treated. The following methods can be used for this mixing: a method of colliding and mixing liquids through a narrow passage under pressure; a method of filling the piping with fillers such as glass tubes to repeatedly separate and merge the flow of the liquid; in the piping The method of installing blades that rotate by power, etc. is usually performed.

In addition, as another method of adding a liquid medium to the concentrated semiconductor processing composition for dilution, there is the following method: separate the pipes for supplying the concentrated semiconductor processing composition and the pipes for supplying the liquid medium. The piping supplies a predetermined amount of liquid to the surface to be processed and mixes it on the surface to be processed. Furthermore, as another method of adding a liquid medium to the concentrated semiconductor processing composition for dilution, there is the following method: a predetermined amount of concentrated semiconductor processing composition and a predetermined amount of liquid are placed in a container. After the medium is mixed, the mixed treatment agent is supplied to the surface to be treated.

Regarding the dilution ratio when a liquid medium is added to the concentrated semiconductor processing composition for dilution, it is preferable to add a liquid medium to dilute 1 part by mass of the concentrated semiconductor processing composition to 1 part by mass to 500 parts by mass Parts (1 times to 500 times), more preferably diluted to 20 parts by mass to 500 parts by mass (20 times to 500 times), particularly preferably diluted to 30 parts by mass to 300 parts by mass (30 times to 300 times). Furthermore, it is preferable to use the same liquid medium as the liquid medium contained in the concentrated semiconductor processing composition for dilution. By placing the semiconductor processing composition in a concentrated state in this way, compared to the case where the processing agent is directly transported and stored, it can be transported or stored in a smaller container. As a result, the cost of transportation or storage can be reduced. In addition, as compared with the case where the processing agent is purified directly by operations such as filtering the processing agent, a smaller amount of the processing agent is purified. Therefore, the purification time can be shortened, thereby enabling mass production.

3. Treatment method The processing method of one embodiment of the present invention includes the step of processing a wiring board containing copper or tungsten as a wiring material using the semiconductor processing composition (processing agent). In more detail, as an aspect of the processing method of the present embodiment, an aspect including the following steps: using the semiconductor processing composition (CMP slurry), for wiring containing copper or tungsten as a wiring material The substrate is polished. In addition, as an aspect of the processing method of this embodiment, an aspect including the following steps: after chemical mechanical polishing of the wiring substrate containing tungsten as the wiring material of the wiring substrate, using the semiconductor processing method The composition (cleaning agent) is cleaned. Hereinafter, an example of the processing method of this embodiment will be described in detail while using the drawings.

3.1. Production of wiring board FIG. 1 is a cross-sectional view schematically showing a manufacturing process of a wiring board used in the processing method of this embodiment. The wiring board is formed through the following processes.

FIG. 1 is a cross-sectional view schematically showing a to-be-processed body before CMP processing. As shown in FIG. 1, the object to be processed 100 has a base 10. The base 10 may include, for example, a silicon substrate and a silicon oxide film formed thereon. Furthermore, although not shown, functional elements such as transistors may be formed on the base 10.

The to-be-processed body 100 is an insulating film 12 in which wiring recesses 20 are sequentially laminated on a substrate 10, and a barrier metal film 14 is provided so as to cover the surface of the insulating film 12 and the bottom and inner wall surfaces of the wiring recesses 20. , And a metal film 16 formed on the barrier metal film 14 that fills the wiring recess 20 and is formed.

As the insulating film 12, for example, a silicon oxide film formed by a vacuum process (for example, a plasma-enhanced tetraethoxysilane film (Plasma Enhanced-Tetraethoxysilane film, PETEOS film), a high-density plasma-enhanced tetraethoxysilane film, Film (High Density Plasma Enhanced-TEOS film, HDP film), silicon oxide film obtained by thermal chemical vapor deposition method, etc.), known as fluorine-doped silicate glass (Fluorine-doped silicate glass, FSG) ) Insulating film, borophosphosilicate film (Boro Phospho Silicate Glass film, BPSG film), insulating film called SiON (Silicon oxynitride), silicon nitride (Si ₃ N ₄ )Wait.

Examples of the barrier metal film 14 include tantalum, titanium, cobalt, ruthenium, manganese, and these compounds. The barrier metal film 14 is most often formed of one of these, and two or more kinds of tantalum and tantalum nitride may also be used in combination.

The metal film 16 needs to completely fill the wiring recess 20 as shown in FIG. 1. Therefore, a metal film of 10,000 Å to 15,000 Å is usually deposited by chemical vapor deposition or electroplating. Examples of the material of the metal film 16 include copper or tungsten. In the case of copper, not only high-purity copper but also an alloy containing copper can be used. The copper content in the copper-containing alloy is preferably 95% by mass or more.

3.2. Grinding steps Then, the metal film 16 other than the portion buried in the wiring recess 20 in the processed body 100 of FIG. 1 is polished at a high speed by CMP until the barrier metal film 14 is exposed (first polishing step). Furthermore, the barrier metal film 14 exposed on the surface is polished by CMP (second polishing step). In this manner, the wiring substrate 200 as shown in FIG. 2 is obtained.

In any of the first polishing step and the second polishing step, the semiconductor processing composition (CMP slurry for chemical mechanical polishing) can be used. By using the semiconductor processing composition as a CMP slurry, corrosion of wiring materials or barrier metal materials after CMP can be suppressed, and contamination can be effectively removed from the surface of the object to be processed. The semiconductor processing composition is particularly effective when processing a wiring board containing tungsten or cobalt as a wiring material.

3.3. Cleaning steps Next, the surface (surface to be processed) of the wiring substrate 200 shown in FIG. 2 is processed using the composition (cleaning agent) for semiconductor processing. By using the semiconductor processing composition as a cleaning agent, corrosion of wiring materials or barrier metal materials after CMP can be suppressed, and contamination can be effectively removed from the surface of the object to be processed.

If a composition containing iron ions and peroxides (Fenton's reagent) described in Japanese Patent Laid-Open No. 10-265766 etc. (Fenton's reagent) is used, the wiring containing tungsten as the wiring material of the wiring substrate After the substrate is chemically mechanically polished, it is very effective to perform the cleaning step using the semiconductor processing composition (cleaning agent). In CMP of a to-be-processed body having tungsten as a wiring material, there are cases in which a CMP slurry containing iron ions and peroxides (hydrogen peroxide, potassium iodate, etc.) is used as an oxidizing agent with high oxidizing power. The iron ions contained in the CMP slurry are easily adsorbed on the surface of the object to be processed, and therefore the surface of the object to be processed is easily contaminated by iron. In this case, the surface of the object to be processed can be treated with dilute hydrofluoric acid to remove iron contamination, but the surface of the object to be polished is etched and easily corroded. However, by using the semiconductor processing composition to perform the cleaning step, iron ions and the like present on the surface of the object to be processed after the CMP is completed can be contained in the hydrophobic cavity inside the ring structure of the component (A). It is removed, and it is difficult to corrode metals such as metal wiring materials due to the effect of the (B) component.

The cleaning method is not particularly limited, and it can be performed by a method in which the semiconductor processing composition (cleaning agent) is brought into direct contact with the wiring substrate 200. As a method of bringing the cleaning agent into direct contact with the wiring substrate 200, a immersion type in which the cleaning agent is filled in a cleaning tank and the wiring substrate is immersed; while the cleaning agent is flowed from a nozzle onto the wiring substrate, the wiring substrate is rotated at a high speed. Spin-coating method; spraying method for cleaning the wiring substrate by spraying cleaning agent. In addition, as an apparatus for performing this method, a batch type processing apparatus that processes multiple wiring boards stored in a cassette at the same time, and a single wiring board that mounts and processes a single wiring board on a holder can be cited. Chip processing equipment, etc.

In the cleaning step, the temperature of the cleaning agent is usually set to room temperature, and it can also be heated within a range that does not impair performance, for example, it can be heated to about 40°C to 70°C.

In addition, in addition to the above-described method of bringing the cleaning agent into direct contact with the wiring substrate 200, it is also preferable to use a processing method using physical force in combination. Thereby, the removal of contamination due to particles attached to the wiring substrate 200 can be improved, and the processing time can be shortened. As a treatment method using physical force, wiping cleaning using a cleaning brush or ultrasonic cleaning can be cited.

Furthermore, it is also possible to wash with ultrapure water or pure water before and/or after the washing step.

4. Example Hereinafter, the present invention will be described through examples, but the present invention is not limited to these examples at all. Furthermore, as long as there is no special description, the "parts" and "%" in this embodiment are the quality standards.

4.1. Example 1 to Example 10, Comparative Example 1 to Comparative Example 4 4.1.1. Preparation of semiconductor processing composition (concentrated CMP slurry) The (A) component and ion exchange water shown in Table 1 were put in a polyethylene container, and then the (B) component shown in Table 1 was put in and stirred for 15 minutes. After that, the water-soluble polymers and organic acids shown in Table 1 were added, then the abrasive grains and the pH adjuster were added in sequence, and then stirred for 15 minutes to obtain Examples 1 to 10 and Comparative Examples 1 to 4 The semiconductor processing composition (concentrated CMP slurry).

4.1.2. Evaluation method ＜Stability evaluation＞ 50 g of the obtained semiconductor processing composition was added to a colorless and transparent glass container, and the state immediately after preparation and after standing in a constant temperature storage at 20° C. for one month was observed by visual observation. The evaluation criteria are as follows. (Evaluation criteria) ·A (good): No accumulation of deposits was observed, and it was in a good state. ·B (Bad): A state where condensate or sediment accumulates on the bottom of the container and cannot be used for practical purposes.

<Evaluation of corrosion characteristics> Cut an 8-inch silicon wafer (an 8-inch silicon substrate with a thermal oxide film on which a tungsten film with a thickness of 2,000 Å is laminated) on which a tungsten (W) film is formed on the surface by a sputtering method It is 1 cm×3 cm and set as a metal wafer test piece. For this test piece, the sheet resistance value was measured using a metal film thickness meter "Σ-5" manufactured by NPS Co., Ltd., and the film thickness was calculated in advance by the following formula based on the sheet resistance value and the volume resistivity of the metal film. Film thickness (Å)=[volume resistivity of metal film (Ω·m)÷sheet resistance value (Ω)]×10 ¹⁰

Then, the semiconductor processing composition immediately after preparation and the semiconductor processing composition after being left in a constant temperature storage at 20°C for one month were diluted with ultrapure water so as to become the dilution ratio described in Table 1. , And then put 100 g in a polyethylene container. After that, the 35% by mass hydrogen peroxide water was converted into hydrogen peroxide, and it was added so as to become 1% by mass and stirred for 15 minutes. Furthermore, the temperature was maintained at 40° C., and the metal wafer test piece on which the tungsten film was formed was immersed in the obtained composition for 60 minutes. After that, it was washed with running water for 10 seconds and dried. The film thickness of the metal wafer test piece after the immersion treatment was measured again, and the reduced film thickness was divided by the immersion time of 60 minutes to calculate the etching rate (unit: Å/min). The evaluation criteria are as follows. The evaluation results are shown in Table 1. (Evaluation criteria) ·A: The etching rate is less than 5 Å/min, which can effectively inhibit the corrosion of tungsten in the grinding step. Very good. ·B: The etching rate is 5 Å/min or more and 10 Å/min or less, which can suppress the corrosion of tungsten in the polishing step to a practical level. good. ·C: The etching rate is 10 Å/min or more, and the tungsten corrosion in the grinding step is large, which is not practical. bad. · D: Evaluation could not be carried out due to the generation of deposits. Very bad.

＜Defect evaluation＞ Use ultrapure water to dilute the semiconductor processing composition immediately after preparation and the semiconductor processing composition after being allowed to stand in a constant temperature storage at 20°C for one month at the dilution ratios described in Table 1, and then apply it to polyethylene 500 g was put into the manufacturing container, 35 mass% hydrogen peroxide water was converted into hydrogen peroxide, and the mixture was added so as to become 1 mass% and stirred for 15 minutes, thereby obtaining a chemical mechanical polishing composition. An 8-inch silicon substrate with a thermal oxide film laminated with a tungsten film with a thickness of 2,000 Å was cut into 3 cm×3 cm and used as a wafer test piece. Using this wafer test piece as a to-be-polished body, a chemical mechanical polishing process was performed for 60 seconds under the following polishing conditions. (Grinding conditions) ·Grinding device: "LM-15C" manufactured by Lapmaster SFT Grinding pad: "IC1000/K-Groove" manufactured by Rodel Nitta Co., Ltd. ·Pressure plate speed: 90 rpm ·Rotating speed of grinding head: 90 rpm ·Pressing pressure of grinding head: 3 psi ·Supply rate of chemical mechanical polishing composition: 100 mL/min

Then, under washing conditions where the supply rate of ion-exchange water was 500 mL/min, water washing treatment on the polishing pad was performed for 10 seconds. For the metal wafer test piece subjected to the chemical mechanical polishing process by the method, the scanning atomic force microscope (Atomic Force Microscope, AFM) manufactured by Bruker Corporation (Dimension FastScan) is used, and the outer frame size is Observe 5 locations at 10 μm. The image analysis software was used to analyze the obtained images of the five parts, and the total number of deposits having a height of 10 nm or more was used as the number of defects. The evaluation criteria are as follows. The evaluation results are shown in Table 1. (Evaluation criteria) ·A: The number of defects is less than 30. Very good grinding results. · B: The number of defects is more than 30 and less than 50. Good grinding results for practical use. C: The number of defects is 50 or more. Unable to provide practical poor grinding results. · D: Evaluation could not be carried out due to the generation of deposits. Very bad.

4.1.3. Evaluation results The composition and evaluation results of the semiconductor processing composition (concentrated CMP slurry) are shown in Table 1 below.

[Table 1] Example Comparative example 1 2 3 4 5 6 7 8 9 10 1 2 3 4 Composition for semiconductor processing (concentrated type) (A) Cyclodextrin and cyclodextrin derivatives type β-cyclodextrin β-cyclodextrin β-cyclodextrin β-cyclodextrin β-cyclodextrin β-cyclodextrin β-cyclodextrin α-Cyclodextrin 2-hydroxypropyl-β-cyclodextrin 2-hydroxyethyl-β-cyclodextrin β-cyclodextrin β-cyclodextrin - β-cyclodextrin M _A (mass %) 0.28 0.056 0.1 0.2 0.1 0.1 0.1 0.1 0.1 0.1 1.8 0.12 - 0.08 (B) Compounds with zwitterionic structure type Sodium Lauryl Amino Diacetate Sodium Lauryl Amino Diacetate Sodium Lauryl Amino Diacetate Sodium Lauryl Amino Diacetate Lauryl amidopropyl betaine Dodecylaminoethylaminoethylglycine Lauryl hydroxy sultaine Sodium Lauryl Amino Diacetate Sodium Lauryl Amino Diacetate Sodium Lauryl Amino Diacetate Sodium Lauryl Amino Diacetate Sodium Lauryl Amino Diacetate Sodium Lauryl Amino Diacetate - M _B (mass%) 0.02 0.015 0.02 0.04 0.02 0.02 0.02 0.02 0.02 0.02 0.04 0.06 0.02 - M _A /M _B 14 3.7 5 5 5 5 5 5 5 5 45 2 - - Abrasive particles type PL-3 PL-3 PL-3 PL-3 PL-3 PL-3 PL-3 PL-3 PL-3 PL-3 PL-3 PL-3 PL-3 PL-3 quality% 4 1.5 2 4 2 2 2 2 2 2 2 2 2 2 Water-soluble polymer Polyacrylic acid (Mw=50,000) (quality%) 0.03 0.02 0.04 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 Polystyrene sulfonic acid (Mw=75,000) (quality%) 0.02 0.02 Organic acid Malonate (quality%) 0.20 0.15 0.20 0.40 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 Maleic acid (quality%) 0.20 Malic acid (quality%) 0.20 pH adjuster KOH KOH KOH KOH KOH - KOH KOH KOH KOH KOH KOH KOH KOH Manufacturing conditions Dilution ratio 2 1.5 2 4 2 2 2 2 2 2 2 2 2 2 Treatment agent pH value 3.3 2.8 2.8 2.8 2.8 2.0 3.5 2.8 2.8 2.8 2.8 2.8 2.8 2.8 type CMP slurry CMP slurry CMP slurry CMP slurry CMP slurry CMP slurry CMP slurry CMP slurry CMP slurry CMP slurry CMP slurry CMP slurry CMP slurry CMP slurry Evaluation item Stability evaluation Just after preparation A A A A A A A A A A A A B A After storage at 20°C for one month A A A A A A A A A A A B B A Corrosion characteristics evaluation Just after preparation A A A A A A A A A A B A A C After storage at 20°C for one month A A A A A A A A A A B D D C Defect evaluation Just after preparation A A A A A A A A A A C C C A After storage at 20°C for one month A A A A A A A A A A C D D A

In Table 1, the numerical value of each component represents mass %. In each example and each comparative example, the total amount of each component is 100% by mass, and the remaining amount is ion-exchanged water.

As shown in Table 1 above, the ratio of the content of (A) component M _A [mass %] to the content of (B) component M _B [mass %] M _A /M _B is a composition for semiconductor processing of 3-15 The corrosion characteristics of the compound (concentrated CMP slurry) for the tungsten film are good, and the defect evaluation after the CMP step using the composition is also a good result. In addition, even after the semiconductor processing compositions of Examples 1 to 10 were stored at 20° C. for one month, the generation of precipitates was not confirmed, and the stability was excellent. The corrosion characteristics and defect evaluation of the semiconductor processing compositions of Examples 1 to 10 after being stored at 20°C for one month were also good results.

On the other hand, like the semiconductor processing composition of Comparative Example 1, when M _A /M _B exceeds 15, it was confirmed that defects tend to be easily generated in the tungsten film. Like the semiconductor processing composition of Comparative Example 2, when M _A /M _{B is} less than 3, after storing at 20°C for one month, the generation of deposits is confirmed, and stability is easily impaired. , And tend to produce defects on the tungsten film. Like the semiconductor processing composition of Comparative Example 3, when component (A) is not contained, the formation of precipitates was confirmed immediately after preparation, and it was confirmed that the stability was extremely poor, and it was easily generated on the tungsten film. Prone to defects. Like the semiconductor processing composition of Comparative Example 4, when the component (B) is not contained, the corrosion inhibitory ability is poor.

4.2. Example 11 to Example 20, Comparative Example 5 to Comparative Example 8 4.2.1. Preparation of semiconductor processing composition (concentrated cleaning agent) The (A) component and ion exchange water shown in Table 2 were put in a polyethylene container, and then the (B) component shown in Table 2 was put in and stirred for 15 minutes. After that, the water-soluble polymers, organic acids, and amines shown in Table 2 were added, and then the pH adjuster was added, followed by stirring for 15 minutes, thereby obtaining the semiconductor processing of Example 11 to Example 20 and Comparative Example 5 to Comparative Example 8. Use composition (concentrated cleaning agent).

4.2.2. Evaluation method ＜Stability evaluation＞ The evaluation is performed according to the same method and evaluation criteria as the <stability evaluation> in "4.1.2. Evaluation method". The results are shown in Table 2.

<Evaluation of corrosion characteristics> Cut an 8-inch silicon wafer (an 8-inch silicon substrate with a thermal oxide film on which a tungsten film with a thickness of 2,000 Å is laminated) on which a tungsten (W) film is formed on the surface by a sputtering method It is 1 cm×3 cm and set as a metal wafer test piece. For this test piece, the sheet resistance value was measured using a metal film thickness meter "Σ-5" manufactured by NPS Co., Ltd., and the film thickness was calculated in advance by the following formula based on the sheet resistance value and the volume resistivity of the metal film. Film thickness (Å)=[volume resistivity of metal film (Ω·m)÷sheet resistance value (Ω)]×10 ¹⁰

Next, the semiconductor processing composition immediately after preparation and the semiconductor processing composition after being left in a constant temperature storage at 20°C for one month were diluted with ultrapure water so as to become the dilution ratio described in Table 2. , And then put 100 g in a polyethylene container. After that, these were kept at 25° C., and the metal wafer test piece on which the tungsten film was formed was immersed in each semiconductor processing composition for 60 minutes. After that, it was washed with running water for 10 seconds and dried. The film thickness of the metal wafer test piece after the immersion treatment was measured again, and the reduced film thickness was divided by the immersion time of 60 minutes to calculate the etching rate (ER (Etching Rate), unit: Å/min). The evaluation criteria are as follows. The evaluation results are shown in Table 2. (Evaluation criteria) ·A: The etching rate is less than 1.5 Å/min, which can effectively inhibit the corrosion of tungsten in the cleaning step. Very good. ·B: The etching rate is 1.5 Å/min or more and less than 5 Å/min, which suppresses the corrosion of tungsten in the cleaning step to a practical level. good. ·C: The etching rate is more than 5 Å/min, and the corrosion rate of tungsten in the cleaning step is high, which is not practical. bad. · D: Evaluation could not be carried out due to the generation of deposits. Very bad.

＜Defect evaluation＞ The colloidal silica water dispersion PL-3 (manufactured by Fuso Chemical Industry Co., Ltd.) was converted into silica and poured into a polyethylene container in an amount equivalent to 1% by mass. Ion-exchanged water and maleic acid as a pH adjuster were added so that the total amount was 100% by mass, and the pH was adjusted to 3. Furthermore, 35 mass% hydrogen peroxide water as an oxidizing agent was converted into hydrogen peroxide, and it was added so that it might become 1 mass %, and it stirred for 15 minutes, and obtained the composition for chemical mechanical polishing. An 8-inch silicon substrate with a thermal oxide film laminated with a tungsten film with a thickness of 2,000 Å was cut into 3 cm×3 cm and used as a wafer test piece. Using this wafer test piece as a to-be-polished body, a chemical mechanical polishing process was performed for 60 seconds under the following polishing conditions. (Grinding conditions) ·Grinding device: "LM-15C" manufactured by Lapmaster SFT Grinding pad: "IC1000/K-Groove" manufactured by Rodel Nitta Co., Ltd. ·Pressure plate speed: 90 rpm ·Rotating speed of grinding head: 90 rpm ·Pressing pressure of grinding head: 3 psi ·Supply rate of chemical mechanical polishing composition: 100 mL/min

Then, under washing conditions where the supply rate of ion-exchange water was 500 mL/min, water washing treatment on the polishing pad was performed for 10 seconds. For the wafer test pieces subjected to the chemical mechanical polishing process using the method described above, a scanning atomic force microscope (AFM), or Dimension FastScan, manufactured by Bruker Corporation, was used to observe 5 specimens with an outer frame size of 10 μm. Location. It was confirmed that the average value of the arithmetic average roughness of the obtained 5 locations was a flat surface wafer test piece of 0.2 nm or less, and it was used for the following defect evaluation.

Use ultrapure water to dilute the semiconductor processing composition immediately after preparation and the semiconductor processing composition after standing in a constant temperature storage at 20°C for one month so as to become the dilution ratio described in Table 2, and then Add 50 mL in a glass beaker and keep it at 25°C. After that, the wafer test piece subjected to the chemical mechanical polishing process was immersed for 15 minutes, washed with running water for 10 seconds and dried, and then 5 locations were observed using AFM with an outer frame size of 10 μm. The image analysis software was used to analyze the obtained images of the five parts, and the total number of deposits having a height of 2 nm or more was regarded as the number of defects. The evaluation criteria are as follows. The evaluation results are shown in Table 2. (Evaluation criteria) ·A: The number of defects is less than 100. Very good grinding results. · B: The number of defects is more than 100 and less than 500. Good grinding results for practical use. C: The number of defects is 500 or more. Unable to provide practical poor grinding results. · D: Evaluation could not be carried out due to the generation of deposits. Very bad.

4.2.3. Evaluation results The composition and evaluation results of the semiconductor processing composition (concentrated cleaning agent) are shown in Table 2 below.

[Table 2] Example Comparative example 11 12 13 14 15 16 17 18 19 20 5 6 7 8 Composition for semiconductor processing (concentrated type) (A) Cyclodextrin and cyclodextrin derivatives type β-cyclodextrin β-cyclodextrin β-cyclodextrin β-cyclodextrin β-cyclodextrin β-cyclodextrin β-cyclodextrin α-Cyclodextrin 2-hydroxypropyl-β-cyclodextrin 2-hydroxyethyl-β-cyclodextrin β-cyclodextrin β-cyclodextrin - β-cyclodextrin M _A (mass %) 1.40 0.37 0.5 1.5 0.5 0.30 1.60 5.00 5.00 5.00 1.8 0.10 - 0.4 (B) Compounds with zwitterionic structure type Sodium Lauryl Amino Diacetate Sodium Lauryl Amino Diacetate Sodium Lauryl Amino Diacetate Sodium Lauryl Amino Diacetate Lauryl amidopropyl betaine Dodecylaminoethylaminoethylglycine Lauryl hydroxy sultaine Sodium Lauryl Amino Diacetate Sodium Lauryl Amino Diacetate Sodium Lauryl Amino Diacetate Sodium Lauryl Amino Diacetate Sodium Lauryl Amino Diacetate Sodium Lauryl Amino Diacetate - M _B (mass%) 0.10 0.10 0.10 0.30 0.10 0.06 0.40 1.00 1.00 1.00 0.10 0.10 0.10 - M _A /M _B 14 3.7 5 5 5 5 4 5 5 5 18 1 - - Water-soluble polymer Polyacrylic acid (Mw=50,000) (quality%) 0.10 0.10 Polystyrene sulfonic acid (Mw=75,000) (quality%) 0.10 0.10 0.10 0.10 0.10 0.10 Organic acid Malonate (quality%) Maleic acid (quality%) 0.12 Malic acid (quality%) Citric acid (quality%) 0.10 0.10 0.10 0.30 0.10 0.40 0.10 0.10 0.10 0.10 amine Piperazine (quality%) 1.00 1.00 1.00 pH adjuster KOH KOH KOH KOH KOH KOH KOH Phosphoric acid Phosphoric acid Phosphoric acid - - - - Manufacturing conditions Dilution ratio 10 10 10 30 10 6 40 100 100 100 10 10 10 10 Treatment agent pH value 4.5 4.5 4.5 4.5 4.5 2.1 4.5 5.0 5.0 5.0 4.5 4.5 4.5 4.5 type detergent detergent detergent detergent detergent detergent detergent detergent detergent detergent detergent detergent detergent detergent Evaluation item Stability evaluation Just after preparation A A A A A A A A A A A B B A After storage at 20°C for one month A A A A A A A A A A A B B A Corrosion characteristics evaluation Just after preparation A A A A A A A A A A B A A C After storage at 20°C for one month A A A A A A A A A A B D D C Defect evaluation Just after preparation B A A A A B A A A A C C C A After storage at 20°C for one month B A A A A B A A A A C D D A

In Table 2 above, the numerical value of each component represents mass %. In each example and each comparative example, the total amount of each component is 100% by mass, and the remaining amount is ion-exchanged water. Here, each component in the Table 1 and the Table 2 will be supplemented.

＜(A) Cyclodextrin and cyclodextrin derivatives＞ ·Α-Cyclodextrin: manufactured by Fujifilm Wako Pure Chemical Co., Ltd., trade name ·Β-Cyclodextrin: manufactured by Fujifilm Wako Pure Chemical Co., Ltd., trade name ·2-Hydroxypropyl-β-cyclodextrin: manufactured by Fujifilm Wako Pure Chemical Co., Ltd., trade name ·2-Hydroxyethyl-β-cyclodextrin: manufactured by Fujifilm Wako Pure Chemical Co., Ltd., trade name ＜(B) Compounds with zwitterionic structure＞ ·Sodium laurylamino diacetate: manufactured by NOF Corporation, trade name "Nissananon (R) LA" ·Laurylamine propyl betaine: manufactured by Kao Co., Ltd., trade name "Amphitol 20AB" ·Laurylaminoethylaminoethylglycine: manufactured by Sanyo Chemical Industry Co., Ltd., trade name "Lebon (Lebon) S" ·Lauryl hydroxysultaine: manufactured by Kao Co., Ltd., trade name "Amphitol 20HD" ＜Abrasive grains＞ ·PL-3: manufactured by Fuso Chemical Industry Co., Ltd., trade name "PL-3", colloidal silica, with an average secondary particle size of 70 nm ＜Water-soluble polymer＞ ·Polyacrylic acid: manufactured by Toagosei Co., Ltd., trade name "AC-10L", Mw=50,000 ·Polystyrenesulfonic acid: manufactured by Akzo Nobel, trade name "Versa-TL 71", Mw=75,000 ＜Organic acid＞ · Malonic acid: manufactured by Shiquan Co., Ltd., trade name "malonic acid" ·Maleic acid: manufactured by Fusang Chemical Industry Co., Ltd., trade name "Water-containing maleic acid" · Malic acid: Showa Chemical Co., Ltd., trade name "DL-malic acid" ·Citric acid: manufactured by Lin Chunyao Industrial Co., Ltd., trade name "Citric Acid (Crystal)" ＜Amine＞ · Piperazine: manufactured by Tosoh Co., Ltd., trade name "Piperazine" ＜pH adjuster＞ ·KOH: manufactured by Kanto Chemical Co., Ltd., trade name "KOH (potassium hydroxide aqueous solution) 48%" · Phosphoric acid: manufactured by Rasa Industrial Co., Ltd., trade name "phosphoric acid"

As shown in Table 2 above, the ratio of the content of (A) component M _A [mass %] to the content of (B) component M _B [mass %] M _A /M _B is a composition for semiconductor processing of 3-15 The corrosion characteristics of the compound (concentrated cleaning agent) for the tungsten film are good, and the defect evaluation after the cleaning step using the composition after the CMP step is also a good result. In addition, even after the semiconductor processing compositions of Examples 11 to 20 were stored at 20° C. for one month, the generation of precipitates was not confirmed, and the stability was excellent. The corrosion characteristics and defect evaluations of the semiconductor processing compositions of Examples 11 to 20 after being stored at 20°C for one month were also good results.

On the other hand, like the semiconductor processing composition of Comparative Example 5, when M _A /M _B exceeds 15, it was confirmed that the tungsten film tends to generate defects easily. Like the semiconductor processing composition of Comparative Example 6, when M _A /M _{B is} less than 3, after storing at 20°C for one month, the generation of deposits is confirmed and stability is easily impaired. , And tend to produce defects on the tungsten film. Like the semiconductor processing composition of Comparative Example 7, when the component (A) is not contained, the formation of precipitates was confirmed immediately after the preparation, and the stability was confirmed to be extremely poor, and it was easily generated on the tungsten film. Prone to defects. Like the semiconductor processing composition of Comparative Example 8, when the component (B) is not contained, the corrosion inhibitory ability is poor.

According to the results of Table 1 and Table 2, it is shown that in _{the case of a semiconductor processing composition in the range of M A} /M _B of 3-15, a concentration of 1.5 times or more and 100 times or less can be guaranteed The storage stability in the morphology, and by diluting to a predetermined concentration during use, it can have both good corrosion inhibition ability and defect inhibition ability for the tungsten film.

The present invention is not limited to the embodiment described above, and various modifications can be made. For example, the present invention includes structures that are substantially the same as the structures described in the embodiments (for example, structures with the same functions, methods, and results, or structures with the same purposes and effects). In addition, the present invention includes a structure in which non-essential parts of the structure described in the embodiment are replaced. In addition, the present invention includes a structure that exerts the same function and effect as the structure described in the embodiment or a structure that can achieve the same purpose. In addition, the present invention includes a structure obtained by adding a known technique to the structure described in the embodiment.

10: Matrix 12: Insulating film 14: Barrier metal film 16: metal film 20: Recess for wiring 100: processed body 200: Wiring board

FIG. 1 is a cross-sectional view schematically showing a manufacturing process of a wiring board used in the processing method of this embodiment. 2 is a cross-sectional view schematically showing a manufacturing process of a wiring board used in the processing method of the present embodiment.

10: Matrix

12: Insulating film

14: Barrier metal film

16: metal film

20: Recess for wiring

100: processed body

Claims (8)

A composition for semiconductor processing, comprising: (A) at least one selected from the group consisting of cyclodextrin and cyclodextrin derivatives, (B) a compound having a zwitterionic structure, and (C) a liquid medium, When the content of the (A) component is M _A [mass %] and the content of the (B) component is M _B [mass %], M _A /M _B =3-15. The semiconductor processing composition according to claim 1, which is used after being diluted from 1 to 100 times. The semiconductor processing composition according to claim 1 or claim 2, wherein the component (B) has at least one functional group selected from the group consisting of a carboxyl group and a sulfonic acid group, and a carbon number of 12 or more And 18 or less alkyl compounds. The semiconductor processing composition according to claim 1 or 2, wherein the cyclodextrin derivative is selected from 2-hydroxypropyl-β-cyclodextrin and 2-hydroxyethyl-β-cyclodextrin At least one of dextrin. The semiconductor processing composition described in claim 1 or claim 2 further contains an organic acid. The semiconductor processing composition described in claim 1 or claim 2 further contains a water-soluble polymer. A processing method including the step of processing a wiring substrate containing tungsten as a wiring material using the semiconductor processing composition according to any one of claims 1 to 6. A processing method comprising the following steps: after chemical mechanical polishing of the wiring substrate containing tungsten as the wiring material of the wiring substrate, using the semiconductor processing composition according to any one of claim 1 to claim 6 To process.

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