TWI751126B - Semiconductor processing composition and processing method - Google Patents

Abstract

The present invention provides a composition for semiconductor processing capable of effectively removing contamination from the surface of an object to be processed while suppressing damage to metal wirings and the like of an object to be processed, and a processing method using the same. The composition for semiconductor processing of the present invention is characterized by containing 3×10 ¹ particles/mL to 1.5 ^{×10 3} particles/mL of particles having a particle diameter of 0.1 μm to 0.3 μm.

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 so-called chemical mechanical polishing (CMP), which is effectively used in the manufacture of semiconductor devices, is to press the object (object to be polished) on the polishing pad, and supply the chemical mechanical polishing aqueous dispersion ( Hereinafter, also abbreviated as "CMP slurry") while sliding the object to be processed and the polishing pad against each other, the technology of chemically and mechanically polishing the object to be processed. The CMP slurry used for such CMP contains chemicals such as an etchant in addition to abrasives. Furthermore, grinding dust is generated by CMP. If these abrasive dusts remain on the object to be processed, it may become a fatal device defect. Therefore, the step of cleaning the object to be processed must be performed after CMP.

On the surface of the object to be processed after CMP, metal wiring materials such as copper and tungsten, insulating materials such as silicon oxide, and barrier metal materials such as tantalum nitride and titanium nitride are exposed. When such dissimilar materials coexist on the surface to be polished, it is necessary to remove only contamination from the surface to be polished, and to handle without causing damage such as corrosion. For example, Patent Document 1 discloses a technique for suppressing corrosion of the surface to be polished where the wiring material and the barrier metal material are exposed by using an acidic composition for semiconductor processing. In addition, for example, Patent Document 2 or Patent Document 3 discloses a technique for treating the surface to be polished where the wiring material and the cobalt-like barrier metal material are exposed using a neutral to alkaline semiconductor processing composition. [Prior Art Document] [Patent Document]

[Patent Document 1] Japanese Patent Laid-Open No. 2010-258014 [Patent Document 2] Japanese Patent Laid-Open No. 2009-055020 [Patent Document 3] Japanese Patent Laid-Open No. 2013-157516

[Problem to be Solved by the Invention] However, with the further miniaturization of circuit structures in recent years, there has been a demand for a processing technology that further suppresses damage to metal wirings and the like of the object to be processed and can effectively remove the surface of the object to be processed remove contamination.

For example, CMP slurry containing iron nitrate and other oxidizing agents (hydrogen peroxide, potassium iodate, etc.) is used in CMP of a target object containing tungsten as a metal wiring. The iron ions contained in the CMP slurry are easily adsorbed on the surface of the object to be treated, so the surface of the object to be treated is easily contaminated with iron. In this case, the iron contamination can be removed by treating the surface of the object to be treated with dilute hydrofluoric acid, but the surface of the object to be treated is easily damaged by etching. Therefore, there is a demand for a treatment technique capable of effectively removing contamination from the surface of the object to be treated while suppressing damage to the metal wiring or the like of the object to be treated as much as possible.

Therefore, some aspects of the present invention provide a composition for semiconductor processing, which suppresses damage to metal wirings and the like of an object to be processed, and a processing method using the same, by solving at least a part of the above-mentioned problems. The damage can effectively remove contamination from the surface of the object to be treated. [means to solve the problem]

The present invention is made to solve at least a part of the above-mentioned problems, and can be realized as the following aspects or application examples.

[Application Example 1] An aspect of the composition for semiconductor processing of the present invention is a composition for semiconductor processing, which is a concentrated composition for semiconductor processing and characterized by containing 3×10 ¹ pieces/mL to 1.5 ×10 ³ particles/mL particles with a particle diameter of 0.1 μm to 0.3 μm.

[Application Example 2] Like the composition for semiconductor processing of Application Example 1, it can be diluted to 1 to 500 times and used.

[Application Example 3] An aspect of the composition for semiconductor processing of the present invention is a composition for semiconductor processing, which is used undiluted and characterized by containing 3×10 ¹ pieces/mL to 1.5 ^{×10 3} pieces Particles with a particle size of 0.1 μm to 0.3 μm per mL.

[Application Example 4] The semiconductor processing composition of any one of Application Examples 1 to 3 may further contain an organic acid.

[Application Example 5] The semiconductor processing composition of any one of Application Examples 1 to 4 may further contain a water-soluble polymer.

[Application Example 6] An aspect of the processing method of the present invention is characterized by including the steps of: using the semiconductor processing composition as in any one of Application Examples 1 to 5, and applying copper or tungsten as a wiring material and containing copper or tungsten as a wiring material At least one selected from the group consisting of tantalum, titanium, cobalt, ruthenium, manganese, and compounds of these metals is processed as a wiring substrate of a barrier metal material.

[Application Example 7] An aspect of the processing method of the present invention is characterized by including the step of: chemically mechanically conducting chemical mechanical processing on the wiring board containing tungsten as a wiring material of the wiring board using a composition containing iron ions and a peroxide. After grinding, the composition for semiconductor processing as in any one of Application Example 1 to Application Example 5 was used for processing. [Effect of invention]

According to the composition for semiconductor processing of the present invention, damage to the metal wiring or the like of the object to be processed can be suppressed, and contamination can be effectively removed from the surface of the object to be processed.

Hereinafter, suitable embodiments of the present invention will be described in detail. In addition, this invention is not limited to the following embodiment, The various modification implemented in the range which does not change the meaning of this invention is included.

1. Composition for Semiconductor Processing A composition for semiconductor processing according to one embodiment of the present invention is characterized by containing 3×10 ¹ to 1.5 ^{×10 3} particles/mL of particles with a particle diameter of 0.1 μm to 0.3 μm. The semiconductor processing composition of the present embodiment may be a concentrated type intended for use after being diluted with a liquid medium such as pure water or an organic solvent, or a undiluted type intended to be used without dilution. In this specification, the term "semiconductor processing composition" is interpreted as including the concept of both the concentrated type and the non-diluted type when the concentrated type or the non-diluted type is not specified.

Such a composition for semiconductor processing is mainly used as a cleaning agent for removing particles, metal impurities, etc. existing on the surface of the object to be processed after CMP, and for peeling off the resist from a semiconductor substrate processed with a resist. A resist stripper for an etchant and a treatment agent such as an etchant for shallow etching the surface of metal wiring and the like to remove surface contamination. The term "treatment agent" in the present invention is a concept including a cleaning agent, a resist stripper, an etchant, and the like for cleaning such a semiconductor surface. Hereinafter, each component contained in the composition for semiconductor processing of the present embodiment will be described in detail.

1.1. Particles with a particle diameter of 0.1 μm to 0.3 μm The semiconductor processing composition of the present embodiment contains 3×10 ¹ /mL to 1.5 ^{× 10 3} particles/mL of particles with a particle diameter of 0.1 μm to 0.3 μm (hereinafter Also known as "specific particles"). It is considered that the composition for semiconductor processing of the present embodiment can effectively scrape off and remove the polishing dust remaining on the surface to be processed in the processing step by containing the specific particles in a predetermined ratio. On the other hand, when the content ratio of the specific particles contained in the composition for semiconductor processing exceeds the above-mentioned range, the specific particles remain on the surface to be processed after the treatment, which induces electrical characteristics of the semiconductor circuit as the object to be processed. It is not preferable because of the decrease in yield due to deterioration and the like. On the other hand, when the content ratio of the specific particles contained in the composition for semiconductor processing is smaller than the above-mentioned range, it is considered that it is difficult to effectively scrape off the abrasive dust adhering to the surface to be processed, and the flatness of the surface to be processed is considered to be deterioration.

Generally, as described in International Publication No. 1999/049997 and the like, in the manufacturing process of a semiconductor device, particles are understood as foreign matter that should be removed as much as possible. However, in the present invention, the conventional concept was overturned, and it was found that when the surface to be treated is treated with a composition for semiconductor treatment containing particles having a particle diameter of 0.1 μm to 0.3 μm in a predetermined ratio, there is a possibility that the semiconductor The characteristics are greatly degraded, and on the contrary, the processing characteristics are improved.

The specific particles contained in the composition for semiconductor processing of the present embodiment are preferably metal particles or metal oxide particles, and more preferably insulating particles.

Such metal particles or metal oxide particles can be used, for example: iron, titanium, aluminum, zirconium, magnesium and oxides of these metals (iron oxide, titanium oxide, aluminum oxide, zirconium oxide, magnesium oxide, etc.), silicon dioxide , stainless steel (SUS201, SUS202, SUS301, SUS302, SUS303, SUS304, SUS305, SUS316, SUS317, SUS403, SUS405, SUS420, SUS430, SUS630, etc.), etc. Among these substances, iron oxide, stainless steel, titanium oxide, silicon dioxide, and oxide are preferred in terms of effectively removing the abrasive dust adhering to the surface to be processed without deteriorating the electrical characteristics of the semiconductor circuit. Aluminum, more preferably silicon dioxide.

In addition, the specific particles preferably contain a ratio (Rmax/Rmin) of a major axis (Rmax) to a minor axis (Rmin), preferably 1.3 or more, more preferably 1.4 or more and 3.0 or less, particularly preferably 1.5 or more and 2.5 or less specific particles of the shape of (hereinafter also referred to as "specifically shaped particles"). Since the semiconductor processing composition of the present embodiment contains particles of a specific shape, the effect of removing the abrasive dust adhering to the surface to be processed is enhanced. Furthermore, since the specific-shaped particle has a concave-convex shape, components such as a water-soluble polymer, an organic acid, and an amine, which will be described later, can be taken into or released from the concave portion. Therefore, it is considered that in the treatment step, these components are released effectively.

When the total mass of the specific particles contained in the composition for semiconductor processing of the present embodiment is set to 100 parts by mass, the specific particles preferably contain 30 parts by mass or more of particles of a specific shape, more preferably 40 parts by mass or more, It is especially preferable to contain 50 mass parts or more.

Here, the major diameter (Rmax) of a particle refers to the longest distance between the ends of the particle image passing through the center of gravity of the particle image and connecting the ends of the particle image for one independent particle image captured by a transmission electron microscope. distance. On the other hand, the short diameter (Rmin) of a particle refers to the distance between the ends of the particle image passing through the center of gravity of the particle image and connecting the ends of the particle image to an independent particle image captured by a transmission electron microscope. shortest distance.

Here, the particle diameter of the particles and the content of the particles in the composition for semiconductor processing can be measured using a particle size distribution analyzer using a laser diffraction method as a measurement principle. The particle diameter in the present invention is the value of the particle diameter (D50) at which the cumulative frequency of the number of particles when the particle number is accumulated from the small particles is 50% when the particle size distribution is measured using the particle size distribution analyzer. Examples of such a laser diffraction particle size distribution analyzer include HORIBA LA-300 series and HORIBA LA-920 series (the above are manufactured by HORIBA, Ltd.). In this particle size distribution measuring apparatus, not only primary particles of particles but also secondary particles formed by agglomeration of primary particles are used as evaluation targets. Therefore, the particle diameter obtained by this particle size distribution measuring apparatus can be set as an index of the dispersion state of the particles contained in the composition for semiconductor processing.

In addition, in CMP of the to-be-polished body containing tungsten as a wiring material, the CMP slurry containing iron ion and peroxide (hydrogen peroxide, potassium iodate, etc.) is used. The iron ions contained in the CMP slurry are easily adsorbed on the surface of the object to be polished, so the surface to be polished is easily contaminated with iron. In this case, it is considered that by cleaning the surface to be polished using the semiconductor processing composition of the present embodiment, the iron contamination of the surface to be polished can be shaved off by specific particles and effectively removed.

1.2. Other components The semiconductor processing composition of the present embodiment may contain water-soluble polymers, organic acids, amines, and other components in addition to the liquid medium as the main component.

1.2.1. Water-soluble polymer The semiconductor processing composition of the present embodiment may contain a water-soluble polymer. The water-soluble polymer has the function of adsorbing on the surface of the treated surface to reduce corrosion. Therefore, when a water-soluble polymer is added to the composition for semiconductor processing, corrosion of the surface to be processed can be reduced. In addition, the term "water-soluble" in the present invention means that the mass dissolved in 100 g of water at 20°C is 0.1 g or more. In addition, the "water-soluble polymer" in the present invention refers to a water-soluble compound in which two or more repeating units are connected in a linear or network form via covalent bonds.

Examples of such water-soluble polymers include polyacrylic acid, polymethacrylic acid, polymaleic acid, polyvinylsulfonic acid, polyallylsulfonic acid, polystyrenesulfonic acid, and salts of these acids; styrene , copolymers of monomers such as α-methylstyrene and 4-methylstyrene and acid monomers such as (meth)acrylic acid and maleic acid, or the condensation of benzenesulfonic acid and naphthalenesulfonic acid with formalin. Polyvinyl alcohol, polyoxyethylene, polyvinyl pyrrolidone, polyvinyl pyridine, polyacrylamide, polyvinyl methyl composed of polymers containing repeating units with aromatic hydrocarbon groups and salts of these polymers; Ethylene-based synthetic polymers such as amide, polyethyleneimine, polyvinyloxazoline, polyvinylimidazole, and polyallylamine; modification of natural polysaccharides such as hydroxyethyl cellulose, carboxymethyl cellulose, and processed starch substances, etc., but not limited to these substances. These water-soluble polymers may be used alone or in combination of two or more.

The water-soluble polymer used in the present embodiment may be a homopolymer or a copolymer obtained by copolymerizing two or more monomers. Such monomers can be used: monomers with carboxyl groups, monomers with sulfonic acid groups, monomers with hydroxyl groups, monomers with polyethylene oxide chains, monomers with amine groups, monomers with heterocycles body etc.

The weight average molecular weight (Mw) of the water-soluble polymer used in the present embodiment is preferably 1 thousand or more and 1.5 million or less, and more preferably 3 thousand or more and 1.2 million or less. In addition, the "weight average molecular weight" as used in this specification means the weight average molecular weight in terms of polyethylene glycol measured by gel permeation chromatography (Gel Permeation Chromatography, GPC).

The content of the water-soluble polymer can be adjusted so that the viscosity at room temperature of the composition for semiconductor processing becomes 2 mPa·s or less. When the viscosity of the composition for semiconductor processing at room temperature exceeds 2 mPa·s, the viscosity may become too high, so that the composition for semiconductor processing may not be stably supplied to the object to be processed. The viscosity of the composition for semiconductor processing is roughly determined by the weight average molecular weight or content of the water-soluble polymer to be added, so it can be adjusted while considering the balance of these.

In addition, the content of the water-soluble polymer may depend on the material 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, which are exposed on the surface of the object to be processed after CMP. Or the composition of the CMP slurry to be used is appropriately changed.

Furthermore, the content of the water-soluble polymer may be appropriately changed according to the degree of dilution of the concentrated semiconductor processing composition of the present embodiment. The lower limit of the content of the water-soluble polymer is preferably 0.001 per 100 parts by mass of the processing agent prepared by diluting the concentrated semiconductor processing composition or the non-diluted semiconductor processing composition (processing agent). The amount is more than or equal to 0.01 part by mass, and the upper limit is preferably less than or equal to 1 part by mass, and more preferably less than or equal to 0.1 part by mass. When the content of the water-soluble polymer is within the above range, the inhibition of corrosion is promoted and the effect of removing particles and metal impurities contained in the CMP slurry from the wiring board is coexisted, and a better processed surface is easily obtained.

1.2.2. Organic acid The semiconductor processing composition of the present embodiment may contain an organic acid. The organic acid preferably has one or more acidic groups such as a carboxyl group and a sulfo group. In addition, the "organic acid" in this invention is a concept which does not include the said water-soluble polymer.

Specific examples of organic acids include: citric acid, maleic acid, malic acid, tartaric acid, oxalic acid, malonic acid, succinic acid, EDTA, acrylic acid, methacrylic acid, benzoic acid, phenyllactic acid, hydroxybenzene Lactic acid, phenylsuccinic acid, naphthalene sulfonic acid and salts of these acids, etc. These organic acids may be used alone or in combination of two or more.

As the organic acid, amino acid may also be used. Examples of the amino acid include compounds represented by the following general formula (1).

（所述通式（1）中，R¹ 表示選自由氫原子、碳數1～10的烴基及具有雜原子的碳數1～20的有機基所組成的組群中的任一個）[hua 1]

(In the general formula (1), R ¹ represents any one selected from the group consisting of a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, and an organic group having 1 to 20 carbon atoms having a hetero atom.)

^{Examples of the hydrocarbon group having 1 to 10 carbon atoms in R 1} in the general formula (1) include a saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms, a cyclic saturated hydrocarbon group having 1 to 10 carbon atoms, and a cyclic saturated hydrocarbon group having 1 to 10 carbon atoms. Among these groups, a saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms is preferred.

^{Examples of the organic group having 1 to 20 carbon atoms in R 1} in the general formula (1) include: a hydrocarbon group having 1 to 20 carbon atoms having a carboxyl group, a hydrocarbon group having 1 to 20 carbon atoms having a hydroxyl group, A hydrocarbon group having 1 to 20 carbon atoms having an amine group, a hydrocarbon group having 1 to 20 carbon atoms having a mercapto group, an organic group having 1 to 20 carbon atoms having a heterocyclic ring, etc. These groups may further contain oxygen, sulfur, halogen and other heteroatoms, a part of which may also be substituted by other substituents.

Examples of the compound represented by the general formula (1) include alanine, arginine, asparagine, aspartic acid, cysteine, glutamine, glutamic acid, glycine, and isoleucine. Amino acid, leucine acid, lysine acid, methionine, phenylalanine, serine, threonine, tyrosine, valine, tryptophan, histidine, 2-amino- 3-aminopropionic acid, etc. These amino acids may be used alone or in combination of two or more.

It is also preferable to use a compound represented by the following general formula (2) as the organic acid.

（所述通式（2）中，R² 表示碳數1～20的有機基）[hua 2]

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

^{Examples of the organic group having 1 to 20 carbon atoms in R 2} in the general formula (2) include: a saturated aliphatic hydrocarbon group having 6 to 20 carbon atoms, an unsaturated aliphatic hydrocarbon group having 6 to 20 carbon atoms, a cyclic A saturated hydrocarbon group having 6 to 20 carbon atoms, an organic group having an unsaturated cyclic hydrocarbon group having 6 to 20 carbon atoms, a carboxyl group having a carbon number of 1 to 20, a hydroxyl group having a carbon number of 1 to 20, A hydrocarbon group having 1 to 20 carbon atoms having an amine group, an organic group having 1 to 20 carbon atoms having a heterocyclic group, etc. Among them, an organic group having 6 to 20 carbon atoms having an unsaturated cyclic hydrocarbon group or a carboxyl group is preferred The hydrocarbon group having 1 to 20 carbon atoms is particularly preferably an organic group having 6 to 20 carbon atoms or a carboxymethyl group having an aryl group. However, the compound represented by the general formula (2) excludes the compound represented by the general formula (1).

Specific examples of the compound represented by the general formula (2) include hydroxyphenyllactic acid, hydroxymalonic acid, and the like, and among these compounds, hydroxyphenyllactic acid is preferred. The exemplified compounds may be used alone or in combination of two or more.

The content of the organic acid depends on the material of the metal wiring material such as copper or tungsten, the insulating material such as silicon oxide, and the barrier metal material such as tantalum nitride or titanium nitride exposed on the surface of the object to be processed after CMP, or the material used. The composition of the CMP slurry is appropriately changed.

Furthermore, the content of the organic acid may be appropriately changed according to the degree of dilution of the concentrated semiconductor processing composition of the present embodiment. Regarding the content of the organic acid, the lower limit is preferably 0.0001 part by mass with respect to 100 parts by mass of the processing agent prepared by diluting the concentrated semiconductor processing composition or the non-diluted type semiconductor processing composition (processing agent) Above, more preferably 0.0005 part by mass or more, and the upper limit is preferably 1 part by mass or less, more preferably 0.5 part by mass or less. When the content of the organic acid is within the above range, impurities adhering to the surface of the wiring material can be effectively removed. In addition, the progress of overetching can be suppressed more effectively, and a favorable processed surface can be obtained.

1.2.3. Amine The semiconductor processing composition of the present embodiment may contain an amine (except for amino acids). It is considered that the amine functions as an etchant. It can be considered that by adding amine, metal oxide films (such as CuO, Cu ₂ O and Cu(OH) ₂ layers) or organic residues (such as benzotriazole ( Benzotriazole, BTA) layer) etch removed.

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

Examples of the alkanolamine include monoethanolamine, diethanolamine, triethanolamine, N-methylethanolamine, N-methyl-N,N-diethanolamine, N,N-dimethylethanolamine, and N,N-diethylethanolamine , N,N-dibutylethanolamine, N-(β-aminoethyl)ethanolamine, N-ethylethanolamine, monopropanolamine, dipropanolamine, tripropanolamine, monoisopropanolamine, dipropanolamine isopropanolamine, triisopropanolamine, etc. The primary amines include methylamine, ethylamine, propylamine, butylamine, pentylamine, 1,3-propanediamine, and the like. Piperidine, piperazine, etc. are mentioned as a secondary amine. Trimethylamine, triethylamine, etc. are mentioned as a tertiary amine. These amines may be used alone or in combination of two or more.

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

The content of the amine depends on the material of metal wiring materials such as copper or tungsten, insulating materials such as silicon oxide, barrier metal materials such as tantalum nitride or titanium nitride, etc. exposed on the surface of the object to be processed after CMP, or the CMP used. The composition of the slurry is appropriately changed.

Furthermore, the content of the amine may be appropriately changed according to the degree of dilution of the concentrated semiconductor processing composition of the present embodiment. Regarding the content of the amine, the lower limit is preferably 0.0001 part by mass or more with respect to 100 parts by mass of the treatment agent prepared by diluting the concentrated semiconductor treatment composition or the non-diluted type semiconductor treatment composition (treatment agent) , more preferably 0.0005 part by mass or more, and the upper limit is preferably 1 part by mass or less, more preferably 0.5 part by mass or less. If the content of the amine is within the above-mentioned range, the metal oxide film and the organic residue on the wiring substrate can be more efficiently removed by etching in the processing step after the CMP.

1.2.4. Liquid medium The semiconductor processing composition of the present embodiment is a liquid containing a liquid medium as a main component. The type of the liquid medium can be appropriately selected for the object to be treated according to the purpose of use of the treatment agent such as cleaning, etching, and resist stripping. For example, when the composition for semiconductor processing is used as a cleaning agent, the liquid medium preferably has water as a main component and can function as a solvent, and is not particularly limited. Examples of such a liquid medium include water, a mixed medium of water and alcohol, a mixed medium containing water and an organic solvent compatible with water, and the like. Among these media, it is preferable to use a mixed medium of water, water and alcohol, and it is more preferable to use water.

In addition, for example, when the composition for semiconductor processing is used as an etchant or a resist stripper, the liquid medium preferably has an organic solvent as a main component and can function as a solvent, and is not particularly limited. Examples of such organic solvents include polar solvents such as ketone-based solvents, ester-based solvents, ether-based solvents, and amide-based solvents, and known organic solvents that can be used in semiconductor processing such as hydrocarbon-based solvents.

Examples of the ketone-based solvent include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone, 4-heptanone, 1-hexanone, 2-hexanone, di- Isobutyl ketone, cyclohexanone, methyl cyclohexanone, phenyl acetone, methyl ethyl ketone, methyl isobutyl ketone, acetone acetone, acetone acetone, ionone, diacetone alcohol, acetone Base alcohol, acetophenone, methyl naphthyl ketone, isophorone, propylene carbonate, γ-butyrolactone, etc.

As the ester-based solvent, for example, chain-shaped ester-based solvents include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, ethyl methoxyacetate, ethoxylate Ethyl ethyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate Esters, diethylene glycol monomethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monophenyl ether acetate, diethylene glycol mono Butyl ether acetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate Ethyl acetate, 3-ethyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, 2-ethoxybutyl Ethyl 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-methyl acetate Oxypentyl acetate, 4-methyl-4-methoxypentyl acetate, propylene glycol diacetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl carbonate, Propyl carbonate, butyl carbonate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, butyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl propionate, ethyl propionate, Propionate, Isopropylpropionate, Methyl-3-methoxypropionate, Ethyl-3-methoxypropionate, Ethyl-3-ethoxypropionate, Propyl- 3-methoxypropionate, etc. Moreover, lactones, such as γ-butyrolactone, etc. are mentioned as a cyclic ester solvent.

Examples of ether-based solvents include glycol ethers 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. Solvents; diisoamyl ether, diisobutyl ether, dioxane, tetrahydrofuran, anisole, perfluoro-2-butyltetrahydrofuran, perfluorotetrahydrofuran, 1,4-dioxane, etc.

Examples of the amide-based solvent include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, hexamethylphosphoric triamine, 1 , 3-dimethyl-2-imidazolidinone, etc. As said other polar solvent, dimethyl sulfite etc. are mentioned.

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

1.2.5. Other components The semiconductor processing composition of the present embodiment may contain necessary components as appropriate, for example, pH adjusters, surfactants, and the like.

<pH adjuster> When the semiconductor processing composition of the present embodiment treats a surface to be treated containing copper as a wiring material, the lower limit of pH is preferably 9 or more, more preferably 10 or more, and pH The upper limit of the value is preferably 14 or less. When processing the surface to be processed containing tungsten as a wiring material, the upper limit of pH is preferably 7 or less, more preferably 6 or less, and the lower limit of pH is preferably 2 or more.

In the semiconductor processing composition of the present embodiment, when the desired pH cannot be obtained by adding the organic acid or amine, the pH may be separately added in order to adjust the pH within the range described above. adjuster. Examples of pH adjusters include hydroxides of alkali metals such as sodium hydroxide, potassium hydroxide, rubidium hydroxide, and cesium hydroxide, organic ammonium salts such as tetramethylammonium hydroxide, and basic compounds such as ammonia. These pH adjusters may be used alone or in combination of two or more.

<Surfactant> Well-known components can be used suitably as a surfactant, and a nonionic surfactant or an anionic surfactant can be used suitably. By adding a surfactant, the effect of removing particles or metal impurities contained in the CMP slurry from the wiring substrate may be improved, and a better processed surface may be obtained.

Examples of nonionic surfactants include polyoxyethylene such as polyoxyethylidene lauryl ether, polyoxyethylidene cetyl ether, polyoxyethylidene stearyl ether, and polyoxyethylidene oleyl ether. Ethylene glycol alkyl ether; polyoxyethylidene aryl ether such as polyoxyethylidene octylphenyl ether, polyoxyethylene nonylphenyl ether, etc.; sorbitan monolaurate, sorbitan mono Sorbitan fatty acid esters such as palmitate and sorbitan monostearate; polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan Polyoxyethylene sorbitan fatty acid esters such as sorbitan monostearate and the like. The exemplified nonionic surfactants may be used alone or in combination of two or more.

Examples of the anionic surfactant include: alkylbenzenesulfonic acids such as dodecylbenzenesulfonic acid; alkylnaphthalenesulfonic acids; alkyl sulfates such as lauryl sulfate; Sulfuric ester of ethyl alkyl ether; naphthalene sulfonic acid condensate; alkyl imino dicarboxylic acid; lignin sulfonic acid, etc. These anionic surfactants can also be used in the form of a salt. In this case, as a counter cation, a sodium ion, a potassium ion, an ammonium ion etc. are mentioned, for example, From a viewpoint of preventing excessively containing potassium or sodium, an ammonium ion is preferable.

In the CMP of the object to be processed containing tungsten as a wiring material, a CMP slurry containing iron ions and peroxides (hydrogen peroxide, potassium iodate, etc.) is used. The iron ions contained in the CMP slurry are easily adsorbed on the surface of the object to be treated, so the surface of the object to be treated is easily contaminated with iron. In this case, since iron ions are positively charged, iron contamination on the surface of the object to be processed may be effectively removed by adding an anionic surfactant to the composition for semiconductor processing.

The content of the surfactant can depend on the material or use of metal wiring materials such as copper or tungsten exposed on the surface of the object to be processed after CMP, insulating materials such as silicon oxide, and barrier metal materials such as tantalum nitride or titanium nitride. The composition of the CMP slurry is appropriately changed.

Furthermore, the content of the surfactant may be appropriately changed according to the degree of dilution of the concentrated semiconductor processing composition of the present embodiment. The content of the surfactant is preferably 0.001 part by mass or more and 1 mass part with respect to 100 parts by mass of the processing agent prepared by diluting the concentrated semiconductor processing composition or the undiluted type semiconductor processing composition (processing agent) copies or less. If the content of the surfactant is within the above range, the corrosion of the object to be treated can be reduced and organic residues can be efficiently removed in the treatment step after the CMP.

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

In the method for producing a composition for semiconductor processing according to the present embodiment, it is preferable to control the amount of particles by filtering with a depth filter or a pleated filter as necessary. The depth filter here is a high-precision filter also called a depth filter or a volume filter. Such a depth filter includes a filter having a layered structure in which filter membranes having a large number of pores are stacked, or a filter in which a fiber bundle is wound. Specific examples of depth filters include: Profile II, Nexis NXA, Nexis NXT, Polyfine XLD, Ultipleat Profile), etc. (all manufactured by Pall Japan), depth cartridge filter, wynd cartridge filter, etc. (all manufactured by Advantec), CP Filters, BM filters, etc. (all by Chisso), Slope-Pure, Dia, Microsyria, etc. (all by Rocky Technology (manufactured by Roki Techno) etc.

For the pleated filter, a microfiltration membrane sheet composed of non-woven fabric, filter paper, wire mesh, etc. is folded, formed into a cylindrical shape, the seams of the pleats of the sheet are liquid-tightly sealed, and the The obtained cylindrical high-precision filter filter is liquid-tightly sealed at both ends. Specific examples include: HDCII, Polyfine II, etc. (all manufactured by Pall Japan), PP pleated cartridge filter (manufactured by Advantec) , Porous Fine (made by Chisso), Sarton Pore, Micropure, etc. (all made by Roki Techno), etc.

The filter is preferably a filter with a nominal filtering accuracy of 0.01 μm to 20 μm. By using a filter whose nominal filtration precision is within the above-mentioned range, a filtrate in which the number of particles having a particle diameter of 20 μm or more per 1 mL when measured by a particle counter is 0 can be obtained efficiently. In addition, since the number of coarse particles captured by the filter is minimized, the usable period of the filter is extended.

2. Treatment agent The term “treatment agent” in the present invention refers to a treatment agent prepared by adding a liquid medium to the concentrated semiconductor processing composition and diluting it, or the non-diluted semiconductor processing composition. The object itself, and refers to the liquid agent used in the actual treatment of the surface to be treated. Dilute the concentrated semiconductor processing composition with a suitable liquid medium to prepare a processing agent, or use the undiluted semiconductor processing composition as a processing agent as it is, and use the processing agent as a cleaning agent or an etchant , resist stripper for use.

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

A method of adding a liquid medium to the concentrated semiconductor processing composition and diluting it includes the following method: the piping for supplying the concentrated semiconductor processing composition and the piping for supplying the liquid medium are merged and mixed in the middle, and the mixture is mixed. The mixed treatment agent is supplied to the surface to be treated. For this mixing, the following methods can be used: a method in which liquids are collided and mixed with each other through a narrow passage under pressure; a method in which a filler such as a glass tube is filled in piping, and the flow of liquids is repeatedly separated and merged; A method commonly performed, such as a method of installing a blade that rotates by power.

In addition, another method of adding a liquid medium to the concentrated semiconductor processing composition and diluting it includes a method in which piping for supplying the concentrated semiconductor processing composition and piping for supplying the liquid medium are provided independently, and each pipe A predetermined amount of liquid is supplied to the surface to be treated and mixed on the surface to be treated. Furthermore, as another method of adding a liquid medium to the concentrated semiconductor processing composition and diluting it, there is a method in which a predetermined amount of the concentrated semiconductor processing composition and a predetermined amount of the liquid medium are added to a container, and the After mixing, the mixed treatment agent is supplied to the surface to be treated.

Regarding the dilution ratio when adding a liquid medium 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 mass parts parts (1 to 500 times), more preferably 20 to 500 parts by mass (20 to 500 times), particularly preferably 30 to 300 parts by mass (30 to 300 times). Furthermore, it is preferable to dilute with the same liquid medium as the liquid medium contained in the above-mentioned concentrated semiconductor processing composition. By setting the composition for semiconductor processing in a concentrated state in this way, it is possible to transport or store the processing agent in a smaller container than the case where the processing agent is directly transported and stored. As a result, the cost of transportation or storage can be reduced. In addition, compared with the case where the treatment agent is directly purified by operations such as filtration, a smaller amount of the treatment agent can be purified, so that the purification time can be shortened, thereby enabling mass production.

3. Treatment method A treatment method according to an embodiment of the present invention includes the steps of: using the semiconductor treatment composition (as the treatment agent, specifically, a cleaning agent, an etchant, a resist stripper, etc.), A wiring substrate containing copper or tungsten as a wiring material and containing at least one selected from the group consisting of tantalum, titanium, cobalt, ruthenium, manganese and compounds of these metals as a barrier metal material is processed. Hereinafter, an example of the processing method of the present embodiment will be described in detail using the drawings.

<Production of Wiring Board> FIG. 1 is a cross-sectional view schematically showing a production process of a wiring board used in the processing method of the present embodiment. This wiring board is formed by going through the following processes.

FIG. 1 is a cross-sectional view schematically showing a to-be-processed object before CMP processing. As shown in FIG. 1 , the object to be processed 100 has a base body 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 body 10 .

The object to be processed 100 is formed by laminating the insulating film 12 provided with the wiring recess 20 on the base 10 in this order, the barrier metal film 14 provided so as to cover the surface of the insulating film 12 and the bottom and inner wall surface of the wiring recess 20 , and the metal film 16 that fills the wiring recess 20 and is formed on the barrier metal film 14 .

The insulating film 12 can be, for example, a silicon oxide film formed by a vacuum process (such as a plasma enhanced tetraethoxysilane film (PETEOS film), a high-density plasma enhanced tetraethoxysilane film ( High Density Plasma Enhanced-TEOS film, HDP film), silicon oxide film obtained by thermal chemical vapor deposition, etc.), insulation called Fluorine-doped silicate glass (FSG) Film, Boro Phospho Silicate Glass film (BPSG film), insulating film called SiON (Silicon oxynitride), silicon nitride (Siliconnitride), etc.

Examples of the barrier metal film 14 include tantalum, titanium, cobalt, ruthenium, manganese, and compounds of these metals. The barrier metal film 14 is usually formed of one of these metals, but two or more of them, such as tantalum and tantalum nitride, may be used in combination.

The metal film 16 must completely fill the wiring recess 20 as shown in FIG. 1 . Therefore, metal films of 10,000 Å to 15,000 Å are usually deposited by chemical vapor deposition or electroplating. The material of the metal film 16 may be copper or tungsten, and 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.

Next, the metal film 16 other than the portion buried in the wiring recess 20 in the object to be processed 100 of FIG. 1 is polished at 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 way, the wiring board 200 as shown in FIG. 2 is obtained.

<Treatment of wiring board> Next, the surface (surface to be processed) of the wiring board 200 shown in FIG. 2 is processed using the above-mentioned processing agent (cleaning agent). According to the processing method of the present embodiment, when processing the wiring substrate in which the wiring material and the barrier metal material coexist on the surface after CMP, the corrosion of the wiring material and the barrier metal material can be suppressed, and the wiring substrate can be efficiently removed oxide film or organic residues on it.

The processing method of the present embodiment is applied to a wiring material containing tungsten as a wiring board using the composition (Fenton's reagent) containing iron ions and peroxides described in Japanese Patent Laid-Open No. 10-265766 and the like It is very effective to carry out chemical mechanical polishing of the wiring substrate. In the CMP of the object to be processed containing tungsten as a wiring material, a CMP slurry containing iron ions and peroxides (hydrogen peroxide, potassium iodate, etc.) is used. The iron ions contained in the CMP slurry are easily adsorbed on the surface of the object to be treated, so the surface of the object to be treated is easily contaminated with iron. In this case, iron contamination can be removed by treating the surface of the object to be treated with dilute hydrofluoric acid, but the surface of the object to be treated is easily damaged by etching. However, the composition for semiconductor processing contains specific particles in a predetermined ratio, and it is considered that the specific particles can effectively remove iron contamination on the surface of the object to be processed by shaving.

The processing method is not particularly limited, and can be performed by a method in which the cleaning agent is brought into direct contact with the wiring board 200 . The methods of directly contacting the cleaning agent with the wiring board 200 include: a dipping method in which a cleaning tank is filled with the cleaning agent and the wiring board is immersed; a rotation method in which the wiring board is rotated at a high speed while the cleaning agent flows down from a nozzle onto the wiring board A method; a method such as a spray type for cleaning a wiring board by spraying a cleaning agent. In addition, the apparatus for performing such a method includes a batch type cleaning apparatus that simultaneously cleans a plurality of wiring boards housed in a cassette, and a single-chip type cleaning apparatus that mounts and cleans one wiring board on a holder. cleaning equipment, etc.

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

In addition to the above-described method of directly contacting the cleaning agent with the wiring board 200, it is also preferable to use a treatment method using physical force in combination. Thereby, the removability of contamination caused by the particles adhering to the wiring board 200 is improved, and the processing time can be shortened. As a treatment method using physical force, wiping cleaning using a cleaning brush or ultrasonic cleaning is exemplified.

Furthermore, you may wash with ultrapure water or pure water before and/or after the washing|cleaning by the processing method of this embodiment.

4. Examples

Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples at all. In addition, "part" and "%" in this Example are a quality standard unless otherwise specified.

4.1. Example 1

4.1.1. Preparation of semiconductor processing composition (concentrated type)

Each component was added to a polyethylene container so that the content ratio shown in Table 1, an appropriate amount of ion-exchanged water was added, and the mixture was stirred for 15 minutes. To this mixture, ion-exchanged water, potassium hydroxide, and sodium hydroxide were added as necessary so that the total amount of all the constituent components would be 100 parts by mass, and the mixture was prepared so that the pH value, K content, and Na content shown in Table 1 were obtained. composition.

To 100 parts by mass of the composition thus obtained, 0.01 part by mass of colloidal silica (trade name "PL-1", manufactured by Fuso Chemical Industry Co., Ltd., primary particle size 15 nm) was added, and the filter was filtered using the filter shown in FIG. 3 . The apparatus 300 performs filtering (filtering step). The filter device 300 shown in FIG. 3 includes a supply tank 210 for storing and supplying the composition before foreign matter removal, a metering pump 220 for flowing the composition before foreign matter removal at a constant flow rate, and a filter element (not shown in the figure). ) and the filter 240 housing (installed) the housing of the filter element, the anti-pulsation actuator 230 located in the middle of the quantitative pump 220 and the filter 240, and the first pressure gauge 270a arranged between the anti-pulsation actuator 230 and the filter 240 , and the second pressure gauge 270b disposed downstream of the filter 240 . Further, the filter device 300 includes a return conduit 260 for returning the semiconductor processing composition from the filter 240 to the supply tank 210 , and a discharge conduit 250 for discharging the semiconductor processing composition filtered by the filter 240 .

In this embodiment, the filter 240 is a membrane filter element “Water Fine” (manufactured by Pall Japan) installed in the housing, with a nominal filtration accuracy of 0.05 μm, 10 inches in length). The fixed pump 220 was an air-driven diaphragm pump, and was set so that the differential pressure before and after the filter was 0.2 MPaG to 0.3 MPaG, and the flow rate of the composition became the flow rate described in Table 1.

The composition was sampled at an appropriate time, and the filtration was stopped when the number of particles of 0.1 μm to 0.3 μm contained in the composition reached the concentration described in Table 1, and the semiconductor processing composition (concentrated type) of Example 1 was prepared. Furthermore, the number of particles per 1 mL of the composition was measured as follows.

Specifically, first, ultrapure water is used so that the number of particles to be measured becomes "30 particles/mL (0.1 μm)" (that is, "30 particles with a particle size larger than 0.1 μm per 1 mL"). Blank assays were repeated. Then, 100 mL of a concentrated semiconductor processing composition (sample) was prepared, and the sample was set in a syringe sampler "KZ-31W". Then, the number of particles with particle diameters of 0.1 μm to 0.3 μm per 1 mL of the sample was measured twice by the sub-liquid particle sensor, and an average value was calculated. The average value was set as the number of particles having a particle diameter of 0.1 μm to 0.3 μm per 1 mL of the composition for semiconductor processing.

4.1.2. Treatment test of wiring board (1) Chemical mechanical polishing step Using a chemical mechanical polishing apparatus "EPO112" manufactured by Ebara Manufacturing Co., Ltd., under the following conditions, a board with a copper wiring pattern (with a PETEOS film of 5000 After the thickness of Å is laminated on a silicon substrate with a diameter of 8 inches, the "SEMATECH 854" mask is used for pattern processing, and a cobalt film with a thickness of 250 Å and a copper seed film with a thickness of 1000 Å are sequentially deposited on it. and a 10,000 Å thick copper-plated film for the test substrate) to be subjected to two-stage chemical mechanical polishing. Furthermore, in the chemical mechanical polishing of the first stage, chemical mechanical polishing is performed on the copper seed film and the copper plating film until the cobalt film is exposed. In the chemical mechanical polishing of the second stage, chemical mechanical polishing is performed on the cobalt film, the copper seed film and the copper plated film until the PETEOS film is exposed.

<Chemical mechanical polishing in the first stage> Aqueous dispersion for chemical mechanical polishing: manufactured by JSR Co., Ltd., "CMS7501/CMS7552" Polishing pad: manufactured by Rodel Nitta Co., Ltd. , "IC1000/SUBA400" Platen speed: 70 rpm Grinding head speed: 71 rpm Grinding head load: 50 g/cm ² Chemical mechanical polishing water-based dispersion supply speed: 200 mL/min Grinding time: 150 seconds

<Chemical mechanical polishing in the second stage> Aqueous dispersion for chemical mechanical polishing: manufactured by JSR Co., Ltd., "CMS8501/CMS8552" Polishing pad: manufactured by Rodel Nitta Co., Ltd. , "IC1000/SUBA400" Platen speed: 70 rpm Grinding head speed: 71 rpm Grinding head load: 250 g/cm ² Chemical mechanical polishing water-based dispersion supply speed: 200 mL/min Grinding time: 60 seconds

(2) Treatment step Ultrapure water (particles with a particle diameter of 0.3 μm or more) was added to the obtained semiconductor processing composition to the obtained surface of the polished substrate at the dilution ratio described in Table 1. 10/mL or less, pH = 6.5) and diluted to prepare a treatment agent (cleaning agent), which was subjected to treatment (cleaning) on the platen under the following conditions. Then, similarly, it is subjected to brush wiping treatment (washing).

<Treatment (cleaning) on the platen> Treatment agent: Treatment agent (cleaning agent) prepared as described above Rotational speed of polishing head: 70 rpm · Loading of polishing head: 100 g/cm ² · Rotational speed of platen: 71 rpm · Treatment agent supply speed : 300 mL/min Processing time: 30 seconds

<Brush erasing treatment (cleaning)> Treatment agent: The treatment agent (cleaning agent) prepared as described above. Upper brush rotation speed: 100 rpm Lower brush rotation speed: 100 rpm Substrate rotation speed: 100 rpm Treatment agent supply Speed: 300 mL/min Processing time: 30 seconds

4.1.3. Evaluation test <Corrosion evaluation> The obtained substrate surface after the treatment was observed at a magnification of 120,000 times using a scanning electron microscope (manufactured by Hitachi High-technology, model "S-4800"). The 0.175 μm copper wiring portion of the pattern was tested to evaluate corrosion. The results are shown in Table 1. In addition, the evaluation criteria are as follows. (Evaluation Criteria) Regarding the number of copper wirings in which corrosion was observed among 10 copper wirings, when the number of copper wirings was 3 or less and no slit was seen between the copper wirings and the barrier metal, it was judged to be very good and expressed as "◎"; ·When there are more than 3 and less than 5 and no slit is seen between the barrier metal and the barrier metal, it is judged to be usable and expressed as "○"; ·If there are more than 5 or less than When a slit is visible between the barrier metals, it is judged as defective and expressed as "X".

<Evaluation of Cleaning (Defect)> Using a wafer defect inspection apparatus (manufactured by KLA-Tencor Co., Ltd., model "KLA2351"), the number of defects on the entire surface of the treated substrate obtained above was measured. The results are shown in Table 1. In addition, the evaluation criteria are as follows. (Evaluation Criteria) Regarding the number of defects on the entire substrate surface, when the number of defects on the entire substrate surface was 250 or less, it was judged to be very good and expressed as "◎"; when it was more than 250 and 500 or less, it was judged to be acceptable. Use and describe as "○"; · In the case of 500 or more, it is judged as defective and expressed as "X".

<Reliability evaluation> Using the obtained treatment agent (cleaning agent), 1,000 substrates subjected to the second-stage chemical mechanical polishing (substrates for testing on which a copper film with a thickness of 5000 Å was laminated) were subjected to the The brush erasing process is continuously performed. Defect inspection was performed on the processed substrate, and a case where the number of defects on the entire substrate surface was more than 250 was regarded as defective. The reliability of the processing agent (cleaning agent) was evaluated by counting the number of defective substrates in 1000 sheets. The results are shown in Table 1. The evaluation criteria are as follows. (Evaluation Criteria) Regarding the number of defective substrates out of 1,000, in the case of 50 or less, it was judged to be very good and expressed as "⊚"; in the case of more than 50 and 100 or less When there are more than 100 pieces, it is judged as defective and expressed as "X".

4.2. Example 2 to Example 26 and Comparative Example 1 to Comparative Example 9 The semiconductor processing composition (concentrated type) was changed to the composition described in Table 1 to Table 2, and set to the composition described in Table 1 to Table 2 Except for the composition of the treatment agent (cleaning agent), the treatment test and evaluation test of the wiring board were carried out in the same manner as in Example 1.

4.3. Example 27 4.3.1. Preparation of the composition for semiconductor processing The composition was changed to the composition described in Table 3, and potassium hydroxide and sodium hydroxide were used as necessary to obtain the pH value, K content, and Na content shown in Table 3 A composition for semiconductor processing (concentrated type) was prepared in the same manner as in Example 1, except that the method was adjusted.

4.3.2. Wiring substrate cleaning test (1) Chemical mechanical polishing step Using a chemical mechanical polishing apparatus "EPO112" manufactured by Ebara Manufacturing Co., Ltd., under the following conditions, a substrate with a copper wiring pattern (a PETEOS film with a After the 5000 Å thickness is laminated on a silicon substrate with a diameter of 8 inches, the "SEMATECH 854" mask is used for pattern processing, and a 250 Å thick cobalt film, a 1000 Å thick tungsten seed crystal film and a tungsten seed crystal film with a thickness of 1000 Å are made on it. One-stage chemical-mechanical polishing was performed on the test substrate formed by sequentially laminating tungsten films with a thickness of 10,000 Å.

<Polishing conditions> Aqueous dispersion for chemical mechanical polishing: Cabot Co., Ltd., "W2000" (slurry containing iron ions and hydrogen peroxide) Polishing pad: Rodel · Nitta) Co., Ltd., "IC1000/SUBA400" · Platen rotation speed: 70 rpm · Grinding head rotation speed: 71 rpm · Grinding head load: 50 g/cm ² · Chemical mechanical polishing aqueous dispersion supply rate: 200 mL /min Grinding time: 150 seconds

(2) Treatment step Ultrapure water (particle size 0.3) was added to the obtained semiconductor processing composition (concentrated type) to the obtained surface of the polished substrate at the dilution ratio described in Table 3. Particles of μm or more are 10 particles/mL or less, pH=6.5) and diluted to prepare a treatment agent (cleaning agent), and then use it for treatment (cleaning) on a platen under the following conditions. Then, similarly, it is used for brush wiping cleaning.

<Treatment (cleaning) on the platen> Treatment agent: the treatment agent (cleaning agent) prepared as described above Polishing head rotation speed: 71 rpm Polishing head load: 100 g/cm ² Platen rotation speed: 70 rpm Treatment agent Supply speed: 300 mL/min Processing time: 30 seconds

<Brush wiping cleaning> Treatment agent: the prepared treatment agent (cleaning agent) Upper brush rotation speed: 100 rpm Lower brush rotation speed: 100 rpm Substrate rotation speed: 100 rpm Treatment agent supply speed: 300 mL/min Processing time: 30 seconds

4.3.3. Evaluation test <Corrosion evaluation> In the same manner as in Example 1, the obtained substrate surface after the treatment was evaluated. The results are shown in Table 3.

<Evaluation of cleaning (defect)> The obtained substrate surface after the treatment was evaluated in the same manner as in Example 1. The results are shown in Table 3.

<Reliability Evaluation> Using the obtained treatment agent (cleaning agent), 1,000 substrates subjected to the chemical mechanical polishing (a test substrate with a tungsten film having a thickness of 3000 Å) were wiped with the brush. Cleaning is performed continuously except cleaning. Defect inspection was performed on the cleaned substrate, and a case where the number of defects on the entire substrate surface was more than 250 was regarded as defective. The reliability of the processing agent (cleaning agent) was evaluated by counting the number of defective substrates in 1000 sheets. The results are shown in Table 3. The evaluation criteria are as follows. (Evaluation Criteria) Regarding the number of defective substrates out of 1,000, in the case of 50 or less, it was judged to be very good and expressed as "⊚"; in the case of more than 50 and 100 or less When there are more than 100 pieces, it is judged as defective and expressed as "X".

4.4. Examples 28 to 31 and Comparative Example 10 The composition for semiconductor processing (concentrated type) was changed to the composition described in Table 3, and the treatment agent (cleaning agent) was set to the composition described in Table 3, except Otherwise, the processing test and evaluation test of the wiring board were carried out in the same manner as in Example 27.

4.5. Examples 32 to 35 and Comparative Examples 11 to 13 Each component was added to a polyethylene container so that the content ratio shown in Table 4 might be obtained, and the mixture was stirred for 15 minutes.

For the composition thus obtained, in addition to using a membrane filter element "PE-Clean (PE-Clean)" (manufactured by Pall Japan, Inc., with a nominal filtration accuracy of 0.05 μm) in the housing of the filter 240, Except for the length of 10 inches), filtration was carried out in the same manner as in Example 1, the composition was sampled at an appropriate time, and the filtration was stopped when the number of particles of 0.1 μm to 0.3 μm contained in the composition reached the concentration described in Table 4, and the preparation The semiconductor processing compositions (non-dilution type) of Examples 32 to 35 and Comparative Examples 11 to 13. A processing test and an evaluation test of a wiring board were carried out in the same manner as in Example 1, except that the obtained composition for semiconductor processing was used as a processing agent (etchant or resist stripper) without dilution.

4.6. Evaluation Results The composition and evaluation results of the composition for semiconductor processing are shown in Tables 1 to 4 below.

[Table 1]

[Table 2]

[table 3]

[Table 4]

In Tables 1 to 4 above, the numerical value of each component represents parts by mass. In each Example and each comparative example, the total amount of each component was 100 parts by mass, and the remainder was ion-exchanged water. In addition, the following components in the above-mentioned Tables 1 to 4 are explained additionally. Polyacrylic acid (Mw=700,000): manufactured by Toagosei Co., Ltd., trade name "Julimar AC-10H" Polyacrylic acid (Mw=55,000): manufactured by Toagosei Corporation, trade name "Julimar" Julimar AC-10L" Polyacrylic acid (Mw = 6,000): manufactured by Toagosei Co., Ltd., trade name "Aron A-10SL" Polymaleic acid (Mw = 2,000): NOF Corporation Co., Ltd., trade name "Nonpol PWA-50W" Polyallylamine (Mw = 25,000): Nittobo Medical Co., Ltd. manufacture, trade name "PAA-25" Polyallylamine (Mw=15,000): manufactured by Nittobo Medical Co., Ltd., trade name "PAA-15" Polystyrenesulfonic acid (Mw=50,000): manufactured by Tosoh Organic Chemical Co., Ltd., Trade name "PS-5H" Styrene-maleic acid copolymer: manufactured by Daiichi Kogyo Co., Ltd., trade name "DKS Discoat N-10" Styrene-maleic acid half ester Copolymer: manufactured by Daiichi Industrial Pharmaceutical Co., Ltd., trade name "DKS Discoat N-14" Sodium Naphthalenesulfonate Formalin Condensate: manufactured by Daiichi Industrial Pharmaceutical Co., Ltd., trade name " Lavelin FD-40" Polyvinyl alcohol (Mw=26,000): manufactured by Kuraray Co., Ltd., trade name "PVA405" Polyethyleneimine (Mw=70,000): Nippon Shokubai Co., Ltd. Co., Ltd., trade name "Epomin P-1000" <Organic acid>

. Serine: manufactured by Riken Chemical Co., Ltd.

． Cysteine: manufactured by Riken Chemical Co., Ltd.

． N-Acetyl-L-cysteine: manufactured by RIKEN CORPORATION

. Histidine: manufactured by Riken Chemical Co., Ltd.

． Arginine: manufactured by Riken Chemical Co., Ltd.

． Aspartic acid: manufactured by RIKEN CORPORATION

． Phenylalanine: manufactured by Kyowa hakko-Bio Co., Ltd.

. Benzoic acid: Product made in DMS (DMS Japan) in Japan

. Hydroxyphenyl lactic acid: manufactured by Tokyo Chemical Industry Co., Ltd.

． Phenylsuccinic acid: manufactured by Tokyo Chemical Industry Co., Ltd.

． Naphthalenesulfonic acid: manufactured by Wako Pure Chemical Industries, Ltd.

. Maleic acid: manufactured by Fuso Chemical Industry Co., Ltd.

<amine>

. Monoethanolamine: manufactured by Lin Junyao Industrial Co., Ltd.

． Isopropanolamine: manufactured by Dongxing Chemical Co., Ltd.

<Other>

. Benzotriazole: manufactured by Chengbei Chemical Industry Co., Ltd., rust inhibitor

. Imidazole: manufactured by Shikoku Chemical Industry Co., Ltd., rust inhibitor

. Ammonium dodecylbenzenesulfonate: manufactured by Tama Chemical Industry Co., Ltd., surfactant

. Ammonium alkyl imino dicarboxylate: manufactured by Takemoto Oil Co., Ltd., interface active sex agent

. TMAH: "Tetramethylammonium Hydroxide", manufactured by Lin Chunyao Industrial Co., Ltd., pH adjuster

. TEAH: "Tetraethylammonium Hydroxide", manufactured by Chunsei Chemical Co., Ltd., pH adjuster

. Choline: manufactured by Tama Chemical Industry Co., Ltd., pH adjuster

． Monomethyltrihydroxyethylammonium hydroxide: manufactured by Yokkaichi Synthetic Co., Ltd., pH adjuster

. Dimethylbis(2-hydroxyethyl)ammonium hydroxide: manufactured by Yokkaichi Synthetic Co., Ltd., pH adjuster

. KOH: manufactured by Kanto Chemical Co., Ltd., pH adjuster

. Ammonium hydroxide: manufactured by Lin Chunyao Industrial Co., Ltd., pH adjuster

<Solvent>

. 2-P: "2-pyrrolidone", manufactured by Wako Pure Chemical Industries, Ltd.

. PG: "Propylene Glycol", manufactured by Wako Pure Chemical Industries, Ltd.

. PGME: "Propylene Glycol Monomethyl Ether", manufactured by Sankyo Chemical Co., Ltd.

. NMP: "N-methylpyrrolidone", manufactured by Mitsubishi Chemical Corporation

Sulfolane: "Cyclobutylene", manufactured by Sankyo Chemical Co., Ltd.

As shown in Tables 1 to 4 above, when the semiconductor processing compositions of Examples 1 to 35 were used, the corrosion state of the substrate surface was suppressed, and the number of defects was also small, so that the processing could be achieved. body in good condition.

The present invention is not limited to the above-described embodiment, and various modifications are possible. For example, the present invention includes substantially the same configuration as the configuration described in the embodiment (for example, configuration having the same function, method, and result, or configuration having the same purpose and effect). Moreover, this invention includes the structure which replaced the non-essential part of the structure demonstrated in embodiment. Moreover, this invention includes the structure which exhibits the same effect as the structure demonstrated in embodiment, or the structure which can achieve the same object. In addition, the present invention includes configurations obtained by adding known techniques to the configurations described in the embodiments.

10‧‧‧Substrate 12‧‧‧Insulating film 14‧‧‧Barrier Metal Film 16‧‧‧Metal Film 20‧‧‧Recess for wiring 100‧‧‧Processed object 200‧‧‧Wiring board 210‧‧‧Supply Box 220‧‧‧Dosing pump 230‧‧‧Anti-pulsation 240‧‧‧Filter 250‧‧‧Exhaust conduit 260‧‧‧Return catheter 270a‧‧‧First pressure gauge 270b‧‧‧Second pressure gauge 300‧‧‧Filtering device

FIG. 1 is a cross-sectional view schematically showing a manufacturing process of a wiring board used in the processing method of the present embodiment. FIG. 2 is a cross-sectional view schematically showing a manufacturing process of a wiring board used in the processing method of the present embodiment. FIG. 3 is a conceptual diagram schematically showing the configuration of the filter device used in the present embodiment.

10‧‧‧Substrate

12‧‧‧Insulating film

14‧‧‧Barrier Metal Film

16‧‧‧Metal Film

20‧‧‧Recess for wiring

100‧‧‧Processed object

Claims (8)

A composition for semiconductor processing, which is a concentrated composition for semiconductor processing, and contains 3×10 ¹ /mL ~ 1.5 ^{× 10 3} /mL metal particles with a particle size of 0.1 μm ~ 0.3 μm and/or The metal oxide particles contain a liquid medium, and the semiconductor processing composition further contains at least two selected from the group consisting of water-soluble polymers, organic acids, amines, pH adjusters, and surfactants. The composition for semiconductor processing according to claim 1, which is used by diluting 1 to 500 times. A composition for semiconductor processing, which is used undiluted and contains metal particles and/or metal oxides with a particle size of 0.1 μm to 0.3 μm in ^{3×10 1} /mL to 1.5 ^{× 10 3 /mL} The particles contain a liquid medium, and the semiconductor processing composition further contains at least two selected from the group consisting of a water-soluble polymer, an organic acid, an amine, a pH adjuster, and a surfactant. The composition for semiconductor processing according to any one of claims 1 to 3 of the claimed scope, further comprising an organic acid. The composition for semiconductor processing according to any one of claims 1 to 3 of the claimed scope, further comprising a water-soluble polymer. The composition for semiconductor processing according to any one of claims 1 to 3, wherein the particles contain a ratio (Rmax/Rmin) of a major axis (Rmax) to a minor axis (Rmin) of 1.3 particles of the above shape. A processing method, comprising the steps of: using the semiconductor as described in any one of items 1 to 6 of the claimed scope The composition for processing is prepared on a wiring board containing copper or tungsten as a wiring material and containing at least one selected from the group consisting of tantalum, titanium, cobalt, ruthenium, manganese and compounds of the metals as a barrier metal material deal with. 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 a composition containing iron ions and peroxides, using as described in items 1 to 1 of the scope of the patent application. The composition for semiconductor processing according to any one of the 6 items is processed.

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