KR20170126782A - Composition for semiconductor process and treatment method - Google Patents

Abstract

Provided are a composition for treating a semiconductor and a treatment method using the same, which can effectively prevent contamination from the surface of an object to be treated by suppressing damage to metal wiring and the like of the object to be treated. The composition for treating a semiconductor according to the present invention is a composition for treating a semiconductor containing potassium and sodium, and when the content of potassium is M_K (ppm) and the content of sodium is M_Na (ppm), M_K/M_Na is 510^3-110^5.

Description

TECHNICAL FIELD [0001] The present invention relates to a composition for semiconductor processing,

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

CMP (Chemical Mechanical Polishing) used in the production of a semiconductor device is a method in which a workpiece to be processed (an object to be polished) is pressed onto a polishing pad and an aqueous dispersion for chemical mechanical polishing (hereinafter simply referred to as " Quot;), while sliding the object to be processed and the polishing pad against each other to chemically and mechanically polish the object to be processed. The CMP slurry used for such CMP contains chemical agents such as an etching agent in addition to abrasive grains (abrasive grains). Then, polishing debris is generated by CMP. If these abrasive grains remain on the object to be processed, a fatal device defect may occur. For this reason, a step of cleaning the object to be processed after CMP is essential.

A metal wiring material such as copper or tungsten, an insulating material such as silicon oxide, or a barrier metal material such as tantalum nitride or titanium nitride is exposed on the surface of the object to be processed after CMP. When such a heterogeneous material coexists on the surface to be polished, it is necessary to remove only contamination from the surface to be polished and to treat the substrate without causing damage such as corrosion. For example, Patent Document 1 discloses a technique for suppressing corrosion of a polished surface to which a wiring material and a barrier metal material are exposed by using an acidic semiconductor processing composition. Further, for example, Patent Document 2 and Patent Document 3 disclose a technique for treating a surface to be polished, in which a barrier metal material such as a wiring material and cobalt is exposed, using a neutral to alkaline semiconductor processing composition.

Japanese Laid-Open Patent Publication No. 2010-258014 Japanese Laid-Open Patent Publication No. 2009-055020 Japanese Laid-Open Patent Publication No. 2013-157516

However, in recent years, along with further miniaturization of the circuit structure, there has been a demand for a treatment technique capable of further suppressing damage to the metal wiring and the like of the subject, and effectively removing the contamination from the surface of the subject.

For example, in CMP of a workpiece having tungsten as a metal wiring, a CMP slurry containing iron nitrate and other oxidizing agents (hydrogen peroxide, potassium iodate, etc.) is used. Since the iron ions contained in the CMP slurry are likely to be adsorbed on the surface of the subject, the surface of the subject is prone to iron contamination. In this case, iron contamination can be removed by treating the surface of the subject using dilute hydrofluoric acid, but the surface of the subject is etched away, and is liable to suffer damage. Therefore, there has been a demand for a treatment technique capable of effectively suppressing contamination from the surface of an object to be treated while suppressing damage to the metal wiring of the object to be treated as much as possible.

Therefore, some of the aspects of the present invention solve at least part of the above-mentioned problems, and it is an object of the present invention to provide a semiconductor processing composition capable of effectively preventing contamination from the surface of a subject by suppressing damage to the metal wiring, And to provide a processing method using the same.

The present invention has been made to solve at least part of the above-mentioned problems, and can be realized as the following aspects or applications.

[Application Example 1]

An aspect of the composition for semiconductor processing according to the present invention is that,

1. A concentrated semiconductor processing composition containing potassium and sodium,

M _K / M _Na = 5 × 10 ^{3 to} 1 × 10 ⁵ , wherein the content of potassium is M _K (ppm) and the content of sodium is M _Na (ppm).

[Application example 2]

In the composition for semiconductor processing of Application Example 1,

It can be diluted 1 to 500 times.

[Application Example 3]

An aspect of the composition for semiconductor processing according to the present invention is that,

A composition for semiconductor processing which is used without dilution and contains potassium and sodium,

M _K / M _Na = 5 × 10 ^{3 to} 1 × 10 ⁵ , wherein the content of potassium is M _K (ppm) and the content of sodium is M _Na (ppm).

[Application example 4]

In the semiconductor processing composition of any one of Application Examples 1 to 3,

In addition, it may contain organic acids.

[Application Example 5]

In the semiconductor processing composition of any one of Application Examples 1 to 4,

In addition, it may contain a water-soluble polymer.

[Application Example 6]

An embodiment of the treatment method according to the present invention is characterized in that,

A wiring board comprising copper or tungsten as a wiring material and at least one selected from the group consisting of tantalum, titanium, cobalt, ruthenium, manganese, and a compound thereof as a barrier metal material, And a step of treating using any one of the semiconductor processing compositions of Application Example 5. [

[Application Example 7]

An embodiment of the treatment method according to the present invention is characterized in that,

The wiring board is chemically mechanically polished using a composition containing iron ions and peroxides and then treated with the semiconductor processing composition of any one of Application Examples 1 to 5 The method comprising the steps of:

According to the composition for semiconductor processing according to the present invention, it is possible to effectively prevent contamination from the surface of the object to be processed by suppressing damage to the metal wiring of the object to be treated and the like.

1 is a cross-sectional view schematically showing a manufacturing process of a wiring board used in a processing method according to the present embodiment.
2 is a cross-sectional view schematically showing a manufacturing process of a wiring board used in a processing method according to the present embodiment.
3 is a conceptual diagram schematically showing a configuration of a filtration apparatus used in the present embodiment.

(Mode for carrying out the invention)

Hereinafter, a preferred embodiment of the present invention will be described in detail. The present invention is not limited to the embodiments described below, but includes various modifications embodied in the scope of the present invention.

1. Composition for semiconductor processing

The composition for semiconductor processing according to one embodiment of the present invention is characterized in that M _K / M (ppm) is obtained when potassium and sodium are contained and the content of potassium is M _K (ppm) and the content of sodium is M _{Na And Na} = 5 × 10 ^{3 to} 1 × 10 ⁵ . The composition for semiconductor processing according to the present embodiment may be a concentrated type for the purpose of being diluted with a liquid medium such as pure water or an organic solvent or may be a non-diluted type for the purpose of being used without being diluted. In the present specification, the term " composition for semiconductor processing " is interpreted as a concept including both a concentrated type and a non-diluted type, unless the concentration type or the non-diluted type is specified.

Such a composition for semiconductor processing is mainly used as a cleaning agent for removing particles and metal impurities existing on the surface of the object to be treated after completion of CMP, a resist stripping agent for removing the resist from the semiconductor substrate processed using the resist, It can be used as a treating agent such as an etching agent for removing surface contamination by shallowly etching the surface. In the present invention, the term " treating agent " is a concept including a cleaning agent for cleaning such a semiconductor surface, a resist stripping agent, an etching agent, and the like. Hereinafter, each component contained in the semiconductor processing composition according to the present embodiment will be described in detail.

1.1. Potassium and sodium

The composition for semiconductor processing according to the present embodiment contains potassium and sodium. In general, as described in Japanese Patent Application Laid-Open No. 2000-208451, alkali metal such as sodium or potassium is recognized as an impurity which should be removed as far as possible in the semiconductor manufacturing process. Therefore, even in various compositions used for semiconductor processing such as CMP slurry, an organic base such as tetramethylammonium hydroxide (TMAH) is preferably used as a base for controlling pH, not an inorganic base such as sodium hydroxide. However, in the present invention, by using the composition for semiconductor processing containing potassium and sodium in a predetermined ratio in a cleaning step such as after CMP polishing, a resist stripping step, an etching step, etc. up to now, It has been found that there is an effect of improving the processing characteristics without significantly deteriorating the semiconductor characteristics.

The content ratio of potassium and sodium in the semiconductor processing composition according to the present embodiment is preferably M _K / M _Na = 5 (ppm), where M _K (ppm) is the potassium content and M _Na X 10 ^{3 to} 1 x 10 ^5, and more preferably 5.5 x 10 ^{3 to} 9 x 10 ⁴ , more preferably 6 x 10 ³ to 9 x 10 ⁴ , and most preferably 7 x 10 ^{3 to} 8 x 10 ⁴ Particularly preferred. When the content of potassium and sodium is within the above range, it is considered that excessive etching and elution of a metal material such as copper or tungsten exposed on the surface to be treated in the semiconductor processing step can be suppressed. On the other hand, when the ratio of sodium to potassium contained in the semiconductor processing composition exceeds the above range, sodium or potassium adheres to the object to be processed, and the yield due to the deterioration of the electrical characteristics of the semiconductor circuit And the like. On the other hand, when the ratio of sodium to potassium contained in the composition for semiconductor processing is less than the above range, the ionic product of sodium or potassium present in the semiconductor processing composition and a metal material such as copper or tungsten exposed on the object side It is considered that excessive etching of the metal material such as copper or tungsten proceeds and the flatness and electric characteristics of the surface to be treated deteriorate.

The semiconductor treatment composition of the condensing type according to the present embodiment, it is preferable, more preferably containing ^{4 × 10 -6 ~6 × 10 0} ppm sodium containing ^{1 × 10 -6 ~1 × 10 1} ppm . It is preferable that the concentration type semiconductor processing composition according to the present embodiment contains potassium at 1 10 ^{-1 to} 5 10 ⁴ ppm and more preferably contains 1.2 10 ^-1 to 4 10 ⁴ ppm desirable.

The non-dilution type semiconductor processing composition according to the present embodiment preferably contains sodium at 1 10 ^{-8 to} 1 10 ^-1 ppm, and preferably contains sodium at 4 10 ^-8 to ⁶ 10 ^-2 ppm More preferable. The non-dilution type semiconductor processing composition according to the present embodiment preferably contains potassium in an amount of 1.2 × 10 ^{-3 to} 5 × 10 ³ ppm, more preferably 1.5 × 10 ^{-3 to} 5 × 10 ² ppm More preferable.

In the semiconductor processing composition according to the present embodiment, potassium and sodium are contained at the above content ratios and the contents of potassium and sodium are within the above ranges, whereby copper or tungsten It is considered that it is possible to more effectively suppress the elution of the metal material such as excessively etched and to maintain stable processing characteristics.

In the semiconductor processing composition according to the present embodiment, potassium or sodium can be contained in the composition for semiconductor processing by compounding potassium or sodium as a water-soluble salt. As such water-soluble salts, for example, hydroxides, carbonates, ammonium salts and halides of sodium or potassium can be used.

In the present invention, the content M _K (ppm) of potassium and the content M _Na (ppm) of sodium contained in the semiconductor processing composition can be measured by ICP emission spectrometry (ICP-AES) (ICP-MS) or atomic absorption spectrophotometry (AA). As the ICP emission spectrometer, for example, " ICPE-9000 (manufactured by Shimadzu Seisakusho Co., Ltd.) " As the ICP mass spectrometer, for example, " ICPM-8500 (manufactured by Shimadzu Seisakusho Co., Ltd.) and ELAN DRC PLUS (manufactured by PerkinElmer Co.) can be used. As the atomic absorption spectrometer, for example, "AA-7000" (manufactured by Shimadzu Seisakusho Co., Ltd.) and "ZA3000 (Hitachi High-Tech Science Co., Ltd.") can be used.

In the CMP of a workpiece having tungsten as a wiring material, a CMP slurry containing iron ions and peroxides (hydrogen peroxide, potassium iodate, etc.) is used. Since the iron ions contained in the CMP slurry are liable to be adsorbed on the surface of the object to be treated, the surface to be polished tends to be contaminated with iron. In this case, cleaning of the surface to be polished using the composition for semiconductor processing according to the present embodiment promotes the formation of a readily soluble salt such as potassium tungstate or sodium tungstate in the cleaning process. Thus, metal contamination on the wiring board can be reduced, and it is considered that the polishing residue can be efficiently removed while reducing the damage to the object to be processed.

1.2. Other components

The semiconductor processing composition according to the present embodiment may contain a water-soluble polymer, an organic acid, an amine, and other components in addition to the liquid medium as the main component.

1.2.1. Water-soluble polymer

The semiconductor processing composition according to the present embodiment may contain a water-soluble polymer. The water-soluble polymer has a function of adsorbing on the surface of an object surface to reduce corrosion. Therefore, when the water-soluble polymer is added to the composition for semiconductor processing, the corrosion on the surface to be treated can be reduced. In the present invention, " water-soluble " means that the mass dissolved in 100 g of water at 20 DEG C is 0.1 g or more. In the present invention, the "water-soluble polymer" refers to a water-soluble compound in which two or more repeating units are linear or meso-shaped and continuous through covalent bonds.

Examples of such a water-soluble polymer include polyacrylic acid, polymethacrylic acid, polymaleic acid, polyvinylsulfonic acid, polyallylsulfonic acid, polystyrenesulfonic acid, and salts thereof;

A repeating unit having an aromatic hydrocarbon group in which a monomer such as styrene,? -Methylstyrene, or 4-methylstyrene, a copolymer of an acid monomer such as (meth) acrylic acid or maleic acid, or an aromatic hydrocarbon group in which benzenesulfonic acid, naphthalenesulfonic acid, And salts thereof;

Based synthetic polymers such as polyvinyl alcohol, polyoxyethylene, polyvinylpyrrolidone, polyvinylpyridine, polyacrylamide, polyvinylformamide, polyethyleneimine, polyvinyloxazoline, polyvinylimidazole, and polyallylamine ;

Modified products of natural polysaccharides such as hydroxyethyl cellulose, carboxymethyl cellulose and modified starch;

, But are not limited thereto. These water-soluble polymers may be used singly 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 kinds of monomers. As such a monomer, a monomer having a carboxyl group, a monomer having a sulfonic acid group, a monomer having a hydroxyl group, a monomer having a polyethylene oxide chain, a monomer having an amino group, a monomer having a heterocyclic ring and the like can be used.

The weight average molecular weight (Mw) of the water-soluble polymer used in the present embodiment is preferably 1,000 to 1,500,000, and more preferably 3,000 to 1,200,000. In the present specification, the "weight average molecular weight" refers to the weight average molecular weight in terms of polyethylene glycol as measured by GPC (gel permeation chromatography).

The content of the water-soluble polymer may be adjusted so that the viscosity of the composition for semiconductor processing at room temperature is 2 mPa · s or less. If the viscosity of the composition for semiconductor processing at room temperature exceeds 2 mPa · s, the viscosity of the composition may become excessively high and the composition for semiconductor processing may not be stably supplied to the object to be processed. Since the viscosity of the composition for semiconductor processing is determined substantially by the weight average molecular weight and the content of the water-soluble polymer to be added, the viscosity may be adjusted in consideration of the balance thereof.

The content of the water-soluble polymer may be selected from the group consisting of a metal wiring material such as copper or tungsten exposed to the surface of the object to be treated after CMP, an insulating material such as silicon oxide, a barrier metal material such as tantalum nitride or titanium nitride, And can be appropriately changed depending on the composition of the slurry.

In addition, the content of the water-soluble polymer can be appropriately changed depending on the degree of dilution of the concentration type semiconductor processing composition according to the present embodiment. The content of the water-soluble polymer is preferably at least 0.001 part by mass, more preferably at least 0.001 part by mass, per 100 parts by mass of the treating agent prepared by diluting the concentrated type semiconductor processing composition or the undiluted type semiconductor processing composition (treating agent) Is not less than 0.01 part by mass, and the upper limit is preferably not more than 1 part by mass, more preferably not more than 0.1 part by mass. When the content of the water-soluble polymer is within the above range, both the suppression of corrosion and the effect of removing particles or metal impurities contained in the CMP slurry from the wiring substrate are promoted, and a better surface to be treated is likely to be obtained.

1.2.2. Organic acid

The semiconductor processing composition according to the present embodiment may contain an organic acid. The organic acid preferably has at least one acidic group such as a carboxyl group or a sulfo group. The term " organic acid " in the present invention is a concept that does not include the aforementioned water-soluble polymer.

Specific examples of the organic acid include citric acid, maleic acid, malic acid, tartaric acid, oxalic acid, malonic acid, succinic acid, ethylenediaminetetracetic acid, acrylic acid, methacrylic acid, benzoic acid, phenyllactic acid, hydroxyphenyllactic acid, phenylsuccinic acid, And the like. These organic acids may be used singly or in combination of two or more.

As the organic acid, an amino acid may be used. Examples of the amino acid include compounds represented by the following general formula (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 represented by 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, an aromatic hydrocarbon group having 6 to 10 carbon atoms A hydrocarbon group, and the like, among which a saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms is preferable.

Examples of the organic group having 1 to 20 carbon atoms and having a hetero atom in R ¹ in the general formula (1) include hydrocarbon groups having 1 to 20 carbon atoms having a carboxyl group, hydrocarbons having 1 to 20 carbon atoms having a hydroxyl group , A hydrocarbon group having 1 to 20 carbon atoms having an amino group, a hydrocarbon group having 1 to 20 carbon atoms having a mercapto group, and an organic group having 1 to 20 carbon atoms having a heterocyclic ring, , Halogen, and the like, or a part thereof may be substituted with another substituent.

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

As the organic acid, it is also preferable to use a compound represented by the following general formula (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 represented by 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 carbon number having a cyclic saturated hydrocarbon group An organic group having 6 to 20 carbon atoms, an organic group having 6 to 20 carbon atoms having an unsaturated cyclic hydrocarbon group, 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 and an organic group having 1 to 20 carbon atoms having a heterocyclic group. Of these, an organic group having 6 to 20 carbon atoms having an unsaturated cyclic hydrocarbon group or a hydrocarbon group having 1 to 20 carbon atoms having a carboxyl group is preferable, An organic group having 6 to 20 carbon atoms having an aryl group or a carboxymethyl group is particularly preferable. 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 and hydroxymalonic acid, and among them, hydroxyphenyllactic acid is preferable. The above-exemplified compounds may be used singly or in combination of two or more kinds.

The content of the organic acid may be appropriately determined depending on the material such as a metal wiring material such as copper or tungsten exposed on the surface of the object to be treated after CMP, an insulating material such as silicon oxide, a barrier metal material such as tantalum nitride or titanium nitride, As shown in FIG.

The content of the organic acid can be appropriately changed depending on the degree of dilution of the concentration type semiconductor processing composition according to the present embodiment. The lower limit of the content of the organic acid is preferably 0.0001 part by mass or more, more preferably 0.0001 part by mass or more, and most preferably 0.001 part by mass or less, per 100 parts by mass of the treating agent prepared by diluting the concentrated semiconductor processing composition or the non- More preferably 0.0005 mass part or more, and the upper limit value is preferably 1 mass part or less, more preferably 0.5 mass part or less. If the content of the organic acid is within the above range, the impurities attached to the surface of the wiring material can be effectively removed. Further, the progress of excessive etching can be suppressed more effectively, and a good surface to be processed can be obtained.

1.2.3. Amine

The composition for semiconductor processing according to the present embodiment may contain an amine (except amino acid). It is considered that the amine has a function as an etching agent. (For example, CuO, Cu ₂ O and Cu (OH) ₂ layers) and organic residues (for example, BTA layers) on the wiring substrate are etched by the addition of an amine So that it can be removed.

The amine is preferably a water-soluble amine. The definition of " water-soluble " is the same as described above, and refers to a mass of 0.1 g or more dissolved in 100 g of water at 20 캜. Examples of the amines include alkanolamines, primary amines, secondary amines, tertiary amines, and the like.

Examples of the alkanolamine include monoethanolamine, diethanolamine, triethanolamine, N-methylethanolamine, N-methyl-N, N-diethanolamine, N, N-dimethylethanolamine, N, , N, N-dibutylethanolamine, N- (? -Aminoethyl) ethanolamine, N-ethylethanolamine, monopropanolamine, dipropanolamine, tripropanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine And the like. Examples of primary amines include methylamine, ethylamine, propylamine, butylamine, pentylamine, and 1,3-propanediamine. Examples of secondary amines include piperidine, piperazine and the like. Examples of tertiary amines include trimethylamine, triethylamine, and the like. 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 because it is highly effective in etching metal oxide film and organic residue on the wiring substrate.

The content of the amine may be selected from the group consisting of a metal wiring material such as copper or tungsten exposed to the surface of the object to be treated after CMP, an insulating material such as silicon oxide, a barrier metal material such as tantalum nitride or titanium nitride, As shown in FIG.

The amine content can be appropriately changed depending on the degree of dilution of the concentration type semiconductor processing composition according to the present embodiment. The content of amine is preferably at least 0.0001 part by mass, more preferably at least 0.001 part by mass, per 100 parts by mass of the treating agent prepared by diluting the concentrated type semiconductor processing composition or the undiluted type semiconductor processing composition (treating agent) More preferably 0.0005 parts by mass or more, and the upper limit is preferably 1 part by mass or less, and more preferably 0.5 parts by mass or less. When the content of amine is within the above range, the metal oxide film and the organic residue on the wiring substrate can be more effectively etched and removed in the cleaning step after the completion of CMP.

1.2.4. Liquid medium

The semiconductor processing composition according to the present embodiment is a liquid containing a liquid medium as a main component. The kind of the liquid medium can be timely selected depending on the intended use of the treating agent such as cleaning, etching, or resist stripping with respect to the object to be treated. For example, when the composition for semiconductor processing is used as a cleaning agent, the liquid medium is preferably one capable of serving as a solvent mainly composed of water, and is not particularly limited. Examples of such a liquid medium include a mixed medium of water, water and alcohol, and a mixed medium containing an organic solvent having compatibility with water and water. Among these, it is preferable to use a mixed medium of water, water and alcohol, and it is more preferable to use water.

When the composition for semiconductor processing is used, for example, as an etching agent or a resist stripper, it is preferable that the liquid medium can serve as a solvent containing an organic solvent as a main component, and is not particularly limited. Examples of such organic solvents include polar solvents such as ketone solvents, ester solvents, ether solvents and amide solvents, and hydrocarbon solvents, and other known organic solvents usable in semiconductor processing.

Examples of the ketone-based solvent include aliphatic ketone solvents such as 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone, , Diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, methylethylketone, methylisobutylketone, acetylacetone, acetonylacetone, ionone, diacetonyl alcohol, acetylcarbinol, acetophenone, methyl Naphthyl ketone, isophorone, propylene carbonate,? -Butyrolactone, and the like.

Examples of ester solvents include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, pentyl acetate, isopentyl acetate, methoxyacetyl ethyl, ethoxyacetyl ethyl, propyleneglycol 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 glycol monobutyl ether acetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 3-methyl- part Acetate, 3-ethyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl acetate, 4- Methoxypentyl acetate, 3-methoxypentyl acetate, 3-methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate, 3-methyl- Methyl 4-methoxypentyl acetate, 4-methyl-4-methoxypentyl acetate, propylene glycol diacetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl carbonate, propyl carbonate, butyl carbonate, Ethyl, propyl pyruvate, butyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl propionate, ethyl propionate, Ethyl propionate, isopropyl propionate, methyl-3-methoxy propionate, ethyl-3-methoxy propionate, ethyl-3-ethoxy propionate and propyl 3- methoxy propionate . Examples of the cyclic ester solvent include lactones such as? -Butyrolactone.

Examples of the ether solvents include glycol ether-based solvents 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; solvent; Diisopentyl ether, diisobutyl ether, dioxane, tetrahydrofuran, anisole, perfluoro-2-butyltetrahydrofuran, perfluorotetrahydrofuran, 1,4-dioxane and the like.

Examples of the amide solvent include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, hexamethylphosphoric triamide, Imidazolidinone, and the like. As the other polar solvent, dimethylsulfoxide and the like can be mentioned.

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

1.2.5. Other components

The composition for semiconductor processing according to the present embodiment may contain a necessary component in a timely manner and may contain, for example, a pH adjuster, a surfactant, and the like.

<pH adjusting agent>

When treating a surface to be treated containing copper as a wiring material, the lower limit value of the pH is preferably 9 or more, more preferably 10 or more, and the upper limit value of the pH is preferably 14 or less Do. When treating the surface of the object including tungsten as the wiring material, the upper limit value of pH is preferably 7 or less, more preferably 6 or less, and the lower limit value of pH is preferably 2 or more.

When a desired pH can not be obtained by adding the aforementioned organic acid or amine to the semiconductor processing composition according to this embodiment, a pH adjuster may be added to adjust the pH within the above range. Examples of the pH adjuster 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 adjusting agents may be used singly or in combination of two or more kinds.

<Surfactant>

As the surfactant, a known component can be used in a timely manner, but a nonionic surfactant or an anionic surfactant can be preferably used. By adding a surfactant, the effect of removing the particles and metal impurities contained in the CMP slurry from the wiring board is enhanced, and a better surface to be treated can be obtained.

Examples of the nonionic surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether and polyoxyethylene oleyl ether; Polyoxyethylene aryl ethers such as polyoxyethylene octyl phenyl ether and polyoxyethylene nonyl phenyl ether; Sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monopalmitate, and sorbitan monostearate; And polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate and polyoxyethylene sorbitan monostearate. The above-exemplified nonionic surfactants may be used singly or in combination of two or more.

Examples of the anionic surfactant include alkyl benzene sulfonic acids such as dodecyl benzene sulfonic acid; Alkyl naphthalenesulfonic acid; Alkyl sulfuric acid esters such as laurylsulfuric acid; Sulfuric acid esters of polyoxyethylene alkyl ethers such as polyoxyethylene lauryl sulfate; Condensates of naphthalene sulfonic acid; Alkyliminodicarboxylic acid; Ligninsulfonic acid, and the like. These anionic surfactants may be used in the form of a salt. In this case, as the counter cation, for example, sodium ion, potassium ion, ammonium ion and the like can be mentioned, but ammonium ion is preferable from the viewpoint of preventing excessive potassium or sodium.

In the CMP of a workpiece having tungsten as a wiring material, a CMP slurry containing iron ions and peroxides (hydrogen peroxide, potassium iodate, etc.) is used. Since the iron ions contained in the CMP slurry are likely to be adsorbed on the surface of the subject, the surface of the subject is prone to iron contamination. In this case, since iron ions are positively charged, iron contamination on the surface of the object to be treated can be effectively removed by adding an anionic surfactant to the composition for semiconductor processing.

The content of the surfactant may be appropriately selected depending on the material such as a metal wiring material such as copper or tungsten exposed on the surface of the object to be treated after CMP, an insulating material such as silicon oxide, a barrier metal material such as tantalum nitride or titanium nitride, And can be appropriately changed depending on the composition.

In addition, the content of the surfactant can be appropriately changed depending on the dilution degree of the concentrated semiconductor processing composition according to the present embodiment. The content of the surfactant is preferably 0.001 part by mass or more and 1 part by mass or less based on 100 parts by mass of the treating agent prepared by diluting the concentrated type semiconductor processing composition or the non-diluted type semiconductor processing composition (treating agent). When the content of the surfactant is within the above range, the organic residue can be efficiently removed while the corrosion of the object to be treated is reduced in the treatment step after the end of CMP.

1.3. Method for preparing composition for semiconductor processing

The composition for semiconductor processing according to this 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, followed by filtration. The mixing order and the mixing method of each of the above-mentioned components are not particularly limited.

In the method for preparing a semiconductor processing composition according to the present embodiment, it is preferable to control the amount of particles by filtering with a depth type or pleats type filter, if necessary. Here, the depth type filter is a high precision filtration filter which is also called a deep filtration or volume filtration type filter. Such a depth type filter includes a laminated structure in which a plurality of apertured filtration membranes are laminated, a fiber bundle is wound up, and the like. Specifically, examples of the depth type filter include profiles II, Nexis NXA, Nexis NXT, Poly Fine XLD, Ultipleplitz profiles (both manufactured by Nippon Polyurethane Industry Co., Ltd.), depth cartridge filters, (All manufactured by Chisso Corporation), Slope Pure, Diamond and Micro Syria (all manufactured by Roki Techno Co., Ltd.), and the like.

As the pleated filter, a microfiltration membrane sheet made of a nonwoven fabric, a filter paper, a metal mesh or the like is corrugated and then formed into a tubular shape, and the butted portion of the corrugation of the sheet is sealed in liquid tightness, And a cylindrical high-precision filtration filter obtained by dewatering liquid ends at both ends. Concretely, there are used HDCII, polyphene II and the like (both manufactured by Nippon Polyurethane Industry Co., Ltd.), PP Pleitz cartridge filter (manufactured by Advantech), Porouspine (manufactured by Chisso Corporation), Sarton Pore, And the like.

The filter preferably has a rated filtration accuracy of 0.01 to 20 占 퐉. By using the fact that the rated filtration accuracy is in the above range, it is possible to efficiently obtain a filtrate having a particle number of 20 μm or more per 1 mL as measured by a particle counter. Further, since the number of coarse particles trapped in the filter is minimized, the usable period of the filter is extended.

2. Treatment agent

The "treatment agent" in the present invention is a composition prepared by diluting a liquid medium added to the above-mentioned concentrated-type semiconductor processing composition or the above-described undiluted semiconductor processing composition itself, Refers to the liquid agent used at the time of The concentration-type semiconductor processing composition described above generally exists in a state in which each component is concentrated. Therefore, each user is required to dilute the above-mentioned concentrated type semiconductor processing composition with a liquid medium appropriately to prepare a treating agent, or to use the undiluted semiconductor processing composition as it is as a treating agent, And is provided for use as a resist stripping agent.

Here, the liquid medium used for the dilution has the same meaning as the liquid medium contained in the above-mentioned semiconductor processing composition, and can be appropriately selected from the above-mentioned liquid medium depending on the kind of the treatment agent.

As a method of adding a liquid medium to a concentrated semiconductor processing composition and diluting it, there is a method in which a piping for supplying a concentrated semiconductor processing composition and a piping for supplying a liquid medium are mixed and mixed in the middle, As shown in Fig. This mixing is a method in which impurities are impinged and mixed through a narrow passage under pressure; A method of filling a pipe such as a glass tube with a filling material and sorting and merging the flow of the liquid repeatedly; And a method of forming a blade that rotates with power in the piping can be employed.

As another method of adding and diluting the liquid medium to the concentration type semiconductor processing composition, a piping for supplying a concentrated semiconductor processing composition and a piping for supplying a liquid medium are independently provided and a predetermined amount Liquid is supplied to the surface to be treated and mixed on the surface to be treated. As another method for diluting the liquid medium with the liquid phase medium for the concentration type semiconductor processing composition, a predetermined amount of the concentrated semiconductor processing composition and a predetermined amount of the liquid medium are mixed and mixed in one container, And a method of supplying the mixed treatment agent.

As a dilution factor when the liquid medium is diluted by adding the liquid medium to the concentration type semiconductor processing composition, 1 part by mass of the concentrated type semiconductor processing composition is diluted with 1 to 500 parts by mass (1 to 500 times) by adding a liquid medium , More preferably 20 to 500 parts by mass (20 to 500 times), and particularly preferably 30 to 300 parts by mass (30 to 300 times). It is also preferable to dilute the liquid medium with the same liquid medium as the liquid medium contained in the above-mentioned concentrated-type semiconductor processing composition. By concentrating the semiconductor processing composition as described above, transporting and storage to a smaller-sized container becomes possible as compared with the case where the treating agent is transported and stored as it is. As a result, the cost of transportation and storage can be reduced. In addition, since a smaller amount of the treatment agent can be purified than when the treatment agent is directly purified by filtration or the like, the purification time can be shortened and mass production can be achieved.

3. Processing method

A treatment method according to one embodiment of the present invention is a treatment method comprising copper or tungsten as a wiring material and at least one selected from the group consisting of tantalum, titanium, cobalt, ruthenium, manganese, And a step of treating the wiring substrate containing the species by using the above-mentioned semiconductor processing composition (the above-mentioned treating agent, specifically, a cleaning agent, an etching agent, a resist stripping agent, etc.). Hereinafter, one example of the processing method according to the present embodiment will be described in detail with reference to the drawings.

&Lt; Fabrication of wiring board >

1 is a cross-sectional view schematically showing a manufacturing process of a wiring board used in the processing method according to the embodiment. Such a wiring board is formed by the following process.

1 is a cross-sectional view schematically showing an object to be processed before CMP processing. As shown in Fig. 1, the object to be treated 100 has a base body 10. The substrate 10 may be composed of, for example, a silicon substrate and a silicon oxide film formed thereon. Although not shown, functional devices such as transistors may be formed in the base 10.

The object to be processed 100 is formed on the base 10 so as to cover the insulating film 12 in which the recess 20 for wiring is formed and the surface of the insulating film 12 and the bottom and inner wall surfaces of the recess 20 for wiring A barrier metal film 14 and a metal film 16 filling the wiring recess 20 and formed on the barrier metal film 14 in that order.

As the insulating film 12, for example, a silicon oxide film formed by a vacuum process (e.g., a PETEOS film (Plasma Enhanced-TEOS film), an HDP film (High Density Plasma Enhanced-TEOS film) ), An insulating film called FSG (Fluorine-doped silicate glass), a boron phosphorus silicate film (BPSG film), an insulating film called SiON (Silicon oxynitride), and silicon nitride.

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

The metal film 16 is required to completely fill the recess 20 for wiring as shown in Fig. For this purpose, a metal film of 10000 to 15000 angstroms is usually deposited by a chemical vapor deposition method or an electroplating method. As the material of the metal film 16, copper or tungsten can be mentioned. In the case of copper, not only copper having high purity but also alloys containing copper can be used. The content of copper in the copper-containing alloy is preferably 95% by mass or more.

Next, of the object to be processed 100 shown in Fig. 1, the metal film 16 other than the portion buried in the wiring recess 20 is polished at a high speed by CMP until the barrier metal film 14 is exposed Polishing process). Further, the barrier metal film 14 exposed on the surface is polished by CMP (second polishing step). In this manner, the wiring board 200 shown in Fig. 2 is obtained.

<Treatment of Wiring Substrate>

Next, the surface (the surface to be treated) of the wiring board 200 shown in Fig. 2 is treated with the above-mentioned treating agent (cleaning agent). According to the processing method of the present embodiment, it is possible to suppress the corrosion of the wiring material and the barrier metal material when the wiring substrate on which the wiring material and the barrier metal material after the completion of the CMP coexist on the surface, Organic residues can be efficiently removed.

The treatment method according to the present embodiment is a treatment method comprising tungsten as a wiring material for a wiring substrate and a composition (Fenton's reagent) containing an iron ion and a peroxide described in JP-A-10-265766 It is very effective to carry out after chemical mechanical polishing. In the CMP of a workpiece having tungsten as a wiring material, a CMP slurry containing iron ions and peroxides (hydrogen peroxide, potassium iodate, etc.) is used. Since the iron ions contained in the CMP slurry are likely to be adsorbed on the surface of the subject, the surface of the subject is prone to iron contamination. 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 surface to be polished is etched and easily damaged. However, the above-mentioned composition for semiconductor treatment contains potassium and sodium at a predetermined ratio, so that the formation of a usable salt such as potassium tungstate or sodium tungstate is promoted in the treatment process. Thus, metal contamination on the wiring board can be reduced, and the polishing residue can be efficiently removed while reducing the damage to the object to be processed.

The treatment method is not particularly limited, but is performed by a method in which the above-described cleaning agent is brought into direct contact with the wiring board 200. As a method for bringing the cleaning agent directly into contact with the wiring board 200, there are a dip type in which a cleaning agent is filled in a cleaning tank to immerse the wiring board; A spin type in which the wiring substrate is rotated at a high speed while the cleaning agent is being supplied from the nozzle onto the wiring substrate; And a spray method in which a cleaning agent is sprayed on the wiring board to clean the wiring board. Examples of the apparatus for carrying out such a method include a batch type processing apparatus for simultaneously processing a plurality of wiring boards accommodated in a cassette, and a single sheet type processing apparatus for mounting and processing one wiring board on a holder.

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

In addition to the method of bringing the aforementioned cleaning agent directly into contact with the wiring board 200, it is also preferable to use a physical treatment method in combination. As a result, the removal of contamination by the particles attached to the wiring board 200 is improved, and the processing time can be shortened. Examples of a treatment method using physical force include scrubbing cleaning using a cleaning brush and ultrasonic cleaning.

Further, cleaning with ultra pure water or pure water may be performed before and / or after cleaning by the treatment method according to the present embodiment.

4. Example

Hereinafter, the present invention will be described by way of examples, but the present invention is not limited to these examples at all. In the present embodiment, &quot; part &quot; and &quot;% &quot; are based on mass unless otherwise specified.

4.1. Example 1

4.1.1. Preparation of composition for semiconductor processing (concentration type)

Each component was added to a container made of polyethylene so as to have a content ratio shown in Table 1, and an ion-exchanged water was added in an appropriate amount, followed by stirring for 15 minutes. To this mixture, ion-exchanged water, potassium hydroxide and sodium hydroxide were added as needed so that the total amount of the components was 100 parts by mass, and the composition was adjusted to the pH, K content and Na content shown in Table 1.

After adding 0.01 part by mass of colloidal silica (trade name &quot; PL-1 &quot;, manufactured by Fusokakaku Corp.) having a primary particle diameter of 15 nm) to 100 parts by mass of the composition thus obtained, (Filtration step). 3 includes a supply tank 210 for storing and supplying the composition before the foreign object is removed, a metering pump 220 for flowing the composition before the foreign object is removed at a constant flow rate, a cartridge filter A pulsation prevention device 230 located in the middle of the quantitative pump 220 and the filter 240, a pulsation prevention device 230, and a filter (not shown) A first pressure gauge 270a disposed between the first and second pressure gauges 240 and 240 and a second pressure gauge 270b disposed downstream of the filter 240. [ The filtration apparatus 300 includes a return conduit 260 for returning the composition for semiconductor processing from the filter 240 to the supply tank 210 and a discharge conduit 260 for discharging the semiconductor processing composition filtered by the filter 240 And a conduit 250.

In the present embodiment, the filter 240 is formed by mounting one membrane filter cartridge "Water Pine" (manufactured by Nihon Foam, Ltd., rated filtration accuracy: 0.05 μm, length 10 inches) in the housing. The metering pump 220 uses a pneumatic diaphragm pump so that the differential pressure before and after the filter is 0.2 to 0.3 MPaG and the flow rate of the composition is the flow rate shown in Table 1.

The timely composition was sampled and filtration was stopped when the number of particles of 0.1 to 0.3 mu m contained in the composition reached the concentration described in Table 1 to prepare the semiconductor processing composition (concentration type) of Example 1. The number of particles per 1 mL of the composition was measured as follows.

For the particle counter, a particle sensor "KS-42 AF" manufactured by Reon Chemical Co., Ltd. was used. Specifically, the blank measurement is repeated with ultrapure water until the number of particles to be measured is "30 pieces / mL (0.1 μm)" (that is, "particles having a particle diameter larger than 0.1 μm are 30 pieces or less in 1 mL") did. Thereafter, 100 mL of a concentrated semiconductor processing composition (sample) was prepared, and this sample was set in a syringe sampler &quot; KZ-31W &quot;. Thereafter, the number of particles having a particle diameter of 0.1 to 0.3 mu m per 1 mL of the sample is measured twice by the liquid particle sensor, and an average value is calculated. This average value was determined as the number of particles having a particle diameter of 0.1 to 0.3 mu m per 1 mL of the composition for semiconductor processing.

4.1.2. Processing test of wiring board

(1) Chemical mechanical polishing process

A PETEOS film having a thickness of 5000 Å was formed on a silicon substrate having a copper wiring pattern of 8 inches in diameter and then patterned with a SEMATECH 854 mask. A cobalt film having a thickness of 250 Å, a copper seed film having a thickness of 1000 Å, 10000A copper plating film in this order) was subjected to a two-step chemical mechanical polishing under the following conditions using a chemical mechanical polishing apparatus "EPO112" manufactured by Eva Lasing Corporation. In the chemical mechanical polishing of the first stage, the copper seed film and the copper plated film were chemically mechanically polished until the cobalt film was exposed. In the second-stage chemical mechanical polishing, the cobalt film, the copper seed film and the copper plated film were chemically mechanically polished until the PETEOS film was exposed.

&Lt; Chemical mechanical polishing of the first stage >

· Aqueous dispersion for chemical mechanical polishing: "CMS7501 / CMS7552" manufactured by JSR Corporation

Polishing pad: "IC1000 / SUBA400" manufactured by Rodel Nitta Co., Ltd.

· Number of revolutions of surface plate: 70 rpm

· Head rotation speed: 71 rpm

· Head load: 50 g / cm 2

· Feed rate of aqueous dispersion for chemical mechanical polishing: 200 mL / min

· Polishing time: 150 seconds

&Lt; Second stage chemical mechanical polishing >

· Aqueous dispersion for chemical mechanical polishing: "CMS8501 / CMS8552" manufactured by JSR Corporation

Polishing pad: "IC1000 / SUBA400" manufactured by Rodel Nitta Co., Ltd.

· Number of revolutions of the table: 70 rpm

· Head rotation speed: 71 rpm

· Head load: 250 g / ㎠

· Feed rate of aqueous dispersion for chemical mechanical polishing: 200 mL / min

· Polishing time: 60 seconds

(2) Treatment process

The surface of the substrate after polishing thus obtained was added with ultrapure water (10 particles / mL or less of particles having a particle diameter of 0.3 mu m or less, pH = 6.5) so as to have a dilution ratio shown in Table 1 to the semiconductor processing composition (concentration type) (Cleaning agent) was prepared by dilution, and was subjected to a surface treatment (cleaning) under the following conditions. Thereafter, the same was provided for the brush scrub treatment (cleaning).

&Lt; Surface treatment (cleaning) >

- Treatment agent: The treating agent (detergent)

· Head rotation speed: 70 rpm

· Head load: 100 g / ㎠

· Number of revolutions of the table: 71 rpm

Processing rate: 300 mL / min

· Processing time: 30 seconds

<Brush scrub treatment (cleaning)>

- Treatment agent: The treating agent (detergent)

Upper brush rotation speed: 100 rpm

Lower brush rotation speed: 100 rpm

· Rotation speed of substrate: 100 rpm

Processing rate: 300 mL / min

· Processing time: 30 seconds

4.1.3. Evaluation test

<Evaluation of corrosion>

The surface of the substrate obtained after the above treatment was observed at a magnification of 120,000 times and a copper wiring portion of 0.175 mu m in the test pattern was observed using a scanning electron microscope (Hitachi High Technologies, model number &quot; S-4800 & And evaluated. The results are shown in Table 1. The evaluation criteria are as follows.

(Evaluation standard)

The number of copper wirings where corrosion was observed in 10 copper wirings,

. When the number of slits is not more than three and no slit is found between the barrier metal and the barrier metal,

If more than 3 and not more than 5 and no slit is found between the barrier metal and the barrier metal,

When the number of slits is more than 5 or the slit is found between the barrier metal and the barrier metal,

.

&Lt; Cleaning (defect) evaluation >

The number of defects on the entire surface of the substrate was measured using the wafer defect inspection apparatus (manufactured by KLA-Tencor Co., Ltd., model number &quot; KLA2351 &quot;) after the treatment. The results are shown in Table 1. The evaluation criteria are as follows.

(Evaluation standard)

The number of defects in the entire surface of the substrate,

· When it is 250 or less, it is judged to be very good, and "◎"

When the number is more than 250 and less than 500, it is judged to be usable,

If it exceeds 500, it is judged to be defective and &quot; x &quot;

.

<Reliability Evaluation>

1000 pieces of substrates (test substrates obtained by laminating a 5000 Å thick copper film) on the second-stage chemical mechanical polishing were subjected to running by brush scrub treatment using the above-mentioned treating agent (cleaning agent). The substrate after the treatment was inspected for defects and when the number of defects in the entire substrate surface was more than 250, The reliability of the treating 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 standard)

The number of defective substrates in 1000 sheets

When the number of sheets is 50 or less, it is judged to be very good, and &quot;

When the number of sheets is more than 50 sheets and less than 100 sheets,

When the number of sheets is more than 100 sheets,

4.2. Examples 2 to 26 and Comparative Examples 1 to 7

Except that the composition for semiconductor processing (concentration type) was changed to the composition shown in Tables 1 to 2 and the treating agent (cleaning agent) of the composition shown in Tables 1 to 2 was used, Test and evaluation tests were conducted.

4.3. Example 27

4.3.1. Preparation of composition for semiconductor processing (concentration type)

Except that the composition shown in Table 3 was changed to potassium hydroxide and sodium hydroxide as necessary to adjust the pH, K content, and Na content shown in Table 3 to the composition for semiconductor processing ( Concentrated type) was prepared.

4.3.2. Cleaning test of wiring board

(1) Chemical mechanical polishing process

A PETEOS film having a thickness of 5000 Å was formed on a silicon substrate having a copper wiring pattern of 8 inches in diameter and then patterned using a SEMATECH 854 mask. A cobalt film having a thickness of 250 Å, a tungsten seed film having a thickness of 1000 Å, A test substrate in which a tungsten plated film of 10000 angstroms were sequentially laminated) was subjected to a one-step chemical mechanical polishing under the following conditions using a chemical mechanical polishing apparatus "EPO112" manufactured by Ebara Seisakusho Co., Ltd.

<Polishing Condition>

&Quot; W2000 &quot; (slurry containing iron ions and hydrogen peroxide), manufactured by Cabot Co.,

Polishing pad: "IC1000 / SUBA400" manufactured by Rodel Nitta Co., Ltd.

· Number of revolutions of the table: 70 rpm

· Head rotation speed: 71 rpm

· Head load: 50 g / cm 2

· Feed rate of aqueous dispersion for chemical mechanical polishing: 200 mL / min

· Polishing time: 150 seconds

(2) Treatment process

The surface of the substrate after polishing thus obtained was added with ultrapure water (10 particles / mL or less of particles having a particle diameter of 0.3 mu m or less, pH = 6.5) so as to have the dilution ratio shown in Table 3 to the semiconductor processing composition (concentration type) (Cleaning agent) was prepared by dilution, and was subjected to a surface treatment (cleaning) under the following conditions. Thereafter, the same was provided for the brush scrub treatment (cleaning).

&Lt; Surface treatment (cleaning) >

- Treatment agent: The treating agent (detergent)

· Head rotation speed: 71 rpm

· Head load: 100 g / ㎠

· Number of revolutions of the table: 70 rpm

Processing rate: 300 mL / min

· Processing time: 30 seconds

<Brush scrub treatment (cleaning)>

- Treatment agent: The treating agent (detergent)

Upper brush rotation speed: 100 rpm

Lower brush rotation speed: 100 rpm

· Rotation speed of substrate: 100 rpm

Processing rate: 300 mL / min

· Processing time: 30 seconds

4.3.3. Evaluation test

<Evaluation of corrosion>

The surface of the substrate thus obtained after the treatment was evaluated in the same manner as in Example 1. The results are shown in Table 3.

&Lt; Cleaning (defect) evaluation >

The surface of the substrate thus obtained after the treatment was evaluated in the same manner as in Example 1. The results are shown in Table 3.

<Reliability Evaluation>

1,000 pieces of the substrate subjected to chemical mechanical polishing (a test substrate having a tungsten film laminated with a thickness of 3000 Å) were subjected to running by brush scrub treatment using the treating agent (cleaning agent) obtained above. The substrate after the treatment was inspected for defects and when the number of defects in the entire substrate surface was more than 250, The reliability of the treating 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 standard)

 The number of defective substrates in 1000 sheets

When the number of sheets is 50 or less, it is judged to be very good, and &quot;

When the number of sheets is more than 50 sheets and less than 100 sheets,

When the number of sheets is more than 100 sheets,

4.4. Examples 28 to 31 and Comparative Examples 8 to 10

A processing test and an evaluation test of the wiring board were carried out in the same manner as in Example 27 except that the composition for semiconductor processing (concentration type) was changed to the composition shown in Table 3 and the treating agent (cleaning agent) having the composition shown in Table 3 was used .

4.5. Example 32

4.5.1. Preparation of composition for semiconductor processing (non-diluted type)

To the polyethylene container, each component was added so as to have a content ratio shown in Table 4, and ion-exchanged water, potassium hydroxide, and sodium hydroxide were added as needed in accordance with the pH, K content and Na content shown in Table 4, Lt; / RTI &gt;

The composition thus obtained was processed in the same manner as in Example 1 except that a filter cartridge "PE-Clean" (manufactured by Nippon Polyurethane Industry Co., Ltd., rated filtration accuracy: 0.05 μm, length 10 inches) was used as the filter 240 in the housing The filtration was stopped, and the filtration was stopped when the number of particles of 0.1 to 0.3 mu m contained in the composition reached the concentration described in Table 4. Thus, the semiconductor processing composition (non-diluted type) of Example 32 was prepared did. A processing test and an evaluation test of the wiring board were carried out in the same manner as in Example 1 except that the thus obtained semiconductor processing composition was used as a processing agent (etching agent) without dilution.

4.6. Example 33

Except that the composition for semiconductor processing (non-diluted type) was changed to the composition shown in Table 4, and the obtained semiconductor processing composition was used as a processing agent (resist stripping agent) without dilution, Test and evaluation tests were conducted.

4.7. Examples 34 to 40 and Comparative Examples 11 to 15

Except that the composition for semiconductor processing (non-diluted type) was changed to the composition shown in Table 4, and the obtained semiconductor processing composition was used as it was without dilution as a treating agent (etching agent or resist stripping agent) The substrate was subjected to a treatment test and an evaluation test.

4.8. Evaluation results

Tables 1 to 4 below show the composition and evaluation results of the respective semiconductor cleaning compositions.

In the above Tables 1 to 4, numerical values of respective components represent mass parts. In each of the Examples and Comparative Examples, the total amount of each component was 100 parts by mass, and the remainder was ion-exchanged water. The following components in Tables 1 to 4 are supplemented.

<Water-soluble polymer>

Polyacrylic acid (Mw = 700,000): trade name "Julimer AC-10H" manufactured by TOAGOSE KOGYO Co.,

Polyacrylic acid (Mw = 55,000): trade name "Julimer AC-10L" manufactured by Toagosei Co., Ltd.

Polyacrylic acid (Mw = 6,000): manufactured by TOAGOSE KOGYO Co., Ltd., trade name "ARON A-10SL"

Polymaleic acid (Mw = 2,000): manufactured by Nichiyu K.K., trade name "NIPPOL PWA-50W"

Polyarylamine (Mw = 25,000): Product name "PAA-25" manufactured by Nittobo Medical Co., Ltd.

Polyarylamine (Mw = 15,000): trade name "PAA-15", manufactured by Nitto Boma Medical Co.,

Polystyrenesulfonic acid (Mw = 50,000): Product name "PS-5H", manufactured by Tohto Kikagaku Kabushiki Kaisha

Styrene-maleic acid copolymer: Daiichi Kyoei Co., Ltd., trade name "DKS DISCOAT N-10"

Styrene-maleic acid half ester copolymer: "DKS Discoat N-14" manufactured by Daiichi Kyoei Co., Ltd.

Na salt of naphthalenesulfonic acid-formalin condensate: manufactured by DAIICHIKO CHEMICAL INDUSTRIES, LTD., Trade name "Lavalin FD-40"

Polyvinyl alcohol (Mw = 26,000): manufactured by Kabushiki Kaisha Kuraray Co., Ltd., trade name "PVA405"

Polyethyleneimine (Mw = 70,000): manufactured by Nippon Shokubai Co., Ltd., trade name "Epomin P-1000"

<Organic acid>

· Serine: manufactured by Nihon RikagakuYakuhin Co., Ltd.

Cysteine: manufactured by Nihon RikagakuYakuhin Co., Ltd.

N-acetyl-L-cysteine: manufactured by Nihon Rikagaku Hinakusha Co., Ltd.

· Histidine: manufactured by Nihon RikagakuYakuhin Co., Ltd.

Arginine: manufactured by Nippon Rikagaku Hinoki Co., Ltd.

Phenylalanine: manufactured by Kyowa Hakko Bio Co., Ltd.

· Benzoic acid: manufactured by DMS Japan

· Hydroxyphenyllactic acid: manufactured by Tokyo Kasei Kogyo Co., Ltd.

Phenylsuccinic acid: manufactured by Tokyo Kasei Kogyo Co., Ltd.

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

· Maleic acid: manufactured by Fusokagakukogyo Co., Ltd.

Asparaginic acid: manufactured by Nihon RikagakuYakuhin Co., Ltd.

<Amine>

· Monoethanolamine: manufactured by Hayashi Junyaku Kogyo Co., Ltd.

· Isopropanolamine: Tocokagaku Co., Ltd.

<Others>

· Benzotriazole: manufactured by Joho Kakakako Corporation, anti-rust agent

· Imidazole: Manufactured by Shokoku Kaketsu Co., Ltd., anti-rust agent

Ammonium dodecylbenzenesulfonate: manufactured by Tamakagakuko Kogyo Co., Ltd., Surfactant

Ammonium alkylaminodicarboxylate: manufactured by Takemoto Yushi Co., Ltd., surfactant

TMAH: &quot; tetramethylammonium hydroxide &quot;, manufactured by Hayashi Co., Ltd., pH adjuster

TEAH: &quot; tetraethylammonium hydroxide &quot; manufactured by Junsei Kagaku Co., Ltd., pH adjusting agent

· Colin: manufactured by Tamakagakuko Kogyo Co., pH adjusting agent

Monomethyltrihydroxyethylammonium hydroxide: manufactured by Yokkaicho Kogyo Co., Ltd. pH adjusting agent

Dimethyl bis (2-hydroxyethyl) ammonium hydroxide: manufactured by Yokkaicho Chemical Co., pH adjusting agent

KOH: manufactured by Kanto Kagaku Co., Ltd. pH adjusting agent

Ammonium hydroxide: manufactured by Hayashi Junyaku Kogyo Co., Ltd. pH adjusting agent

<Solvent>

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

DMI: &quot; 1,3-dimethyl-2-imidazolidinone &quot; manufactured by Tokyo Kasei Kogyo K.K.

GBL: "Gamma butyrolactone" manufactured by Tokyo Kasei Kogyo Co., Ltd.

PG: "propylene glycol" manufactured by Wako Pure Chemical Industries, Ltd.

PGME: "propylene glycol monomethyl ether" manufactured by Kyo Kakaku Corporation

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

Sulfolane: &quot; Sulfolane &quot; manufactured by Sankyogaku Kabushiki Kaisha

As apparent from Tables 1 to 4, when the composition for semiconductor processing according to Examples 1 to 40 is used, all of the corrosion of the substrate surface is suppressed and the number of defects is also reduced, there was.

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, a configuration having the same function, method, and result, or a configuration having the same purpose and effect). The present invention also includes a configuration in which a non-essential portion of the configuration described in the embodiments is replaced. Further, the present invention includes a configuration that brings about the same operational effects as the configuration described in the embodiment, or a configuration that can achieve the same purpose. The present invention also includes a configuration in which known technologies are added to the configurations described in the embodiments.

10: Gas
12: Insulating film
14: barrier metal film
16: metal film
20: recess for wiring
100:
200: wiring board
210: Supply tank
220: metering pump
230: Pulse wave protection
240: filter
250: exhaust conduit
260: return conduit
270a: first pressure gauge
270b: second pressure gauge
300: Filtration device

Claims (7)

1. A concentrated semiconductor processing composition containing potassium and sodium,
_Wherein M _K / M _Na = 5 × 10 ^{3 to} 1 × 10 ⁵ , wherein the content of potassium is M _K (ppm) and the content of sodium is M _Na (ppm). The method according to claim 1,
Wherein the composition is diluted 1 to 500 times. A composition for semiconductor processing which is used without dilution and contains potassium and sodium,
_Wherein M _K / M _Na = 5 × 10 ^{3 to} 1 × 10 ⁵ , wherein the content of potassium is M _K (ppm) and the content of sodium is M _Na (ppm). 4. The method according to any one of claims 1 to 3,
Further, a composition for treating a semiconductor containing an organic acid. 4. The method according to any one of claims 1 to 3,
The composition for semiconductor processing further contains a water-soluble polymer. 1. A wiring board comprising copper or tungsten as a wiring material and at least one material selected from the group consisting of tantalum, titanium, cobalt, ruthenium, manganese and compounds thereof as a barrier metal material. A treatment method comprising a treatment using the semiconductor treatment composition according to any one of claims 1 to 3. The wiring substrate is chemically mechanically polished using a composition containing iron ions and peroxides as a wiring material of the wiring substrate, and the wiring substrate is subjected to chemical mechanical polishing, and then the semiconductor processing composition according to any one of claims 1 to 3 is used And processing the mixture.

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