JP2001064689A - Cleaning liquid for semiconductor parts - Google Patents

Abstract

PROBLEM TO BE SOLVED: To reduce the load on the environment and to leave CMP polishing abrasive grains such as silica and alumina on a semiconductor component such as a semiconductor substrate after chemical mechanical polishing (CMP).
To provide a cleaning liquid having a high cleaning effect on impurities such as Fe, Mn, Al, Ce, Cu, W, and Ti based on metal impurities or metal wiring contained therein. SOLUTION: A cleaning liquid for a semiconductor component containing a water-soluble (co) polymer (salt) containing a sulfonic acid (salt) group and / or a carboxylic acid (salt) group as an essential component.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cleaning solution for semiconductor components, and more particularly to a semiconductor manufacturing process for cleaning the surface of a semiconductor component such as a semiconductor substrate after chemical mechanical polishing (CMP). The present invention relates to a cleaning liquid for semiconductor parts.

[0002]

2. Description of the Related Art As a new flattening technique in a semiconductor device manufacturing process, chemical mechanical polishing (CMP) has attracted attention, and it has been compared with a conventional reflow technique or an etch-back technique such as RIE (reactive ion etching). And there is an advantage that good flattening can be realized with less dependency on pattern. This kind of CMP
Is applied to, for example, metal flattening of a multilayer or flattening of an interlayer insulating film. Conventionally, various methods have been proposed as a method of cleaning a substrate after chemical mechanical polishing as a step of planarizing an interlayer insulating film. The most versatile is R, which is often used in the semiconductor manufacturing process.
CA cleaning. The RCA cleaning includes a cleaning step using a mixture of ammonia, hydrogen peroxide and water, and a cleaning step using a mixture of hydrochloric acid, hydrogen peroxide and water.

Further, there have been proposed methods of etching the surface of an interlayer insulating film with a dilute hydrofluoric acid solution, and performing acid cleaning when using an alkaline polishing agent. The most frequently used post-treatment for the chemical mechanical polishing step is that after brush scrub cleaning, for example, SC with an alkaline cleaning liquid of ammonia: hydrogen peroxide: water (weight ratio) of 1: 1: 5.
1) Cleaning is performed to remove particles adhered to the substrate surface in the polishing step. Further, an aqueous solution of citric acid is used for cleaning metal impurities adsorbed on the substrate surface after CMP, and an aqueous solution of citric acid or ethylenediaminetetraacetic acid (EDTA) is used together with hydrogen fluoride. It has been known. Further, a cleaning solution containing an organic acid such as citric acid and a complexing agent is also known.

However, it is difficult to remove metal impurities such as abrasive particles remaining on the substrate after chemical mechanical polishing to a level that does not cause a problem, and it is necessary to use a high concentration of the cleaning liquid in order to obtain a cleaning effect. There is a problem that the burden on the environment such as waste liquid treatment is large.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a method for reducing the burden on the environment and remaining on a semiconductor component such as a semiconductor substrate after chemical mechanical polishing (CMP).
Fe, Mn, A based on CMP abrasive grains such as alumina, metal impurities or metal wiring contained in CMP
An object of the present invention is to provide a cleaning liquid having a high cleaning effect on impurities such as l, Ce, Cu, W, and Ti.

[0006]

The present invention relates to a water-soluble (co) polymer (salt) containing a sulfonic acid (salt) group and / or a carboxylic acid (salt) group as an essential component (hereinafter referred to as "water-soluble (salt) (Co) polymer (salt) ”). The semiconductor component cleaning liquid preferably contains a water-soluble (co) polymer (salt) containing a sulfonic acid (salt) group and a carboxylic acid (salt) group as essential components. Further, as the monomer having the sulfonic acid (salt) group as a component, 2-methyl-1,3-butadiene-1-
Sulfonic acid (salt) is preferred. Furthermore, the cleaning liquid for semiconductor components of the present invention is preferably used for cleaning semiconductor components after chemical mechanical polishing.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION A water-soluble (co) polymer (salt) containing a sulfonic acid (salt) group and / or a carboxylic acid (salt) group as an essential component, which is a main component of the cleaning solution for semiconductor parts of the present invention, is as follows. For example, a monomer having a sulfonic acid (salt) group and / or a carboxylic acid (salt) group, or, if necessary, (co) polymerizing a monomer component composed of these and another monomer. Can be obtained.

Here, as the monomer having a sulfonic acid (salt) group, for example, a conjugated dienesulfonic acid (salt) represented by the following general formula (I) (eg, 2-methyl-1,3
-Butadiene-1-sulfonic acid) (Wherein, R ^{1 to} R ⁶ are a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 20 carbon atoms or —SO ₃ X, wherein X is a hydrogen atom, a metal atom, an ammonium group Or at least one of R ^{1 to} R ⁶ is —SO ₃ X), (meth) acrylamide-
2-methylpropanesulfonic acid (salt) having the following general formula (I
An unsaturated (meth) allyl ether monomer represented by I) [for example, 3-allyloxy-2-hydroxypropanesulfonic acid (salt), 3-methallyloxy-2-hydroxypropanesulfonic acid (salt)],

[0009]

Wherein R ⁷ is a hydrogen atom or a group having 1 to 1 carbon atoms.
8 are the same or different, and represent 0 or an integer of 1 to 100 (provided that a + b + c + d = 0
To 100), the (OC ₂ H ₄ ) unit and the (OC ₃ H ₆ ) unit are bonded in an arbitrary order, Y and Z are sulfonic acid groups or hydroxyl groups, and at least one of Y and Z is It is a sulfonic acid group. ], 2-hydroxy-3-acrylamidopropanesulfonic acid (salt), styrenesulfonic acid (salt), methallylsulfonic acid (salt), vinylsulfonic acid (salt), allylsulfonic acid (salt), isoamylenesulfonic acid (Salts) and the like. Preferably, 2-methyl-1,3-butadiene-1-sulfonic acid (salt), (meth) acrylamido-2-methylpropanesulfonic acid (salt), 3-allyloxy-2-hydroxypropanesulfonic acid (salt), Styrenesulfonic acid (salt). Particularly preferred is 2-methyl-1,3-butadiene-1-sulfonic acid (salt). These sulfonic acid (salt) group-containing monomers can be used alone or in combination of two or more.

The monomer containing a carboxylic acid (salt) group as a constituent unit is not particularly limited as long as it is a monomer containing a carboxylic acid group and having a polymerizable double bond.
Examples include acrylic acid, methacrylic acid, α-haloacrylic acid, maleic acid, maleic anhydride, itaconic acid, vinyl acetic acid, allyl acetic acid, fumaric acid, phosphinocarboxylic acid, β-carboxylic acid, and salts thereof. Can be Preferably, acrylic acid, methacrylic acid, itaconic acid or salts thereof are good. Monomers having a polymerizable double bond containing these carboxylic acid (salt) groups,
One type may be used alone, or two or more types may be used in combination.

The water-soluble polymer of the present invention must contain at least one of a sulfonic acid group and / or a carboxylic acid group, and a sulfonic acid group homopolymer containing no carboxylic acid group has a sulfonic acid group. A carboxylic acid polymer that is not included or a copolymer that contains a sulfonic acid group and a carboxylic acid group as essential components may be used. Preferably, a carboxylic acid polymer containing no sulfonic acid group and a copolymer containing a sulfonic acid group and a carboxylic acid group as essential components, and more preferably a copolymer containing a sulfonic acid group and a carboxylic acid group as essential components It is united. In a copolymer containing a sulfonic acid group and a carboxylic acid group as essential components, the amount of the sulfonic acid (salt) group-containing monomer is 2% in the monomer component.
The carboxylic acid (salt) group-containing monomer is used in an amount of 98 to 20 mol%, preferably 9 to 50 mol%, more preferably 5 to 50 mol%, and still more preferably 10 to 35 mol%.
It is 5 to 50 mol%, more preferably 90 to 65 mol%.

Furthermore, in the water-soluble (co) polymer (salt) having a sulfonic acid (salt) group and / or a carboxylic acid (salt) group of the present invention, the sulfonic acid (salt) group and / or the carboxylic acid (salt) ) In addition to the monomer containing a group as a constitutional unit, one or more kinds of other monomers copolymerizable therewith can be copolymerized. Other copolymerizable monomers include, for example, unsaturated alcohols such as vinyl alcohol, allyl alcohol, methyl vinyl alcohol, ethyl vinyl alcohol, and vinyl glycolic acid, hydroxymethyl (meth) acrylate, and hydroxyethyl (meth) ) Acrylate, hydroxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, glycerol mono (meth) acrylate, glycerol di (meth) acrylate, polytetramethylene glycol mono (meth) acrylate,
Hydroxyl group-containing (meth) such as polytetramethylene glycol di (meth) acrylate, butanediol (meth) acrylate, and hexanediol (meth) acrylate
Acrylic esters, aromatic vinyl compounds such as styrene, α-methylstyrene, vinyltoluene, and p-methylstyrene; (meth) methyl (meth) acrylate, ethyl (meth) acrylate, and octyl (meth) acrylate ) Alkyl acrylates, butadiene,
Aliphatic conjugated dienes such as isoprene, 2-chloro-1,3-butadiene and 1-chloro-1,3-butadiene;
Vinyl cyanide compounds such as (meth) acrylonitrile,
Acrylamide, methacrylamide, alkyl (meth)
Examples include amide compounds such as acrylamide, and phosphonic or phosphoric acid compounds such as vinylphosphonic acid. When these other monomers are copolymerized, the content is preferably 30 mol% or less in the monomer components.

In the present invention, a method for producing the water-soluble (co) polymer (salt) having a sulfonic acid (salt) group and / or a carboxylic acid (salt) group as an essential component is as follows, for example. is there. That is, the reaction temperature of the monomer component in the presence of a known polymerization initiator such as hydrogen peroxide, sodium persulfate, or potassium persulfate is usually adjusted to 20 to 200.
° C, preferably at 40 to 150 ° C for 0.1 to 20 hours,
The polymerization reaction is preferably carried out for 1 to 15 hours, and (co)
A polymer (salt) can be produced. As one prescription, the polymerization can be carried out by sequentially adding the monomer components used for the polymerization. Here, the term "sequential polymerization" means to introduce a monomer component into a polymerization system in a predetermined amount per unit time or in a variable amount.

In the above (co) polymerization reaction, a polymerization solvent can be used to smoothly carry out the reaction. As the polymerization solvent, water or a mixture of water and an organic solvent miscible with water is used. Can be. Specific examples of the organic solvent are not particularly limited as long as they can be mixed with water, and include, for example, tetrahydrofuran, 1,4-dioxane, alcohols and the like.

Further, the water-soluble (co) polymer (salt) used in the present invention has a weight average molecular weight of 1,000.
It is from 0,000 to 500,000, preferably from 3,000 to 300,000, and more preferably from 5,000 to 300,000. If it is less than 1,000, the cleaning effect may not be sufficiently exhibited.
If it exceeds 100,000, gelation and the like are involved, and handling becomes difficult.

The cationic species of the water-soluble (co) polymer (salt) containing the sulfonic acid (salt) group and / or carboxylic acid (salt) group of the present invention as an essential component is as follows. Although not particularly limited, hydrogen, an alkali metal, an alkaline earth metal, ammonium, an amine, and the like are preferable to make the compound water-soluble. Examples of the alkali metal include sodium and potassium, and examples of the amine include methylamine, ethylamine, propylamine, dimethylamine, diethylamine, triethylamine, butylamine dibutylamine, alkylamines such as tributylamine, ethylenediamine, diethylenetriamine,
Examples thereof include polyamines such as triethylenetetramine, morpholine, and piperidine, and examples of the alkaline earth metal include calcium and magnesium. Preferred are hydrogen, potassium, ammonium and alkylamine. In addition, having these cationic species (co)
In order to obtain a polymer (salt), a monomer having a preferred cationic species may be (co) polymerized, or an acid-type monomer may be copolymerized and then neutralized with a corresponding alkali. Is also good. It is also possible to exchange (co) polymers (salts) with other cationic species by various ion exchange techniques. These cations may be used alone.
It is also possible to use two or more kinds in combination.

In the present invention, sulfonic acid (salt) is used.
The water-soluble (co) polymer (salt) having a group as a constituent can also be used by hydrogenating a part of the remaining double bond of the base polymer as a precursor. In this case, a known hydrogenation catalyst can be used, and examples thereof include a catalyst and a method described in JP-A-5-222115. After hydrogenation of the base polymer, sulfonation can also be performed by the method described below, but there is no problem if the (co) polymer (salt) is sulfonated and then hydrogenated.

The base polymer used in the present invention may be any of random type, block type copolymer such as AB type or ABA type without any particular limitation. Preferred base polymers include, for example, isoprene homopolymer, butadiene homopolymer, isoprene-styrene random copolymer, isoprene-styrene block copolymer, styrene-isoprene-styrene ternary block copolymer, butadiene-styrene random copolymer. Polymers, butadiene-styrene block copolymers, styrene-butadiene-styrene block copolymers, and hydrogenated products of these (co) polymers, ethylene-propylene-diene terpolymers, and the like, and are preferable. An aromatic monomer-conjugated diene block copolymer, more preferably a styrene-isoprene-based block copolymer.

The water-soluble (co) polymer (salt) having a sulfonic acid (salt) group as a constituent component of the present invention can be prepared by subjecting the above base polymer to a known method, for example, a new experimental course (volume 14). III, p. 1773) or JP-A-2-22.
It can be obtained by sulfonation according to the method described in JP 7403-A.

That is, the base polymer can be sulfonated at a double bond portion in the polymer using a sulfonating agent. In this sulfonation, the double bond is opened to form a single bond, or a hydrogen atom is replaced with a sulfonic acid (salt) while the double bond remains. When another monomer is used, for example, an aromatic unit may be sulfonated in addition to a diene unit portion in a double bond portion. The sulfonating agent in this case is preferably sulfuric anhydride, a complex of sulfuric anhydride and an electron donating compound, sulfuric acid, chlorosulfonic acid,
Fuming sulfuric acid, bisulfite (Na salt, K salt, Li salt, etc.)
Are used.

Here, as the electron donating compound, N,
Ethers such as N-dimethylformamide, dioxane, dibutyl ether, tetrahydrofuran, diethyl ether; pyridine, piperazine, trimethylamine,
Amines such as triethylamine and tributylamine;
Sulfides such as dimethyl sulfide and diethyl sulfide; nitrile compounds such as acetonitrile, ethyl nitrile and propyl nitrile; and the like, of which N, N-dimethylformamide and dioxane are preferable.

The amount of the sulfonating agent is usually from 0.2 to 2.0 mol, preferably from 0.3 to 1.2 mol, as calculated as sulfuric anhydride, relative to 1 mol of the diene unit in the base polymer. If it is less than 0.2 mol, it is difficult to obtain a water-soluble sulfonic acid polymer, while if it exceeds 2.0 mol, the amount of unreacted sulfonating agent such as sulfuric anhydride increases, and after neutralization with alkali, Is produced, and the purity is undesirably reduced.

In the sulfonation, a solvent inert to a sulfonating agent such as sulfuric anhydride can be used. Examples of the solvent include halogenated compounds such as chloroform, dichloroethane, tetrachloroethane, tetrachloroethylene and dichloromethane. Hydrocarbons; nitromethane,
Nitro compounds such as nitrobenzene; and aliphatic hydrocarbons such as liquid sulfur dioxide, propane, butane, pentane, hexane, and cyclohexane. These solvents may be used as a mixture of two or more.

The reaction temperature for this sulfonation is usually -7
0 to + 200 ° C, preferably -30 to + 50 ° C,
If the temperature is lower than -70 ° C, the sulfonation reaction is slow, which is not economical. On the other hand, if the temperature exceeds + 200 ° C, a side reaction occurs, and the product may be blackened or insolubilized, which is not preferable. Thus, an intermediate (a sulfonate of the base polymer, hereinafter referred to as “intermediate”) in which a sulfonating agent such as sulfuric anhydride is bonded to the base polymer is produced.

In the water-soluble sulfonated product of the present invention, the double bond is opened to form a single bond to which a sulfonic acid (salt) is bonded by reacting the intermediate with water or a basic compound, or It is obtained by replacing a hydrogen atom with a sulfonic acid (salt) while leaving a double bond. Examples of the basic compound include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, and lithium hydroxide; sodium methoxide, sodium ethoxide, potassium methoxide, sodium tert-butoxide, and potassium methoxide.
alkali metal alkoxides such as t-butoxide; carbonates such as sodium carbonate, potassium carbonate and lithium carbonate; methyl lithium, ethyl lithium, n-butyl lithium, sec-butyl lithium, amyl lithium, propyl sodium, methyl magnesium chloride, ethyl magnesium Organometallic compounds such as bromide, propylmagnesium iodide, diethylmagnesium, diethylzinc, triethylaluminum, triisobutylaluminum; aqueous ammonia, trimethylamine,
Examples include amines such as triethylamine, tripropylamine, tributylamine, pyridine, aniline, and piperazine; and metal compounds such as sodium, lithium, potassium, calcium, and zinc. These basic compounds can be used alone or in combination of two or more. Among these basic compounds, alkali metal hydroxides and aqueous ammonia are preferable, and sodium hydroxide and lithium hydroxide are particularly preferable.

The basic compound is used in an amount of 2 mol or less, preferably 1.3 mol, per mol of the sulfonating agent used.
If it is less than 2 moles, and if it exceeds 2 moles, the amount of unreacted basic compounds increases, and the purity of the product is undesirably reduced. In the reaction between the intermediate and a basic compound, the basic compound can be used in the form of an aqueous solution, or can be used by dissolving it in an organic solvent inert to the basic compound. Examples of the organic solvent include, in addition to the above various organic solvents, aromatic hydrocarbon compounds such as benzene, toluene, and xylene; methanol, ethanol, propanol,
Examples include alcohols such as isopropanol and ethylene glycol. These solvents may be used as a mixture of two or more.

When the basic compound is used as an aqueous solution or an organic solvent solution, the basic compound concentration is usually
It is about 1 to 70% by weight, preferably about 10 to 50% by weight. The reaction temperature is usually -30 to +150.
° C, preferably 0 to + 120 ° C, more preferably +5
It is carried out at 0 to + 100 ° C, and can be carried out at normal pressure, reduced pressure or increased pressure. Further, the reaction time is usually 0.1 to 24 hours, preferably 0.5 to 24 hours.
~ 5 hours.

The cleaning liquid for semiconductor parts of the present invention is usually prepared by adding the water-soluble (co) polymer (salt) containing a sulfonic acid (salt) group and / or a carboxylic acid (salt) group to water and / or water.
Or, in a hydrophilic organic solvent (hereinafter also referred to as “solvent”),
0.1 to 20% by weight, particularly preferably 1.0 to 10% by weight, is dissolved. If the concentration of the water-soluble (co) polymer (salt) is less than 0.1% by weight, the cleaning effect is not sufficiently exhibited, while if the concentration is more than 20% by weight, an effect commensurate with the concentration is expected. Not efficient.

Examples of the solvent include water and hydrophilic organic solvents such as alcohols, ethers and ketones. Among them, those containing water as a main component, particularly water are preferred. Among the above hydrophilic organic solvents, specific examples of alcohols include methanol, ethanol, n-propyl alcohol, i-propyl alcohol, n-butyl alcohol, sec-butyl alcohol, t-butyl alcohol, n-hexyl alcohol, n-octyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene monomethyl ether acetate, diacetone alcohol, and the like. . Further, specific examples of ethers include tetrahydrofuran and dioxane, and specific examples of ketones include acetone, methyl ethyl ketone,
Examples thereof include methyl isobutyl ketone and diisobutyl ketone. These hydrophilic organic solvents can be used alone or in combination of two or more.

The cleaning liquid for semiconductor parts of the present invention includes:
In addition to the (co) polymer (salt) of the present invention, other known detergent components can be used in combination. As other cleaning components, for example, ethylenediaminetetraacetic acid (EDT)
A), trans-1,2-cyclohexanediaminetetraacetic acid (CyDTA), nitrilotriacetic acid (NTA), diethylenetriaminepentaacetic acid (DTPA), N- (2-
(Hydroxyethyl) ethylenediamine-N, N ', N'
-In addition to compounds such as triacetic acid (EDTA-OH) and polyaminocarboxylic acids such as salts thereof, oxalic acid, citric acid, ammonia, hydrogen peroxide, hydrochloric acid, hydrogen fluoride and the like can be mentioned. In general, these compounds are used in the form of a free acid or a salt, and it is preferable to use them in the form of a salt such as an ammonium salt, a potassium salt, and an amine salt which do not adversely affect the properties for semiconductor production. These compounds can be used alone or in combination of two or more. The amount of these compounds used is not particularly limited, but is usually not more than 5 times the weight of the (co) polymer (salt) of the present invention. In addition, various alkaline solutions may be used in combination in order to enhance the cleaning effect.

The cleaning liquid for semiconductor components of the present invention is mainly used for removing metal impurities based on abrasive particles remaining on semiconductor components after CMP. The method can be adopted. Further, before or after performing the cleaning using the cleaning liquid of the present invention, it is possible to further increase the efficiency of removing metal impurities by using a known cleaning liquid or performing a cleaning method. Although the pH of the cleaning solution of the present invention is not particularly limited, it can be generally used at 3 to 11. Outside this range,
This is not preferable because the cleaning ability may be reduced or the metal portion may be corroded. The operating temperature is usually 5 to 5
0 ° C.

The cleaning liquid for semiconductor parts of the present invention has a low environmental load, and has CMP polishing abrasives such as silica and alumina remaining on the semiconductor parts after chemical mechanical polishing.
Since it has a cleaning effect on impurities such as Fe, Mn, Al, Ce, Cu, W, and Ti based on metal impurities or metal wiring contained in CMP, semiconductors such as semiconductor substrates, interlayer insulating films, and metal wiring are provided. Useful for cleaning parts.

[0034]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the following examples. The percentages and parts in the examples are on a weight basis unless otherwise specified. Various measurements in the examples were performed as follows.

Weight-average molecular weight The weight-average molecular weight (Mw) is obtained by converting the result determined by gel permeation chromatography (GPC) using a calibration curve prepared using sodium polystyrene sulfonate as a standard sample. here,
The GPC measurement conditions are as follows. Column: G3000PWXL [manufactured by Tosoh Corporation] Column: GMPWXL [manufactured by Tosoh Corporation] Column: GMPWXL [manufactured by Tosoh Corporation] The columns were connected in series in the following order, and a sample was introduced from the column side. Detector: Differential refractometer RI-8021 [manufactured by Tosoh Corporation] Eluent: water / acetonitrile / sodium sulfate = 2,1
00/900/15 (weight ratio) Flow rate; 1.0 ml / min Temperature; 40 ° C. Sample concentration; 0.2% Sample injection volume; 400 μl

Reference Example 1 175 g of a 40% aqueous solution of potassium 2-methyl-1,3-butadiene-1-sulfonate, 287 g of an 80% aqueous solution of acrylic acid, 90 g of water and 35% aqueous hydrogen peroxide
5 g is dissolved in an inner volume 2 containing 350 g of water.
Into the L container, the mixture was added dropwise over 10 hours while stirring under reflux. After completion of the dropwise addition, the mixture was kept under reflux for 2 hours to obtain a copolymer (salt). The weight average molecular weight of the copolymer (salt) is 1
It was 0000.

Reference Example 2 In Reference Example 1, a 40% concentration of 2-methyl-1,3-
175 g of an aqueous solution of potassium butadiene-1-sulfonate was added to 500 g of an aqueous solution of potassium acrylamido-2-methylsulfonate at a concentration of 20%, and 287 g of an aqueous solution of acrylic acid having a concentration of 80% was added to an aqueous solution of itaconic acid having a concentration of 30%
A copolymer (salt) was obtained in the same manner as in Reference Example 1 except that the amount was changed to 62 g. The weight average molecular weight of the copolymer (salt) was 13,000.

Reference Example 3 In Reference Example 1, a 40% concentration of 2-methyl-1,3-
175 g of an aqueous solution of potassium butadiene-1-sulfonate was added to a 20% aqueous solution of ammonium styrenesulfonate 2
50 g and 287 of 80% strength aqueous acrylic acid solution
g was changed to 312 g of an aqueous 80% methacrylic acid solution, and the same procedure as in Reference Example 1 was carried out to obtain a copolymer (salt).
I got The weight average molecular weight of the copolymer (salt) is 15.0
00.

Reference Example 4 In Reference Example 1, a 40% concentration of 2-methyl-1,3-
175 g of an aqueous solution of potassium butadiene-1-sulfonate was added to 250 g of the aqueous solution, and 287 g of an aqueous solution of acrylic acid having a concentration of 80% was converted to 666 g of an aqueous solution of itaconic acid having a concentration of 30%.
Except having changed to g, it carried out similarly to Reference Example 1 and obtained the copolymer (salt). The weight average molecular weight of the copolymer (salt) is
It was 13,000.

Reference Example 5 The same procedure as in Reference Example 1 was carried out except that 40% concentration of 2-methyl-1,3-
A sulfonic acid polymer (salt) was obtained in the same manner as in Reference Example 1 except that 175 g of an aqueous solution of potassium butadiene-1-sulfonate was changed to 550 g of the aqueous solution, and 287 g of an aqueous solution of acrylic acid having a concentration of 80% was changed to 0. Was. The weight average molecular weight of the polymer (salt) was 10,000.

Reference Example 6 In Reference Example 1, a 40% concentration of 2-methyl-1,3-
175 g of an aqueous solution of potassium butadiene-1-sulfonate was reduced to 0 g, and 287 g of an aqueous solution of 80% acrylic acid was used.
Was changed to 400 g, and a carboxylic acid polymer (salt) was obtained in the same manner as in Reference Example 1. The weight average molecular weight of the polymer (salt) was 15,000.

Examples 1 to 3 A silicon wafer with an oxide film, which was immersed in an aqueous ferric nitrate solution and contaminated in advance, was measured for the concentration of Fe on the surface of the wafer using a total reflection X-ray fluorescence apparatus. The surface concentration of Fe is 15.0
It was 00 × 10 ¹⁰ (atoms / cm ² ). Next, washing was performed at 40 ° C. for 3 minutes in an aqueous solution of 1% (Example 1), 5% (Example 2), and 10% (Example 3) prepared using the copolymer (salt) of Reference Example 1. After washing with water and drying, the concentration of Fe on the wafer surface was measured again to evaluate the ability to remove Fe.

Examples 4 to 6 The same procedures as in Examples 1 to 3 were carried out except that the copolymer (salt) of Reference Example 1 was changed to the copolymer (salt) of Reference Example 2. Examples 7 to 9 The same procedure was performed as in Examples 1 to 3, except that the copolymer (salt) of Reference Example 1 was changed to the copolymer (salt) of Reference Example 3. Examples 10 to 12 The same procedure was performed as in Examples 1 to 3, except that the copolymer (salt) of Reference Example 1 was changed to the copolymer (salt) of Reference Example 4.

Examples 13 to 15 Examples 13 to 15 were carried out in the same manner as in Examples 1 to 3, except that the copolymer (salt) of Reference Example 1 was changed to the polymer (salt) of Reference Example 5. Examples 16 to 18 The same procedure was performed as in Examples 1 to 3, except that the copolymer (salt) of Reference Example 1 was changed to the polymer (salt) of Reference Example 6.

Comparative Example 1 The procedure of Examples 1 to 3 was repeated except that a 10% aqueous solution of citric acid was used instead of the aqueous solution of the copolymer (salt) of Reference Example 1. As shown in Table 1, it can be seen that the cleaning liquid of the present invention is excellent in the ability to remove Fe.

[0046]

[Table 1]

[0047]

The cleaning liquid for semiconductor components of the present invention is an excellent cleaning liquid which has a small load on the environment and can efficiently remove metal impurities remaining on the semiconductor component after chemical mechanical polishing.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Toshio Ono 2--11-11 Tsukiji, Chuo-ku, Tokyo FSR term in JSR Corporation (reference) 4H003 BA12 DA15 DB01 EB28 EB30 FA03

Claims (4)

[Claims] 1. A cleaning liquid for semiconductor components containing a water-soluble (co) polymer (salt) containing a sulfonic acid (salt) group and / or a carboxylic acid (salt) group as an essential component. 2. The cleaning solution for a semiconductor component according to claim 1, comprising a water-soluble (co) polymer (salt) containing a sulfonic acid (salt) group and a carboxylic acid (salt) group as essential components. 3. The cleaning solution for semiconductor parts according to claim 1, wherein the monomer having a sulfonic acid (salt) group as a component is 2-methyl-1,3-butadiene-1-sulfonic acid (salt). . 4. The cleaning liquid for semiconductor parts according to claim 1, which is used for cleaning semiconductor parts after chemical mechanical polishing.