JP2006041494A - Cleaning composition for semiconductor component, and manufacturing method of semiconductor device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a cleaning composition for semiconductor component which has superior cleaning properties with respect to impurities remaining on a to-be-polished surface of a semiconductor component after chemical mechanical polishing, and further reduces burden on environment, and to provide a method for manufacturing a semiconductor device comprising a step for cleaning, by using the cleaning composition for semiconductor component. <P>SOLUTION: The cleaning composition for semiconductor component comprises a water-soluble polymer (a), having a specific molecular weight and a compound (b) represented by a formula (1): NR<SB>4</SB>OH, wherein each R is independently a hydrogen atom or an alkyl group of 1 to 6 carbon atoms. The method for manufacturing the semiconductor device comprises a step of chemical mechanical polishing the semiconductor component, and then cleaning with the cleaning composition for semiconductor component. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a semiconductor component cleaning composition and a method for manufacturing a semiconductor device. More specifically, the present invention relates to a semiconductor component cleaning composition containing a specific water-soluble polymer and a specific compound, and a method of manufacturing a semiconductor device including a step of cleaning with the semiconductor component cleaning composition.

  In the manufacturing process of a semiconductor device, chemical mechanical polishing (CMP) has attracted attention. Chemical mechanical polishing has an advantage that the planarization process can be shortened as compared with the conventional RIE (reactive ion etching) or other etch-back technique or reflow technique. Further, chemical mechanical polishing is less susceptible to pattern dependence and has the advantage that good planarization can be realized. Such chemical mechanical polishing is applied to, for example, planarization of metal wirings and interlayer insulation films in a multilayer wiring board.

  However, when a semiconductor component used in a semiconductor device is planarized by chemical mechanical polishing, the abrasive particles, sodium ions, potassium ions contained in the polishing aqueous dispersion used for chemical mechanical polishing after chemical mechanical polishing. It is known that impurities such as these remain on the polished surface of the semiconductor component. Since these impurities adversely affect the characteristics of the semiconductor device, they must be removed by cleaning.

  Under such circumstances, in order to clean a substrate having metal wiring, the following cleaning liquid has been proposed. For example, a cleaning liquid containing oxalic acid, ammonium oxalate or polyaminocarboxylic acid (see Patent Document 1), a cleaning treatment containing an organic acid such as citric acid and a complexing agent such as hexametaphosphoric acid (see Patent Document 2) , A detergent containing a surfactant having an alkyl group and an ethylene oxide structure (see Patent Document 3), and a detergent using a combination of two complexing agents such as a combination of ethylenediaminetetrakismethylphosphonic acid and acetic acid (See Patent Document 4), semiconductor component cleaning liquids containing a water-soluble (co) polymer having sulfonic acid groups and / or carboxyl groups as essential components (see Patent Document 5), and the like.

However, when the cleaning liquid as described above is used, it is difficult to sufficiently remove impurities such as abrasive particles, polishing waste, sodium ions and potassium ions remaining on the substrate after chemical mechanical polishing. there were. In addition, in order to exert the cleaning effect, it is necessary to use a high concentration cleaning liquid, and there is a problem that a burden on the environment such as waste liquid treatment is large.
Japanese Patent Application Laid-Open No. 11-131093 Japanese Patent No. 3219020 JP-A-11-112418 JP-A-9-157692 JP 2001-64689 A

  An object of the present invention is to solve the above-described conventional technique, which has a high cleaning effect on impurities remaining on a polished surface of a semiconductor component after chemical mechanical polishing and has a load on the environment. An object of the present invention is to provide a composition for cleaning semiconductor components with a small amount.

  Another object of the present invention is to provide a method of manufacturing a semiconductor device including a step of cleaning with the above-described semiconductor component cleaning composition.

  As a result of diligent research to solve the above-mentioned problems, the present inventors have found that a composition for cleaning a semiconductor component containing a water-soluble polymer having a specific molecular weight and ammonium hydroxide has a high cleaning effect against impurities and is effective for the environment. The inventors have found that the load is small and have completed the present invention.

That is, the composition for cleaning semiconductor components according to the present invention is:
Formulated with a water-soluble polymer (a) having a weight average molecular weight of 1,000 to 100,000 in terms of sodium polystyrene sulfonate measured by gel permeation chromatography, and a compound (b) represented by the following formula (1) It is characterized by being made.
NR ₄ OH (1)
(In Formula (1), R represents a hydrogen atom or a C1-C6 alkyl group each independently.)
At least one of the water-soluble polymer (a) and the compound (b) may exist in at least one of a dissociated state and a dissociated state and recombined with a counter ion.

The water-soluble polymer (a) preferably has a carboxyl group.
The compound (b) is preferably tetramethylammonium hydroxide.
It is preferable that the composition for cleaning a semiconductor component further contains at least one selected from the group consisting of an antioxidant (c) and a complexing agent (d). A substrate is preferred.

A method for manufacturing a semiconductor device according to the present invention includes:
The semiconductor component is characterized by including a step of chemical mechanical polishing and then cleaning with the above semiconductor component cleaning composition, and the semiconductor component is preferably a copper wiring board.

  According to the present invention, there is provided a semiconductor component cleaning composition having a high cleaning effect on impurities such as abrasive particles, sodium ions and potassium ions remaining on a polished surface of a semiconductor component after chemical mechanical polishing and having a low environmental impact. Can be provided.

  In addition, by cleaning with the semiconductor component cleaning composition, it is possible to provide a method for manufacturing a semiconductor device in which the characteristics of the semiconductor device are not adversely affected.

Hereinafter, the present invention will be specifically described.
The composition for cleaning semiconductor components according to the present invention comprises a water-soluble polymer (a) having a weight average molecular weight in terms of sodium polystyrene sulfonate measured by gel permeation chromatography of 1,000 to 100,000 and the following formula (1): )
NR ₄ OH (1)
(In Formula (1), R represents a hydrogen atom or a C1-C6 alkyl group each independently.)
It is preferable that the compound (b) represented by these is mix | blended and these are mix | blended with a suitable solvent. The composition may further contain at least one selected from the group consisting of an antioxidant (c) and a complexing agent (d).

<Water-soluble polymer (a)>
The water-soluble polymer (a) is gel permeation chromatography (the solvent is water /
The polystyrene-sulfonate sodium weight average molecular weight measured with a mixed solvent of acetonitrile / sodium sulfate (weight ratio = 2,100 / 900/15) is 1,000 to 100,000, and 2,000 to 30,000. It is more preferable that it is 3,000 to 20,000. By using the water-soluble polymer (a) having a weight average molecular weight in this range, it is possible to obtain a semiconductor component cleaning composition having high detergency and easy handling.

  The water-soluble polymer (a) is not particularly limited as long as the weight average molecular weight is in the above range, but preferably has a carboxyl group. Examples of the water-soluble polymer (a) having a carboxyl group include a homopolymer of a monomer having a carboxyl group, a copolymer composed of two or more monomers having a carboxyl group, or a monomer having a carboxyl group. The copolymer etc. which 1 type (s) or 2 or more types and another monomer consists of 1 type (s) or 2 or more types are mentioned.

  As a monomer which has the said carboxyl group, the monomer which has a carboxyl group and a polymerizable double bond simultaneously in a molecule | numerator is mentioned, for example. Specific examples of the monomer 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- Examples thereof include carboxylic acid. Among these, acrylic acid, methacrylic acid, and itaconic acid are preferable because excellent detergency can be obtained.

  When the water-soluble polymer (a) is a copolymer of a monomer having a carboxyl group and another monomer, examples of the other monomer include unsaturated alcohol compounds and aromatic vinyl compounds. , Hydroxyl group-containing (meth) acrylic acid ester compounds, (meth) acrylic acid alkyl ester compounds, aliphatic conjugated diene compounds, vinylcyan compounds, amide compounds having a polymerizable double bond, phosphonic acids having a polymerizable double bond, etc. Is mentioned.

  Specific examples of the unsaturated alcohol compound include vinyl alcohol, allyl alcohol, methyl vinyl alcohol, ethyl vinyl alcohol, and vinyl glycolic acid. Specific examples of the aromatic vinyl compound include styrene, α-methylstyrene, vinyltoluene, and p-methylstyrene. Specific examples of the hydroxyl group-containing (meth) acrylic acid ester compound include hydroxymethyl (meth) acrylate, 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, polytetramethylene glycol di (meth) acrylate, butanediol (meth) acrylate, hexanediol (meta ) Acrylate and the like. Specific examples of the (meth) acrylic acid alkyl ester compound include methyl (meth) acrylate, ethyl (meth) acrylate, octyl (meth) acrylate, and the like. Specific examples of the aliphatic conjugated diene compound include butadiene, isoprene, 2-chloro-1,3-butadiene, 1-chloro-1,3-butadiene, and the like. Specific examples of the vinylcyan compound include (meth) acrylonitrile. Specific examples of the amide compound having a polymerizable double bond include (meth) acrylamide and alkyl (meth) acrylamide. Specific examples of the phosphonic acid having a polymerizable double bond include vinylphosphonic acid. In addition, as an alkyl group in the said illustration, a C1-C8 linear or branched alkyl group etc. are mentioned, for example.

When the water-soluble polymer (a) is a copolymer of a monomer having a carboxyl group and another monomer, the content of the structural unit derived from the other monomer is the total structural unit. It is preferable that it is 30 mol% or less.

  When the water-soluble polymer (a) is a (co) polymer of the above-mentioned monomer having a carboxyl group, or a copolymer of a monomer having a carboxyl group and another monomer, these The (co) polymer can be obtained, for example, by the following polymerization method.

  Using the monomer component, the polymerization reaction is carried out in the presence of a suitable polymerization initiator at 20 to 120 ° C., preferably at 40 to 100 ° C., for 0.1 to 20 hours, preferably 1 to 15 hours. Thus, the (co) polymer can be produced. Here, the (co) polymer can be produced by sequential polymerization in which monomer components used for polymerization are sequentially added. Specifically, this sequential polymerization represents a polymerization method in which the monomer component is charged into the polymerization system within a predetermined time by changing the addition amount at a constant amount per unit time. Use of this method is preferable because the polymerization reaction can be performed with good reproducibility.

  In the polymerization reaction, a solvent can coexist. Examples of such a polymerization solvent include water, water, and a mixture of organic solvents that can be mixed with water. Specific examples of the organic solvent include tetrahydrofuran, 1,4-dioxane, alcohol having 1 to 4 carbon atoms, and the like. Of these, water is preferable as the polymerization solvent.

In addition, it is preferable not to allow soaps to coexist in the polymerization reaction.
In the semiconductor component cleaning composition of the present invention, the water-soluble polymer (a) is preferably added in an amount of 0.01 to 1% by mass, more preferably 0.02 to 0.5% by mass, based on the entire composition. It is desirable that In addition, the water-soluble polymer (a) may be contained in the composition in any state as it is, in a dissociated state, or in a state where the dissociated water-soluble polymer (a) is recombined with a counter ion. Good.

  When the water-soluble polymer (a) has a carboxyl group, a part of the carboxyl group may form a salt. Examples of the counter cation that forms the salt include ammonium ions. The content of carboxyl groups forming the salt is preferably 50 mol% or less with respect to the total number of carboxyl groups.

<Compound (b)>
The compound (b) is ammonium hydroxide represented by the formula (1).
Examples of the compound (b) include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetraisopropylammonium hydroxide, tetrabutylammonium hydroxide, and tetraisobutylammonium hydroxide. Among these, tetramethylammonium hydroxide and tetraethylammonium hydroxide are preferable, and tetramethylammonium hydroxide is particularly preferable because excellent detergency can be obtained.

The said compound (b) can be used individually or in mixture of 2 or more types.
The composition is preferably formed by blending the compound (b) with respect to the whole composition, preferably 0.01 to 1% by mass, more preferably 0.02 to 0.5% by mass. Moreover, the said compound (b) may be contained in the composition in any state of the state as it is, the dissociated state, and the state which the dissociated compound (b) recombined with the counter ion.

<Antioxidant (c)>
The composition preferably further contains an antioxidant (c) in order to prevent oxidation of the metal wiring part.

  Examples of the antioxidant (c) include lactones and other antioxidants. Specific examples of the lactones include L-ascorbic acid, erythorbic acid, and ascorbic acid stearyl acid ester. Specific examples of the other antioxidants include gallic acid, chlorogenic acid, oxalic acid, catechin, and dibutylhydroxytoluene.

Among these, L-ascorbic acid, erythorbic acid, gallic acid, and oxalic acid are preferable in terms of excellent antioxidant performance.
The said antioxidant (c) may be used individually by 1 type, or may be used in combination of 2 or more types.

The composition may comprise 5 parts by weight or less, more preferably 0.1 to 3.5 parts by weight of the antioxidant (c) with respect to 1 part by weight of the water-soluble polymer (a). preferable.
<Complexing agent (d)>
The composition preferably further contains a complexing agent (d) in order to prevent re-deposition of metal impurities.

  Examples of the complexing agent (d) include aminopolycarboxylic acids, polybasic acids (excluding oxalic acid), amino acids, and other amino group-containing compounds. Specific examples of the aminopolycarboxylic acids include ethylenediaminetetraacetic acid (EDTA), trans-1,2-cyclohexanediaminetetraacetic acid (CyDTA), diethylenetriaminepentaacetic acid (DTPA), and N- (2-hydroxyethyl) ethylenediamine. -N, N ', N'-triacetic acid (EDTA-OH), nitrilotriacetic acid, hydroxyethyliminodiacetic acid and the like. Specific examples of the polybasic acid (excluding oxalic acid) include maleic acid, malonic acid, tartaric acid, malic acid, succinic acid, and citric acid. Specific examples of the amino acid include glycine, alanine, aspartic acid, methionine and the like. Specific examples of the other amino group-containing compounds include ethylenediamine and ammonia.

Among these, ethylenediaminetetraacetic acid, citric acid, glycine, alanine, ethylenediamine, and ammonia are preferable because of excellent anti-redeposition performance of metal impurities.
The complexing agent (d) may be used alone or in combination of two or more.

The composition is formed by blending the complexing agent (d) with 5 parts by mass or less, more preferably 0.1 to 3.5 parts by mass with respect to 1 part by mass of the water-soluble polymer (a). It is preferable.
<Other ingredients>
Since the said composition improves a detergency, in the range which does not impair the objective of this invention, it can contain another component as needed.

Examples of the other components include other detergent components and surfactant components.
Examples of the other cleaning agent components include inorganic acids such as hydrochloric acid and hydrofluoric acid, and peroxides such as hydrogen peroxide.

The above-mentioned other detergent components may be used alone or in combination of two or more.
The above composition is formed by blending the above-mentioned other detergent components with respect to 1 part by mass of the water-soluble polymer (a), preferably 5 parts by mass or less, more preferably 0.1 to 3.5 parts by mass. It is preferable.

Examples of the surfactant include an anionic surfactant, a nonionic surfactant, and a cationic surfactant.
Specific examples of the anionic surfactant include carboxylates such as fatty acid soaps and alkyl ether carboxylates; sulfonates such as alkylbenzene sulfonates, alkylnaphthalene sulfonates, and α-olefin sulfonates; Examples thereof include sulfate esters such as higher alcohol sulfates and alkyl ether sulfates; and phosphate ester salts such as alkyl phosphates.

  Specific examples of the nonionic surfactant include ether types such as polyoxyethylene alkyl ether, ether ester types such as glycerin ester polyoxyethylene ether, ester types such as polyethylene glycol fatty acid ester, glycerin ester, and sorbitan ester. Etc.

Specific examples of the cationic surfactant include aliphatic amine salts and aliphatic ammonium salts.
The above surfactants may be used alone or in combination of two or more.

The composition is preferably formed by blending the surfactant with respect to the entire composition, preferably 1% by mass or less, more preferably 0.5% by mass or less.
<Solvent>
Examples of the solvent used in the semiconductor cleaning composition according to the present invention include water, water, and a mixture of organic solvents that can be mixed with water. Of these, water is preferred because of its low environmental burden.

Examples of the organic solvent that can be mixed with water include the solvents exemplified as the organic solvent used in the polymerization of the water-soluble polymer (a).
<Semiconductor component cleaning composition>
In the semiconductor component cleaning composition according to the present invention, the total amount of sodium and potassium contained in the composition is preferably 0.02 ppm or less, more preferably 0.01 ppm or less, particularly preferably 0.005 ppm or less. It is desirable to be. The amount of sodium and potassium is a polymerization initiator, polymerization solvent, monomer, compound (b), antioxidant (c), complexing agent (d), used for the polymerization reaction of the water-soluble polymer (a), It can be controlled by appropriately selecting other components, solvents, etc., or purifying them appropriately.

  As the polymerization initiator, for example, hydrogen peroxide, ammonium persulfate and the like are preferably used, and it is preferable to avoid the use of an initiator containing sodium or potassium as a counter cation such as sodium persulfate.

Moreover, the said refinement | purification can be performed by selecting suitable means, such as distillation and the contact of the compound and ion exchange resin, according to the property of the compound, for example.
You may mix | blend each component of the composition for semiconductor components cleaning based on this invention so that it may become the said content in the step which prepares a composition. Moreover, after mix | blending each said component and preparing a composition in the state concentrated, this composition may be diluted and used for a washing | cleaning process. When preparing the said composition in the concentrated state, it is preferable that the concentration degree is 2-500 times with respect to the said compounding quantity, and it is more preferable that it is 10-100 times.

The composition according to the present invention is preferably used for cleaning semiconductor components. Among the above semiconductor components, it is more preferably used for cleaning a copper wiring board.
<Method for Manufacturing Semiconductor Device>
The method for manufacturing a semiconductor device according to the present invention includes a step of chemically mechanically polishing a semiconductor component, and then cleaning the semiconductor component with the semiconductor component cleaning composition.

  Examples of the semiconductor component include a wiring board, a magnetic head, and a magnetic disk. Specific examples of the wiring board include a wiring board made of an insulating film and a metal pattern as a wiring material, and a multilayer wiring board on which an interlayer insulating film is formed.

  More specifically, the wiring substrate comprising the insulating film and a metal pattern as a wiring material is more specifically, for example, a wafer made of silicon or the like, and an insulating film formed on the wafer and having a wiring recess such as a groove. And a substrate comprising a barrier metal film formed so as to cover the insulating film and the groove, and a film made of a wiring material filling the groove and formed on the barrier metal film. Can be mentioned. Such a wiring board is subjected to chemical mechanical polishing according to a known method, and after the excess wiring material and barrier metal material are removed, the wiring board is subjected to a cleaning process.

  More specifically, the multilayer wiring board on which the interlayer insulating film is formed is, for example, a substrate in which an insulating film is laminated on a wiring board that has been subjected to chemical mechanical polishing according to a known method and further subjected to a cleaning process. Can be mentioned. Such a multilayer wiring board is further subjected to chemical mechanical polishing according to a known method, and after the insulating film is planarized, it is subjected to a cleaning process.

The semiconductor component is preferably a wiring board made of copper as a wiring material.
Examples of the insulating film include a film formed by a vacuum process such as a chemical vapor deposition method. Specifically, a silicon oxide film (a PETEOS film (Plasma Enhanc) is used.
ed-TEOS film), HDP film (High Density Plasma Enhanced-TEOS film), silicon oxide film obtained by a thermal CVD method, etc.), boron phosphorus silicate film (BPSG film) obtained by adding a small amount of boron and phosphorus to SiO ₂ , Examples thereof include an insulating film called FSG (Fluorine-doped silicon glass) in which fluorine is doped in SiO ₂ , an insulating film called SiON (Silicon Oxide Nitride), a silicon nitride, and a low dielectric constant insulating film.

Examples of the low dielectric constant insulating film include alkoxysilane, silane, alkylsilane, arylsilane, and siloxane in the presence of oxygen, carbon monoxide, carbon dioxide, nitrogen, argon, H ₂ O, ozone, ammonia, and the like. , Interlayer insulating films made of polymers obtained by plasma polymerization of silicon-containing compounds such as alkylsiloxanes, interlayer insulating films made of polysiloxane, polysilazane, polyarylene ether, polybenzoxazole, polyimide, silsesquioxane, etc. Examples thereof include a silicon oxide insulating film having a dielectric constant.

  The low dielectric constant silicon oxide insulating film can be obtained, for example, by applying a raw material on a wafer by a spin coating method and then heating in an oxidizing atmosphere. Specifically, the low dielectric constant silicon oxide-based insulating film thus obtained is composed of HSQ film (Hydrogen Silsesquioxane film) made of triethoxysilane, tetraethoxysilane and a small amount of methyltrimethoxysilane. Examples thereof include an MSQ film (Methyl Silsesquioxane film) used as a raw material and an insulating film having a low dielectric constant using other silane compounds as a raw material.

  Furthermore, when the insulating film having a low dielectric constant is manufactured, an insulating film that is further reduced in dielectric constant by mixing appropriate organic polymer particles or the like with the raw material is also used. In the insulating film, the organic polymer is burned off during the heating process to form vacancies during the manufacturing process, so that the dielectric constant can be further reduced. Examples of suitable organic polymer particles include New Pole PE61 (trade name, manufactured by Sanyo Chemical Industries, Ltd., polyethylene oxide-polypropylene oxide-polyethylene oxide block copolymer).

The chemical mechanical polishing (CMP) step can be performed by a known method using a known polishing aqueous dispersion. It is preferable to use an aqueous dispersion containing silica as abrasive particles as the polishing aqueous dispersion because the effects of the present invention can be more effectively exhibited in the cleaning step after chemical mechanical polishing.

  There is no restriction | limiting in particular in the said washing | cleaning process, It can carry out by a well-known washing | cleaning method. Examples of the cleaning method include an immersion method, a brush scrub method, and an ultrasonic cleaning method. The washing temperature is preferably 5 to 50 ° C. The washing time is preferably 1 to 5 minutes in the dipping method, and preferably 0.2 to 2 minutes in the brush scrub method.

In the semiconductor device manufacturing method according to the present invention, the sodium ion concentration in the cleaned semiconductor device can be 5 × 10 ¹⁰ atoms / cm ² or less, preferably 5 × 10 ⁹ atoms / cm ² or less. The potassium ion concentration is 5 × 10 ¹¹ atoms / cm ² or less, preferably 5 × 10 ¹⁰ atoms / cm ^2.
cm ² or less. In the semiconductor device manufacturing method, the residual amount of abrasive particles in the cleaned semiconductor device can be 1,000 particles / surface or less, preferably 500 particles / surface or less. The value of the residual amount of abrasive particles is a value converted to the entire surface of the 8-inch diameter substrate.

[Example]
EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples.

In this specification, the weight average molecular weight (Mw) of the water-soluble polymer was determined by converting a value measured under the following conditions using a calibration curve prepared using sodium polystyrenesulfonate as a standard sample.
Columns: Three columns of G3000PWXL, GMPWXL and GMPWXL (all trade names, manufactured by Tosoh Corporation) were connected in series in this order.
Detector: differential refractometer RI-8021 (trade name, manufactured by Tosoh Corporation)
Eluent: water / acetonitrile / sodium sulfate = 2,100 / 900/15 (weight ratio)
Flow rate: 1.0 mL / min Temperature: 40 ° C
Sample concentration: 0.2% by mass
Sample injection volume: 400 μL
[Synthesis Example 1] Synthesis of water-soluble polymer (synthesis of acrylic acid polymer)
In a 2 liter container charged with 1,000 g of ion-exchanged water and 14 g of 35% by mass hydrogen peroxide solution, 500 g of 20% by mass acrylic acid aqueous solution was evenly added over 10 hours while stirring under reflux. It was dripped. After completion of dropping, the mixture was kept under reflux for 2 hours to obtain an acrylic acid polymer (1) having Mw = 6,000.

Moreover, except having changed the usage-amount of hydrogen peroxide water, it carried out similarly to the said synthesis | combination, and obtained acrylic acid polymer (2)-(4) of Mw = 700, 2,000, and 4,000, respectively.
[Synthesis Example 2] Synthesis of water-soluble polymer (synthesis of acrylic acid / methacrylic acid copolymer)
A mixture of 1400 g of a 50% by mass aqueous acrylic acid solution and 100 g of a 50% by mass aqueous methacrylic acid solution was refluxed in a container having a volume of 2 liters charged with 400 g of ion-exchanged water and 100 g of 32% by mass of hydrogen peroxide. It was added dropwise over 10 hours with stirring. After completion of dropping, the mixture was kept under reflux for 2 hours to obtain an acrylic acid / methacrylic acid copolymer (1) having Mw = 24,000. The copolymerization ratio of acrylic acid in the obtained copolymer was 93% by mass.

[Synthesis Example 3] Synthesis of water-soluble polymer (Synthesis of acrylic acid / acrylamide copolymer)
A mixture of 1200 g of a 20% by mass acrylic acid aqueous solution and 300 g of a 20% by mass acrylic amide aqueous solution was refluxed in a 2 liter container charged with 400 g of ion-exchanged water and 100 g of 35% by mass hydrogen peroxide. The solution was uniformly added dropwise over 10 hours with stirring. After completion of the dropwise addition, the mixture was further kept under reflux for 2 hours to obtain an acrylic acid / acrylamide copolymer (1) having Mw = 78,000. In addition, the copolymerization ratio of acrylic acid in the obtained copolymer was 80% by mass.

  Further, an acrylic acid / acrylamide copolymer (Mw = 140,000) (2) except that the hydrogen peroxide solution was changed to 50 g, the acrylic acid aqueous solution was changed to 1000 g, and the acrylic acid amide aqueous solution was changed to 500 g. ) The copolymerization ratio of acrylic acid was 66% by mass.

[Synthesis Example 4] Synthesis of water-soluble polymer (Synthesis of acrylic acid polymer contaminated with sodium ion)
An acrylic acid polymer (Na) having Mw = 6,000 was obtained in the same manner as in Synthesis Example 1 except that 12 g of a 5% by mass sodium persulfate aqueous solution was used in place of the hydrogen peroxide solution. Here, the value which converted the total amount of sodium ion contained in the reaction mixture after superposition | polymerization per water-soluble polymer was 1,200 ppm.

[Example 1]
(Preparation of semiconductor component cleaning composition)
A solution containing the acrylic acid polymer (3) with Mw = 2,000 synthesized in Synthesis Example 1 is mixed with ion-exchanged water in an amount equivalent to 10% by mass in terms of polymer and equivalent to 2% by mass of tetramethylammonium hydroxide. Then, a concentrated product of the semiconductor component cleaning composition was prepared.

The concentrated product was diluted 50 times with ion-exchanged water to prepare a semiconductor component cleaning composition.
(1) Evaluation of etching rate of copper An 8-inch diameter substrate on which an unpatterned copper film is laminated (Advanced Technology Development Facility, Inc., a copper film having a thickness of 1,500 nm is formed on a silicon wafer. The laminated substrate) was cut into a 30 mm × 30 mm rectangle. This rectangular piece was immersed in the diluted semiconductor component cleaning composition at 25 ° C. for 24 hours. After the immersion, the copper etching rate was calculated from the decrease in the copper film thickness. The results are shown in Table 2.

(2) Evaluation of Influence on Low Dielectric Constant Insulating Film (2-1) Production of Low Dielectric Constant Insulating Film A low dielectric constant insulating film “LKD5109” (trade name) on a silicon substrate with a thermal oxide film having a diameter of 8 inches. , Manufactured by JSR Co., Ltd.) was applied by spin coating to form a coating film. The substrate was heated in an oven at 80 ° C. for 5 minutes and then at 200 ° C. for 5 minutes. Subsequently, under vacuum, it was heated at 340 ° C. for 30 minutes, then at 360 ° C. for 30 minutes, then at 380 ° C. for 30 minutes, and further heated at 450 ° C. for 1 hour. As a result, a colorless and transparent low dielectric constant film having a thickness of 2000 mm was formed on the substrate. The dielectric constant of this film was 2.2.

(2-2) Evaluation of change in relative dielectric constant The substrate on which the above-mentioned film was formed was immersed in the diluted semiconductor component cleaning composition at 25 ° C. for 60 minutes, and then the increase in relative dielectric constant was measured. . The results are shown in Table 2.

(3) Evaluation of removal ability of sodium contamination (3-1) Preparation of sodium-contaminated substrate 8 inch diameter silicon substrate with PETEOS film (Advanced Technology)
ogy Development Facility, Inc. A chemical mechanical polishing apparatus “EPO112” (manufactured by Ebara Manufacturing Co., Ltd.) was mounted on a silicon wafer (a substrate made by laminating a PETEOS film having a thickness of 1,000 nm on a silicon wafer). This was treated with a 1% sodium sulfate aqueous solution under the following conditions to obtain a substrate having an insulating film contaminated with sodium. The amount of sodium contamination of this substrate was 9 × 10 ¹⁴ atoms / cm ² .
Polishing pad: IC1000 (Rohm and Haas Electronic Materials)
Sodium sulfate aqueous solution supply amount: 200 mL / min
Plate rotation speed: 60rpm
Head rotation speed: 63rpm
Head pressing pressure: 3 psi
Processing time: 1 minute (3-2) Cleaning of contaminated substrate The above-mentioned contaminated PETEOS substrate is mounted on the cleaning roll part of EPO112, and the diluted semiconductor component cleaning composition is used under the following conditions. Washed. The amount of sodium contamination of the substrate after cleaning was measured. The results are shown in Table 2.
Roll brush rotation speed: upper roll brush 120 rpm, lower roll brush 120 rpm
Substrate rotation speed: 60 rpm
Semiconductor component cleaning composition supply amount: 500 mL / min each on the upper and lower surfaces of the substrate
Cleaning time: 30 seconds (4) Evaluation of removal ability of residual abrasive particles (4-1) Chemical mechanical polishing process 8-inch diameter substrate on which a copper film without pattern is laminated (Advanced Technology Development, Inc., A substrate obtained by laminating a copper film having a film thickness of 1,500 nm on a silicon wafer was mounted on a chemical mechanical polishing apparatus “EPO112” (manufactured by Ebara Corporation), and chemical mechanical polishing was performed under the following conditions.
Polishing pad: IC1000 (trade name, manufactured by Rohm and Haas Electronic Materials)
Aqueous dispersion type for polishing: “CMS8301” (trade name, manufactured by JSR Corporation, aqueous dispersion containing silica as abrasive grains), and 31% by mass of hydrogen peroxide solution was converted to the amount of pure hydrogen peroxide. An amount corresponding to 0.1% by mass with respect to the total amount of the aqueous dispersion was added and used.
Abrasive aqueous dispersion supply amount: 200 mL / min
Plate rotation speed: 93rpm
Head rotation speed: 100 rpm
Head pressing pressure: 3 psi
Polishing time: 1 minute The remaining abrasive particles after chemical mechanical polishing were measured with a surface defect inspection apparatus “KLA2351” (trade name, manufactured by KLA Tencor) at a pixel size = 0.62 μm and a threshold = 90. The number of abrasive particles remaining on the substrate after chemical mechanical polishing was 25 per substrate.

(4-2) Removal of residual abrasive particles The substrate was washed in the same manner as the washing of the contaminated substrate in (3-2). The amount of abrasive particles on the substrate after washing was measured in the same manner as in (4-1) above. The results are shown in Table 2.

(5) Influence on dishing of copper wiring (5-1) Chemical mechanical polishing process Chemical substrate polishing apparatus with test pattern “854 CMP” (trade name, Advanced Technology Development, Inc.) having a copper pattern of 8 inches in diameter. It was mounted on “EPO112” (manufactured by Ebara Corporation) and subjected to chemical mechanical polishing under the same conditions as in (4-1) above. In the substrate after chemical mechanical polishing, the wiring width is 100 μm.
It was 30 nm when the dishing amount of the wiring part of m was measured.

(5-2) Evaluation of dishing change About the said board | substrate, it wash | cleaned similarly to the washing | cleaning of the contaminated board | substrate of said (3-2). About the board | substrate after washing | cleaning, the dishing amount in the same site | part as said (5-1) was measured. The results are shown in Table 2.

[Examples 2 to 15 and Comparative Examples 1 to 6]
A composition for cleaning semiconductor parts was prepared in the same manner as in Example 1 except that the composition of the concentrated product for cleaning semiconductor parts was changed as shown in Table 1. This semiconductor component cleaning composition was evaluated in the same manner as in Example 1. The results are shown in Table 2.

[Comparative Example 7]
A composition for cleaning semiconductor components was prepared by adding 1% by mass of hydrogen peroxide to ion-exchanged water. This semiconductor component cleaning composition was evaluated in the same manner as in Example 1. The results are shown in Table 2.

[Comparative Example 8]
Ion exchange water was evaluated in the same manner as in Example 1 instead of the semiconductor component cleaning composition. The results are shown in Table 2.

[Examples 16 to 25 and Comparative Examples 9 to 12]
(Preparation of semiconductor component cleaning composition)
A concentrated product of the semiconductor component cleaning composition was prepared in the same manner as in Example 1 except that the composition of the concentrated product of the semiconductor component cleaning composition was changed as shown in Table 3. The concentrated product was diluted 25 times with ion-exchanged water to prepare a semiconductor component cleaning composition.

In Table 3, “EDTA” represents ethylenediaminetetraacetic acid. “-” Indicates that the component corresponding to the corresponding column was not blended.
(1) Evaluation of copper etching rate The copper etching rate was calculated in the same manner as in “(1) Evaluation of copper etching rate” described in Example 1. The results are shown in Table 4.

(2) Evaluation of Influence on Low Dielectric Constant Insulating Film A silicon substrate “000LKD304” (trade name, Advanced Technology Development, Inc., manufactured by Advanced Technology Development, Inc.) An insulating film “LKD5109” (a substrate having a relative dielectric constant of 2.2 manufactured by JSR Co., Ltd.) without a pattern having a film thickness of 4000 mm is used as the diluted semiconductor component cleaning composition. After immersion for 60 minutes at 25 ° C., the increase in relative dielectric constant was measured. The results are shown in Table 4.

(3) Evaluation of Cleaning Capability after Chemical Mechanical Polishing Process (3-1) Chemical Mechanical Polishing Process A test substrate “854 CMP” (trade name, Advanced Technology Development, Inc.) with a copper pattern of 8 inches in diameter was used. It is mounted on the chemical mechanical polishing equipment “EPO112” (manufactured by Ebara Corporation), and “IC1000” (trade name, manufactured by Rohm and Haas Electronic Materials) is used as a polishing pad under the following conditions. Two-stage polishing was performed.

<First polishing process>
Abrasive aqueous dispersion types: CMS7401 and CMS7452 (both trade names, manufactured by JSR Corporation, aqueous dispersion containing silica as abrasive grains), ion-exchanged water, and 4% by mass of ammonium sulfate aqueous solution were used at a volume ratio of 1: 1. : 2: 4 mixed and used.
Abrasive aqueous dispersion supply amount: 300 mL / min
Plate rotation speed: 60rpm
Head rotation speed: 60rpm
Head pressing pressure: 3 psi
Polishing time: 140 seconds <Second polishing step>
Aqueous dispersion type for polishing: CMS8401 and CMS8452 (both trade names, manufactured by JSR Corporation, aqueous dispersion containing silica as abrasive grains) and ion-exchanged water were mixed at a volume ratio of 1: 2: 3. used.
Abrasive aqueous dispersion supply amount: 200 mL / min
Plate rotation speed: 50 rpm
Head rotation speed: 50 rpm
Head pressing pressure: 5 psi
Polishing time: 60 seconds Excess copper and barrier metal other than the “854 CMP” wiring portion were removed by this two-stage polishing.

(3-2) Cleaning of substrate after polishing Two-step cleaning was performed under the following conditions.
<Washing on the surface plate>
Instead of removing the chemical mechanical polishing substrate from the chemical mechanical polishing apparatus, the diluted semiconductor component cleaning composition is used instead of the polishing aqueous dispersion, and cleaning on the surface plate is performed under the following conditions. went.
Semiconductor component cleaning composition supply rate: 500 mL / min
Plate rotation speed: 50 rpm
Head rotation speed: 50 rpm
Head pressing pressure: 2 psi
Cleaning time: 30 seconds <Washing with a roll brush>
The substrate after cleaning on the surface plate was mounted on a cleaning roll part of EPO112, and cleaning with a roll brush was performed under the following conditions using the same semiconductor component cleaning composition as the surface plate cleaning.
Roll brush rotation speed: upper roll brush 120 rpm, lower roll brush 120 rpm
Substrate rotation speed: 60 rpm
Semiconductor component cleaning composition supply rate: 500 mL / min each above and below the substrate
Cleaning time: 30 seconds (3-3) Evaluation of substrate after cleaning With respect to the substrate after the above-mentioned two-step cleaning, the amount of abrasive particles remaining on the surface to be cleaned, the number of scratches, the number of small dots and surface roughness were measured by the following methods .

  Using a surface defect inspection apparatus “KLA2351” (trade name, manufactured by KLA Tencor), the total number of defects was measured on the entire surface of the substrate after cleaning with a pixel size = 0.62 μm and a threshold = 90. Among them, 100 randomly extracted defects were checked on the KLA2351 monitor, and the ratios of the defects were scratches and small dots were determined. By multiplying the value by the total number of defects, the number of scratches and the number of small dots per entire surface to be polished were calculated. Moreover, the presence or absence of surface roughness was judged by observing the surface state in the vicinity of the defect projected on the monitor.

  Here, the “small dot” means a dark deposit on the surface to be polished among the surface defects counted by the surface defect inspection apparatus “KLA2351”. This is presumed that the copper oxide eluted from the surface to be polished during the chemical mechanical polishing process re-deposited on the surface to be polished.

  The results are shown in Table 4.

Claims (8)

The water-soluble polymer (a) whose weight average molecular weight of polystyrene sulfonate conversion measured by the gel permeation chromatography is 1,000-100,000 and the compound (b) represented by the following formula (1) are blended. A composition for cleaning semiconductor parts, comprising:
NR ₄ OH (1)
(In Formula (1), R represents a hydrogen atom or a C1-C6 alkyl group each independently.)   At least one of the water-soluble polymer (a) and the compound (b) exists in at least one of a dissociated state and a dissociated state and recombined with a counter ion, The composition for cleaning a semiconductor component according to claim 1.   The composition for cleaning a semiconductor component according to claim 1 or 2, wherein the water-soluble polymer (a) has a carboxyl group.   The composition for cleaning a semiconductor component according to claim 1, wherein the compound (b) is tetramethylammonium hydroxide.   5. The composition for cleaning a semiconductor component according to claim 1, further comprising at least one selected from the group consisting of an antioxidant (c) and a complexing agent (d). .   The semiconductor component cleaning composition according to claim 1, wherein the semiconductor component is a copper wiring board.   A method for manufacturing a semiconductor device comprising the steps of chemical mechanical polishing a semiconductor component and then cleaning the semiconductor component with the composition for cleaning a semiconductor component according to claim 1. The method of manufacturing a semiconductor device according to claim 7, wherein the semiconductor component is a copper wiring board.