JP2001064688A - Detergent for semiconductor part, cleaning of semiconductor part, composition for polishing and polishing - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a detergent having a slight load on environment and high cleaning effects on impurities remaining on a semiconductor part such as a semiconductor substrate after chemomechanical polishing(CMP). SOLUTION: This detergent for a semiconductor part consists essentially of a (co)polymer (salt) prepared by copolymerizing monomer components comprising at least one kind of monomer selected from the group of a monomer having sulfonic acid (salt) group, a monomer having carboxylic acid (salt) group, a monomer having hydroxyl group and a monomer having a skeleton derived from ethylene oxide or propylene oxide and a monomer having nitrogen atom.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cleaning agent for semiconductor components and a method for cleaning semiconductor components, and more particularly to a method for cleaning the surface of a semiconductor component such as a semiconductor substrate before and after chemical mechanical polishing (CMP) in a semiconductor manufacturing process. The present invention relates to a semiconductor component cleaning agent used for cleaning and a semiconductor component cleaning method. The present invention also relates to a polishing composition and a polishing method, and more particularly to a polishing composition and a polishing method used for polishing surfaces of semiconductor components such as semiconductor substrates, recording medium components, optical components and the like.

[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. Is known. Further, a cleaning solution containing an organic acid such as citric acid and a complexing agent is also known. However, in the above-mentioned cleaning liquid, 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 any problem, and it is necessary to have a high concentration in order to obtain a cleaning effect. There is a problem that the burden on the environment such as waste liquid treatment is large.

In addition, chemical mechanical polishing (CM) conventionally used in a flattening process for semiconductor parts such as semiconductor substrates and interlayer insulating films, recording medium parts and optical parts.
As the polishing composition used in P), for example, a polishing composition in which polishing abrasive grains such as diamond, alumina, and SiC of submicron to several tens of micron order are dispersed in water is known. Kaihei 1-205973
JP, JP-A-62-25187, JP-A-9-19-1
43455). However, when these polishing compositions are used, the dispersibility of the polishing abrasive grains, and the dispersion removal and prevention of reattachment of polishing dust generated by polishing are insufficient, so that pits, scratches, Irregularities such as orange peel and cracks are likely to occur, the polishing rate cannot be increased, and productivity is poor. Polishing compositions having a high polishing effect are also known, but since they are expensive, there is a limit to cost reduction.

[0006] In recent years, with the development of electronic devices, there is a demand for higher recording density of magnetic disk recording devices.
To increase the density, it is necessary to reduce the flying height of the magnetic head from the magnetic disk. If the flying height is small, if there is a protrusion on the hard disk surface, it will cause a head crash,
There is a risk of damaging the hard disk and magnetic head.
In addition, even a minute projection that does not lead to a head crash tends to cause various errors when reading and writing information due to disturbance of magnetic properties of the projection. Therefore, in the polishing step of the hard disk substrate, it is important to form a polished surface having excellent smoothness. As a magnetic disk substrate,
In addition to conventional aluminum substrates, glassy carbon substrates, which are brittle materials, are also used.
A relatively inexpensive polishing composition suitable for forming a surface having a high polishing rate and a high degree of smoothness has not been provided.

[0007]

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 agent having a high cleaning effect on impurities such as l, Ce, Cu, W, and Ti, and a method for cleaning semiconductor components. Further, an object of the present invention is suitable for chemical mechanical polishing (CMP) of a semiconductor component such as a semiconductor substrate and an interlayer insulating film, a recording medium component and an optical component, and flattening and polishing the surface of an object to be polished. Another object of the present invention is to provide a polishing composition and a polishing method capable of increasing the speed.

[0008]

The present invention relates to (a) a monomer having a sulfonic acid (salt) group, a monomer having a carboxylic acid (salt) group, a monomer having a hydroxyl group and ethylene oxide or A copolymer obtained by copolymerizing at least one monomer selected from the group of monomers having a skeleton derived from propylene oxide, and (b) a monomer having a nitrogen atom. The present invention relates to a cleaning agent for semiconductor components containing a polymer (salt) as a main component. It is preferable that the cleaning agent for a semiconductor component further includes at least one surfactant selected from the group consisting of an anionic surfactant, a cationic surfactant, and a nonionic surfactant. Further, it is preferable to use the above-mentioned semiconductor component cleaning agent for cleaning semiconductor components after chemical mechanical polishing. Also,
The present invention relates to a method for cleaning a semiconductor component, comprising cleaning the semiconductor component using the above-mentioned cleaning agent for a semiconductor component. Furthermore, the present invention relates to a polishing composition comprising at least an abrasive and a polishing aid comprising the above-mentioned cleaning agent for semiconductor components. It is preferable that a solvent is further added to the polishing composition. The polishing composition is preferably used for chemical mechanical polishing. Furthermore, the present invention relates to a polishing method characterized by polishing an object to be polished using the above-mentioned polishing composition.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The copolymer (salt) which is the main component of the cleaning agent for semiconductor parts of the present invention comprises (a) sulfonic acid (salt)
At least one selected from the group consisting of monomers having a group, monomers having a carboxylic acid (salt) group, monomers having a hydroxyl group, and monomers having a skeleton derived from ethylene oxide or propylene oxide. It is obtained by copolymerizing a monomer and a monomer component consisting of (b) a monomer having a nitrogen atom.

Here, the monomer having a sulfonic acid (salt) group includes, for example, isoprenesulfonic acid, (meth)
Acrylamide-2-methylpropane sulfonic acid, styrene sulfonic acid, methallyl sulfonic acid, vinyl sulfonic acid, allyl sulfonic acid, isoamylene sulfonic acid, and unsaturated (meth) allyl ethers represented by the following general formula (I) Monomers [e.g., 3-allyloxy-2-hydroxypropanesulfonic acid, 3-methallyloxy-2-hydroxypropanesulfonic acid],

[0011]

[Wherein, R ¹ 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
-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. ], Sulfoethyl (meth) acrylate, a conjugated diene sulfonic acid represented by the following general formula (II) (for example, 2-methyl-1,3-butadiene-1-sulfonic acid)

[0013]

(Wherein, R ^{2 to} R ⁷ are a hydrogen atom and a carbon number of 1)
Or an alkyl group having 8 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 an amino group, and at least one of R ^{2 to} R ⁷ is -SO ₃ X), (meth) acrylamido-2-methylpropane sulfonic acid), 2-hydroxy-3-acrylamide propane sulfonic acid, and salts thereof, and the like. Preferred are isoprenesulfonic acid, (meth) acrylamido-2-methylpropanesulfonic acid and salts thereof. Particularly preferred are isoprenesulfonic acid, (meth) acrylamido-2-methylpropanesulfonic acid, and salts thereof. These sulfonic acid (salt) group-containing monomers can be used alone or in combination of two or more.

The monomer having a carboxylic acid (salt) group is not particularly limited as long as it is a monomer having a carboxylic acid group and having a polymerizable double bond. Examples thereof include itaconic acid, itaconic anhydride, (Meth) acrylic acid, maleic acid, maleic anhydride, fumaric acid, fumaric anhydride, citraconic acid, citraconic anhydride, glutaconic acid, vinyl acetic acid, allyl acetic acid, phosphinocarboxylic acid, α-haloacrylic acid, β-carboxylic acid Acids or salts thereof, methyl (meth) acrylate, ethyl (meth) acrylate,
(Meth) acrylic acid alkyl esters such as octyl (meth) acrylate, and the like. Preferably,
Itaconic acid, itaconic anhydride, acrylic acid, methacrylic acid or salts thereof, and particularly preferably itaconic acid. These monomers containing a carboxylic acid (salt) group and having a polymerizable double bond can be used alone or in combination of two or more.

Examples of the monomer having a hydroxyl group include:
Unsaturated alcohols such as vinyl alcohol, allyl alcohol, methyl vinyl alcohol, ethyl vinyl alcohol, and vinyl glycolic acid, hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and 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 mono (meth) )
Hydroxy group-containing (meth) acrylates such as acrylate, hexanediol mono (meth) acrylate, pentaerythritol mono (meth) acrylate, and hydroxyphenoxyethyl (meth) acrylate. Preferred is hydroxyethyl (meth) acrylate. One or more of the above monomers can be used.

The monomer having a skeleton derived from ethylene oxide or propylene oxide includes polyoxyethylene monomethacrylate (addition product of 2 to 20 moles of alkylene oxide) and a structure represented by the following general formula (III) Compound, Wherein R ⁸ is a hydrogen atom or a methyl group, R ⁹ is an aliphatic group or an aromatic group having 1 to 18 carbon atoms, and A is a methylene group, a propylene group, or a tetramethylene group. Can be Preferred is polyoxyethylene monomethacrylate (ethylene oxide 5 mol adduct). One or more of the above monomers can be used.

The amount of the component (a) contained in the monomer component of the present invention is preferably from 10 to 99 mol%, more preferably from 30 to 95 mol%, in the monomer component. If it is less than 10 mol%, the metal (ion) removal ability is reduced when used as a cleaning agent, and when used as an abrasive composition, a sufficient polishing rate may not be obtained, which is not preferable. . On the other hand, if it exceeds 99 mol%, the ability to remove particles decreases when used as a cleaning agent, and when used as an abrasive composition, scratches may increase, which is not preferable.

The monomer (a) having a sulfonic acid group, the monomer having a carboxylic acid group, the monomer having a hydroxyl group, and the monomer having a skeleton derived from ethylene oxide or propylene oxide are as follows: Usually, one or more kinds can be used, but preferably, a monomer having a sulfonic acid group alone, a combination of a monomer having a sulfonic acid group and a monomer having a carboxylic acid group, and a monomer having a sulfonic acid group are used. A monomer having a skeleton derived from ethylene oxide or propylene oxide, a monomer having a sulfonic acid group, a monomer having a carboxylic acid group and a monomer having a skeleton derived from ethylene oxide or propylene oxide. It is a combination of monomers.

(B) As the monomer having a nitrogen atom,
Monomers having a functional group such as an amine and an amide are exemplified. Specifically, (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, Nn-propyl (meth) acrylamide, N
-Isopropyl (meth) acrylamide, N-dimethyl (meth) acrylamide, N-diethyl (meth) acrylamide, N-di-n-dipropyl (meth) acrylamide, N-methyl-N-ethyl (meth) acrylamide, N-vinyl Formamide, N-vinylpyrrolidone,
2-vinylpyridine, 4-vinylpyridine and the like can be mentioned. Preferably, they are acrylamide, N-dimethyl (meth) acrylamide, and vinylpyridine. One or two or more monomers having a nitrogen atom can be used in combination.

The amount of the monomer (b) having a nitrogen atom contained in the monomer component of the present invention is preferably 1 to 90 mol%, more preferably 5 to 70 mol%, in the monomer component. %
It is. When the amount is less than 1 mol%, the particle removing ability is reduced when used as a cleaning agent, and when used as an abrasive composition, scratches may increase, which is not preferable. On the other hand, if it exceeds 90 mol%, the metal (ion) removal ability decreases when used as a cleaning agent, and a sufficient polishing rate may not be obtained when used as an abrasive composition. Not preferred.

The copolymer (salt) of the present invention can be obtained by copolymerizing other copolymerizable monomers in addition to the above monomer components. Other monomers include aromatic vinyl compounds such as styrene, α-methylstyrene, vinyltoluene, and p-methylstyrene, butadiene, isoprene, 2-chloro-1,3-butadiene, 1-chloro-1,3. -Aliphatic conjugated dienes such as butadiene, vinyl cyanide compounds such as (meth) acrylonitrile, and phosphoric acid compounds. One or more of the above monomers can be used. When these other monomers are copolymerized, the content is preferably 30 mol% or less in the monomer components.

In the present invention, the component (a) and the component (b)
A method for producing a copolymer (salt) from a monomer component containing the component is, for example, as follows. That is, the reaction temperature of the monomer component in the presence of a known polymerization initiator such as hydrogen peroxide, sodium persulfate, and potassium persulfate,
Usually at 20-200 ° C, preferably at 40-150 ° C,
The polymerization reaction is carried out for 0.1 to 20 hours, preferably 1 to 15 hours, to produce a copolymer (salt).
As one prescription, copolymerization can be carried out by sequentially adding monomer components used for 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-mentioned copolymerization reaction, a polymerization solvent can be used in order to smoothly carry out the reaction. As the polymerization solvent, water or a mixture of water and an organic solvent miscible with water can be used. . 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 weight average molecular weight of the copolymer (salt) of the present invention is 1,000 to 500,000, preferably 3,000 to 300,000, more preferably 5,000.
0 to 300,000. If it is less than 1,000, the cleaning effect may not be sufficiently exhibited, while if it exceeds 500,000,
It is difficult to handle due to gelation.

The copolymer (salt) of the present invention is preferably acrylamide / acrylic acid copolymer (salt), methacrylamide / itaconic acid copolymer (salt), dimethylacrylamide / acrylamide-2-methylpropanesulfone Acid copolymer (salt), N-methyl (meth) acrylamide / hydroxyethyl methacrylate / acrylamide-2-methylsulfonic acid copolymer (salt), acrylamide / polyoxyethylene monomethacrylate / acrylamide-2-methylpropanesulfonic acid / Acrylic acid copolymer (salt), acrylamide / acrylic acid / acrylamide-2-methylpropanesulfonic acid copolymer (salt), and vinylpyridine / acrylic acid copolymer (salt).

The copolymer (salt) of the present invention is preferably water-soluble for use as a cleaning agent for semiconductor components. In order to make the polymer water-soluble, a copolymer (salt) having a counter ion of a cationic species may be used. The cationic species is not particularly limited, but is preferably hydrogen, an alkali metal, an alkaline earth metal, ammonia, an amine, or the like. Examples of the alkali metal include sodium and potassium.
Alkaline earth metals include calcium and magnesium, and amines include methylamine, ethylamine, propylamine, dimethylamine, diethylamine, triethylamine, butylamine dibutylamine, alkylamines such as tributylamine, ethylenediamine, diethylenetriamine, and triethylenetetramine. Examples thereof include polyamine, morpholine, and piperidine. Preferably, hydrogen, potassium, ammonia,
It is an alkylamine. Further, in order to obtain a copolymer (salt) having these cationic species, a monomer having a preferred cationic species may be copolymerized, or after copolymerizing an acid type monomer, It may be neutralized with alkali. It is also possible to exchange the copolymer (salt) with other cationic species by various ion exchange techniques. These cations may be used alone or in combination with two or more.
More than one species can be used in combination.

The cleaning agent for semiconductor components of the present invention has a copolymer (salt) concentration of 0.1 to 20% by weight, especially in water and / or a hydrophilic organic solvent (hereinafter also referred to as "solvent"). It is preferable to use it after dissolving it preferably in an amount of 1.0 to 10% by weight. When the concentration of the copolymer (salt) is 0.1
If the amount is less than 10% by weight, the cleaning effect is not sufficiently exhibited.
When the concentration is higher than 20% by weight, an effect corresponding to the concentration cannot be expected and the efficiency is not high.

Among the above solvents, distilled water, deionized water, tap water, industrial water and the like can be appropriately selected as water. Other solvents include alcohols, ethers, ketones, and the like. Above all, those mainly composed of water,
Water is particularly preferred. Among the hydrophilic organic solvents, specific examples of alcohols include methanol, ethanol, and 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 can be mentioned. Further, specific examples of ethers include tetrahydrofuran and dioxane, and specific examples of ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, and the like. These hydrophilic organic solvents can be used alone or in combination of two or more.

The cleaning agent for semiconductor components of the present invention comprises the copolymer (salt) and at least one kind selected from the group consisting of an anionic surfactant, a cationic surfactant, and a nonionic surfactant. A surfactant may be further added. Examples of the anionic surfactant include a sulfate of a higher alcohol, an alkylbenzene sulfonate, an aliphatic sulfonate, an aliphatic organic acid salt, and a phosphoric acid. Preferred are oleates such as ammonium oleate, laurate, rosinate, dodecylbenzene sulfonate, and polyoxyethylene alkyl ether sulfate. Examples of the cationic surfactant include lauryl trimethyl ammonium chloride, octyl trimethyl ammonium bromide, dioctyl dimethyl ammonium chloride and the like. Preferably, it is lauryl trimethyl ammonium chloride.

Examples of the nonionic surfactant generally include an alkyl ester type such as polyethylene glycol, an alkyl ether type such as triethylene glycol monobutyl ether, an ester type such as polyoxysorbitan ester, and an alkylphenol type. Preferably, it is triethylene glycol monobutyl ether. Further, as the surfactant, an amphoteric surfactant can be used, and a carboxylate, a sulfate, a sulfonate, and a phosphate are used as an anion portion, and an amine salt and a quaternary ammonium salt are used as a cation portion. And the like.

The amount of the surfactant to be used is preferably 0.01 to 5% by weight, more preferably 0.1 to 5% by weight, based on the copolymer (salt). It is 0.05 to 2% by weight, particularly preferably 0.1 to 1% by weight. If the amount is less than 0.01% by weight, a remarkable cleaning effect may not be obtained.
Even if it exceeds 10% by weight, the effect corresponding to the added amount cannot be obtained.
In addition, there may be a problem of foaming.

The cleaning agent for semiconductor parts of the present invention includes:
It is also possible to use other known detergent components in combination. Other detergent components include, for example, ethylenediaminetetraacetic acid (EDTA), trans-1,2-cyclohexanediaminetetraacetic acid (CyDTA), nitrilotriacetic acid (NT
A), diethylenetriaminepentaacetic acid (DTPA),
N- (2-hydroxyethyl) ethylenediamine-N,
In addition to compounds such as N ', N'-triacetic acid (EDTA-OH) and polyaminocarboxylic acids such as salts thereof, oxalic acid, citric acid, gluconic acid, succinic acid, tartaric acid, fumaric acid, malic acid, pyrophosphoric acid, Organic acids such as lactic acid and benzoic acid, hydrogen fluoride, hydrogen peroxide, carbonic acid, hydrochloric acid, perchloric acid, nitric acid, sulfuric acid, sulfurous acid, persulfuric acid, phosphoric acid, phosphorous acid,
Examples include inorganic acids such as hypophosphorous acid and organic acids having these as a functional group.

In general, these compounds are used in the form of a free acid or a salt, and do not adversely affect the properties for semiconductor production, such as proton type, ammonium salt, amine salt, and alkali such as lithium, sodium and potassium. It is preferably used in the form of salts such as salts with metals, alkaline earth metals such as magnesium and calcium, zinc, aluminum, nickel and iron. Among them, salts of ammonia, amine, potassium and the like are more preferable,
Most preferred are salts with ammonia and potassium. These compounds can be used alone, or
It is also possible to use two or more kinds. The amount of these compounds to be used is not particularly limited, but is usually not more than 5 times the weight of the copolymer (salt) of the present invention. Also, in order to improve the cleaning effect, various alkaline solutions, ozone water,
Functional water such as redox water may be used in combination.

The cleaning agent 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 following method can be adopted. Before or after performing the cleaning using the cleaning agent of the present invention, use of a known cleaning agent, or a known cleaning method such as immersion cleaning, paddle cleaning, spray cleaning, brush cleaning, or ultrasonic cleaning is performed. By doing so, it is possible to further increase the efficiency of removing metal impurities.

Although the pH of the cleaning agent of the present invention is not particularly limited, it can be generally used at 1 to 12, preferably 2 to 10,
More preferably, it is 3-9. Outside this range, the cleaning ability may be reduced or the metal portion may be corroded, which is not preferable. PH can be adjusted by appropriately selecting the type of counter ion species or by adding an acid or a base. For example, used for counter ion,
The pH can be adjusted by changing the ratio of alkali components such as H ⁺ and ammonia ions (NH ₃ ⁺ ). The working temperature is usually 5 to 50C.

The cleaning agent for a semiconductor component of the present invention has a low environmental load, and has CMP abrasive grains such as silica and alumina remaining on the semiconductor component 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.

The semiconductor component cleaning agent of the present invention is used as a polishing aid in a polishing composition, which is used for polishing surfaces of semiconductor components such as semiconductor substrates, recording medium components and optical components. Can also be used. As the abrasive, those commonly used as abrasive grains can be used as appropriate. As the polishing particle size, for example, diamond particles, alumina particles, silicon carbide (SiC) particles, magnesium oxide particles, cerium oxide particles, zirconium oxide particles, chromia (Cr ₂ O ₃ ) particles, fumed silica particles, colloidal silica particles, etc. Is mentioned. For polishing semiconductor substrates, recording medium substrates and optical components, etc.,
Among them, alumina particles, SiC particles, cerium oxide particles, zirconium oxide particles, fumed silica particles, colloidal silica particles, and the like are exemplified, and alumina particles, fumed silica particles, and colloidal silica particles are preferable. Among the alumina particles, γ-alumina particles, δ
-Alumina particles, θ-alumina particles, η-alumina particles and amorphous alumina particles are preferred. These may be used alone or in combination of two or more.

Generally, abrasive grains include a crushed type obtained by crushing large particles and classifying them into a desired particle size, and a spherical type formed by a colloid solution. As a crushing type, for example, in a wet slurry method, a fine particle is crushed by a fine crusher (such as a ball mill), and coarse particles are obtained by gravity sedimentation and centrifugal separation. In a dry method, a crushing and classification is performed by a jet stream. And the like. When compared at the same particle size, the crushed type has a larger specific surface area than the spherical type,
The polishing rate is also high. When polishing an interlayer insulating film or a metal film as the abrasive of the present invention, either type can be used, but a crushing type is preferred.

The average grain size of the abrasive grains is preferably 0.0
01-10.0 μm, more preferably 0.01-5.
0 μm, particularly preferably 0.02 to 3.0 μm.
If it is less than 0.001 μm, the polishing rate will be significantly reduced, while if it exceeds 10.0 μm, it will be difficult to maintain the flatness of the surface of the object to be polished. Further, abrasives having large and small particle sizes can be used in combination. The average particle size is obtained, for example, by measuring the particle size obtained by SEM observation or TEM observation.

The hardness of the abrasive grains is determined by Knoop hardness (JIS
Z2251) is preferably 600 to 10,000, more preferably 1,000 to 5,000, and particularly preferably 1,500 to 3,000. Knoop hardness of 600
If the amount is less than the above, a sufficient polishing rate cannot be obtained, and the productivity is reduced. On the other hand, if it exceeds 10,000, the flatness of the surface of the object to be polished is reduced and the quality is deteriorated. The specific surface area of the abrasive grains is preferably 0.1 to 50 m ² / g, and the specific gravity is preferably 2 to 5, and more preferably 3 to 4. When the specific gravity is within this range, it is preferable in terms of handleability, dispersibility during polishing, and recovery and reuse.

The above-mentioned abrasive is used together with a polishing aid as a slurry-like polishing composition. The mixing ratio of the abrasive in the polishing composition can be appropriately selected according to the viscosity of the polishing composition and the quality required for the object to be polished, but is preferably 0.01 to 40% by weight. More preferably 0.1 to 35% by weight, particularly preferably 1 to 30% by weight
It is. If it is less than 0.01% by weight, the desired polishing properties cannot be obtained, while if it exceeds 40% by weight, the viscosity of the composition becomes too high, which is not preferable.

When the polishing composition of the present invention contains a polishing aid comprising the semiconductor component cleaning agent of the present invention, the polishing effect is increased and the flatness of the polished surface is increased.
The following reasons are considered. That is, the polishing aid is adsorbed to the polishing waste generated by polishing, the cohesive force acting between the polishing wastes is reduced, and the polishing wastes are uniformly dispersed in the polishing composition from the surface of the object to be polished. It is quickly removed, and the surface of the object to be polished always exposes a new surface. The abrasive is
By adsorbing the polishing aid, the dispersion is uniformly dispersed and maintained on the polishing pad surface, the amount of abrasive used for polishing increases, the load applied to each abrasive decreases, and the abrasive Acts uniformly on the surface of the object to be polished. Furthermore, the polishing aid comprising the semiconductor component cleaning agent of the present invention has high stability and can perform polishing even under high pressure conditions, so that the polishing rate can be increased.

The polishing aid of the present invention is a copolymer (salt) obtained by copolymerizing a monomer component containing a monomer having a nitrogen atom.
And a cleaning agent for semiconductor components containing as a main component. The amount of the polishing aid of the present invention to be used is preferably 0.001 to 10% by weight, more preferably 0.01 to 5% by weight in the polishing composition. If the content is less than 0.001% by weight, sufficient polishing characteristics may not be obtained, while
If the content exceeds 10% by weight, the effect of the addition is not improved and the composition is not effective.

In the present invention, the relationship between the amounts of the abrasive and the polishing aid is determined by the ratio of the concentration of the abrasive and the polishing aid in the polishing composition [the concentration of the abrasive (% by weight) / the ratio of the polishing aid]. Concentration (% by weight)], preferably 0.1 / 30 to 40 / 0.01,
More preferably, it is blended so as to be 1/20 to 30 / 0.1, particularly preferably 5/10 to 25/1. 0.1
If it is less than / 30, the polishing effect is reduced, while 4
If it exceeds 0 / 0.01, the effect of blending the polishing aid will not be sufficiently exhibited.

The solvent used in the polishing composition of the present invention is the above-mentioned water and / or hydrophilic organic solvent. Usually, a polishing aid composed of the above-mentioned cleaning agent for semiconductor components is mixed with a solvent and abrasive grains to obtain a slurry-like polishing composition. Examples of the solvent include the same solvents as those described above as the solvent used by dissolving the semiconductor component cleaning agent. The solvents can be used alone or in combination of two or more. The solid concentration in the polishing composition of the present invention is preferably 1 to 60% by weight, more preferably 5 to 40% by weight, and particularly preferably 10 to 30% by weight.
It is. If the solid content is less than 1% by weight, sufficient polishing properties may not be obtained, while if it exceeds 60% by weight, the effect of addition is not improved and it is not effective.

The pH of the polishing composition of the present invention is not particularly limited, but it can be generally 1 to 13, preferably 2 to 12, and more preferably 3 to 11. Outside this range, the polishing aid becomes unstable, the polishing ability may be reduced, or the metal portion may be corroded, which is not preferable. The adjustment of the pH can be performed in the same manner as the adjustment of the pH of the cleaning agent. The polishing composition of the present invention, in addition to the above polishing aid,
Known additives such as various thickeners, dispersants, and rust inhibitors can be added. These additives are preferably contained in the polishing aid of the present invention in an amount of 0 to 3% by weight.

The polishing composition of the present invention is mainly used for polishing semiconductor parts, recording medium parts and optical parts. Examples of the material of the object to be polished include metal films such as tungsten, copper, and aluminum used in the semiconductor manufacturing process, metals such as Ni-P plated aluminum alloys, silicon, glassy carbon materials, and the like. Examples include brittle materials such as glass and ceramics such as Al ₂ O ₃ .TiC. Examples of the glassy carbon material include those having a structure in which graphite is dispersed in a matrix of amorphous carbon.

The shape of the object to be polished is, for example,
Discs, plates, slabs, prisms, lenses, and various other shapes are available. In the polishing using the polishing composition of the present invention, the object to be polished is roughly polished (wrapped) to have a surface roughness of usually 0.01 to 1 μm, preferably 0.05 to 0.5 μm. Use things. The surface roughness in the present invention is the center line average roughness Ra, and is measured using a Tally 0 step manufactured by Rank Taylor Hobson.

The method for using the polishing composition of the present invention is not particularly limited, and a known method can be employed. For example,
Polishing can be performed with a double-side polishing machine 9B manufactured by SPEED FAM Co., Ltd. The processing pressure is usually 10 to 2,000
gf / cm ² , preferably 50 to 500 gf / cm ² ,
The processing time is usually 0.5 to 150 minutes, preferably 1 to 150 minutes.
The processing temperature is usually 5 to 70C, preferably 5 to 50C for 100 minutes. The polishing pad hardness (JIS
(According to K6301) is generally 86 to 99, preferably 88 to 95, because the harder the material, the higher the surface flatness. As a material of the polishing pad,
For example, a resin composite such as a resin such as a foamed polyurethane or a composite of a polyester nonwoven fabric and a polyurethane may be used. Further, the lower platen rotation speed is usually 5-1.
00 rpm, preferably 10 to 60 rpm, the flow rate of the polishing composition is usually 3 to 300 ml / min, preferably 10 to 300 ml / min.
~ 200 ml / min.

The polishing composition of the present invention comprises a semiconductor component such as a semiconductor substrate and an interlayer insulating film, and a brittle material such as a glassy carbon substrate, a glass substrate and a ceramic substrate.
Suitable for chemical mechanical polishing (CMP) of recording medium parts and optical parts, the surface of the object to be polished can be flattened, and the polishing rate can be increased. In the present invention, "substrate"
Is not limited to a shape having a flat portion, but also includes a shape having a curved portion.

[0051]

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 a value determined by gel permeation chromatography (GPC) and converted 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 are connected in series in the order of 〜, and a sample is 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

[0053] The copper film-coated wafer substrate of 2.5 inches in diameter The surface roughness was 0.1μm by polishing rough polishing with the polishing composition, it was polished by a double-side polishing machine. The surface roughness (center line average roughness Ra) of the object to be polished was measured using a Tally 0 step manufactured by Rank Taylor Hobson. The processing conditions are as follows. Double-side polishing machine: LGP-510, Model LGP-510 Processing pressure: 150 gf / cm ² Processing time: 2 minutes Processing temperature: 25 ° C. Polishing pad hardness: 90 (based on JIS K6301) Lower platen rotation speed: 50 rpm For polishing Composition flow rate: 50 ml / min

Polishing Rate The wafer substrate with a copper film was polished under the same conditions as above, and the polishing rate (μm / min) was determined by the following equation (IV). Polishing rate (μm / min) = [thickness of copper film before polishing (μm) −thickness of copper film after polishing (μm)] / polishing time (minutes) (IV) The thickness (μm) of the film is determined by measuring the sheet resistance by a direct current four-probe method using a resistivity measuring machine (manufactured by NPS, model Σ-5), and from the sheet resistance value and the resistivity of copper, the following formula is used. (V). Thickness of copper film (μm) = [sheet resistance value (Ω / cm ² ) × resistivity of copper (Ω / cm ² )] × 10 ⁴ (V)

Scratch Number Using an optical microscope, the surface of the substrate polished at a magnification of 50 was observed at six locations at 60 ° intervals, and the number of scratches was measured. The depth of the scratch is Zygo's Zyg
Measured at o. The evaluation criteria are as follows. ：: Less than 0.5 scratches having a depth of 0.05 μm or more in one visual field. Δ: 0.5 to 1 scratches having a depth of 0.05 μm or more in one visual field. ×: Scratch having a depth of 0.05 μm or more is 1 in one visual field.
Beyond books.

Reference Example 1 49 g of a 20% aqueous solution of acrylamide and 20%
A solution prepared by dissolving 452 g of an aqueous acrylic acid solution having a concentration of 14 g and 14 g of a 35% aqueous hydrogen peroxide solution was stirred in a 2-liter container containing 1,000 g of water while stirring under reflux.
It was dropped evenly over time. After completion of the dropwise addition, the mixture was kept under reflux for 2 hours, then neutralized with an aqueous ammonia solution to make the counter ion (NH ₃ ⁺ ), and the ammonium salt of the acrylamide / acrylic acid copolymer (10/90 molar ratio) (A) I got The weight average molecular weight of the copolymer (salt) is 10,000.
Met.

Reference Example 2 In Reference Example 1, 49 g of a 20% aqueous acrylamide solution and 452 g of a 20% aqueous acrylic acid solution were used.
Was changed to 70 g of a 20% aqueous solution of methacrylamide and 430 g of a 20% aqueous solution of itaconic acid, in the same manner as in Reference Example 1, except that ammonium in the acrylamide / itaconic acid copolymer (20/80 molar ratio) was used. The salt (B) was obtained. The weight average molecular weight of the copolymer (salt) is 1
It was 0000.

Reference Example 3 In Reference Example 1, 49 g of a 20% strength aqueous acrylamide solution was replaced with 20% strength aqueous dimethyl acrylamide solution 5
To 4 g, 452 g of a 20% aqueous solution of acrylic acid
% Acrylamide-2-methylpropanesulfonic acid aqueous solution was changed to 447 g, and the counter ion was changed to (H ⁺ ). A copolymer (20/80 molar ratio) (C) was obtained. The weight average molecular weight of the copolymer was 10,000.

Reference Example 4 In Reference Example 1, 49 g of a 20% aqueous acrylamide solution and 452 g of a 20% aqueous acrylic acid solution were used.
With 20% concentration of N-methyl (meth) acrylamide 2
7 g, 20% strength hydroxyethyl methacrylate 3
5 g and 439 g of an aqueous solution of acrylamido-2-methylpropanesulfonic acid, and the counter ion was (H ⁺ )
The procedure was performed in the same manner as in Reference Example 1 except that N-methyl (meth) acrylamide / hydroxyethyl methacrylate / acrylamide-2-methylpropanesulfonic acid copolymer (10/10/80 molar ratio) (D) was used. Obtained. The weight average molecular weight of the copolymer was 9,000.

Reference Example 5 In Reference Example 1, 49 g of a 20% aqueous acrylamide solution and 452 g of a 20% aqueous acrylic acid solution were used.
With 20% strength aqueous acrylamide solution 18 g, 20%
Change in the concentration of the polyoxyethylene monomethacrylate (ethylene oxide 5 mol adduct) aqueous solution 77 g, acrylamido-2-methylpropane sulfonic acid solution 107g and 20% strength aqueous solution of acrylic acid 299 g, a counterion (H ⁺⁾ Acrylamide / polyoxyethylene monomethacrylate / acrylamide-2-methylpropanesulfonic acid / acrylic acid copolymer (5/5/10/80 molar ratio) (E) was prepared in the same manner as in Reference Example 1 except that Obtained. The weight average molecular weight of the copolymer is 1
It was 5,000.

Reference Example 6 In Reference Example 1, 49 g of an aqueous acrylamide solution and 452 g of a 20% aqueous acrylic acid solution were replaced with 20 g of a 20% aqueous acrylamide solution, 20 g of a 20% aqueous acrylic acid solution, and 20% acrylamide aqueous solution.
Acrylamide / acrylic acid / acrylamide-2-methylpropanesulfonic acid copolymer was carried out in the same manner as in Reference Example 1, except that 461 g of an aqueous solution of 2-methylpropanesulfonic acid was used, and the counter ion was changed to (H ⁺ ). (10/1
(0/80 molar ratio) (F). The weight average molecular weight of the copolymer was 12,000.

REFERENCE EXAMPLE 7 In Reference Example 1, 49 g of an aqueous acrylamide solution and 452 g of a 20% aqueous acrylic acid solution were used, 70 g of a 20% aqueous 4-vinylpyridine aqueous solution, 431 g of a 20% aqueous acrylic acid solution, and a counter ion were (H ⁺ ) To give a 4-vinylpyridine / acrylic acid copolymer (10/90 molar ratio) (G).
The weight average molecular weight of the copolymer was 12,000.

Examples 1 to 7 A silicon wafer with a SiO ₂ film was prepared by
It was immersed in a 3% Fe (NO ₃ ) ₂ aqueous solution and a 3% CuSO ₄ aqueous solution sequentially for 3 minutes, washed lightly with water, and subjected to contamination treatment.
This contaminated silicon wafer with a SiO ₂ film was transferred to a total reflection X-ray fluorescence device (device name: TREX-6) manufactured by Technos Corporation.
10T), the concentrations of Cu, Fe, and K on the wafer surface were measured. The surface concentration of Cu is 100 × 10 ¹⁰ (atoms /
cm ² ), and the surface concentration of Fe is 15,000 × 10
¹⁰ (atoms / cm ² ), the surface concentration of K is 90 × 10
¹⁰ (atoms / cm ² ). Next, 2% aqueous solutions of the copolymers (salts) (A to G) of Reference Examples 1 to 7 were prepared as washing liquids. The contaminated silicon wafer with a SiO ₂ film was washed in a cleaning solution at 40 ° C. for 3 minutes, washed with water, dried, and the concentrations of Cu, Fe, and K on the wafer surface were measured again, and Cu, Fe, and Cu were measured.
The ability to remove K was evaluated. Table 1 shows the results.

Example 8 The procedure of Example 3 was repeated except that 0.05% of triethylene glycol monobutyl ether was added to the 2% aqueous solution prepared using the copolymer (C) of Reference Example 3.
The same was done. Table 1 shows the results.

Example 9 In Example 3, except that lauryltrimethylammonium chloride was added to a 2% aqueous solution prepared using the copolymer (C) of Reference Example 3 so that the concentration became 0.05%.
The same was done. Table 1 shows the results.

Example 10 In Example 3, 0.02% ammonium oleate was added to a 2% aqueous solution prepared using the copolymer (C) of Reference Example 3.
The same operation was performed except that the content was added to 5%. Table 1 shows the results.

Comparative Example 1 The procedure of Example 1 was repeated, except that a 10% aqueous citric acid solution was used instead of the aqueous copolymer (salt) solution of Reference Example 1. Table 1 shows the results. As shown in Table 1,
The cleaning agent of the present invention, compared with the comparative example using citric acid,
It can be seen that the ability to remove Cu, Fe, and K and the ability to remove particles are excellent.

[0068]

[Table 1]

Examples 11 to 20 Alumina abrasives (AKP10-α alumina, manufactured by Sumitomo Chemical Co., Ltd.) as an abrasive (purity 99.9%, average particle size 1.0 μm, specific surface area 2.0 m ²⁾ / G) at the concentrations shown in Table 2 and 6.7% of a 30% aqueous solution of hydrogen peroxide with respect to the polishing composition, and the copolymers (salts) of Reference Examples 1 to 7 were used.
(AG) and, if necessary, a surfactant,
Was mixed and stirred at the concentrations shown in Table 1 to obtain a polishing composition. The amounts shown in Table 2 are concentrations (%) based on the polishing composition containing water as a solvent. PH was 4-10.
Using the above polishing composition, polishing was performed with a double-side polishing machine. The polished substrate was washed with a cleaning liquid, and the polished surface was evaluated. Table 2 shows the results.

Comparative Example 2 The same operation as in Example 10 was carried out except that no copolymer (salt) was used. Table 2 shows the results. As shown in Table 2, when the polishing composition of the present invention is used, the polishing rate can be increased while the number of scratches on the object to be polished is low and the flatness is maintained.

[0071]

[Table 2]

In the above examples, when the polishing was carried out using the polishing composition of the present invention, the surface roughness of the object to be polished was low.
In addition, the polishing rate could be increased. In addition, the polishing composition of the present invention had a stable dispersion of the abrasive, was excellent in fluidity, and was excellent in handleability. Furthermore, the clogging of the polishing pad was small, and the frequency of cleaning and replacement of the polishing pad was reduced.

[0073]

According to the present invention, when a semiconductor component is cleaned using the cleaning agent for a semiconductor component of the present invention, the environmental load is reduced, and metal impurities remaining on the semiconductor component after chemical mechanical polishing are efficiently removed. Can be removed. Further, the polishing composition of the present invention is a semiconductor substrate, a semiconductor component such as an interlayer insulating film, a glassy carbon substrate, a glass substrate, a brittle material such as a ceramic substrate, such as recording medium components and optical components. Suitable for chemical mechanical polishing (CMP), the surface roughness of the object to be polished is low, and the polishing rate can be increased.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Toshio Ono 2--11-24 Tsukiji, Chuo-ku, Tokyo Inside JSR Corporation (72) Inventor Katsuhiro Ishikawa 2-11-24 Tsukiji, Chuo-ku, Tokyo JSR F term (reference) 4H003 AB03 AB46 AE05 BA12 DA15 DA16 DB01 EB28 EB30 ED02 ED29 FA03 FA05

Claims (8)

[Claims] 1. A monomer having a sulfonic acid (salt) group, a monomer having a carboxylic acid (salt) group, a monomer having a hydroxyl group, and a skeleton derived from ethylene oxide or propylene oxide. A main component is a copolymer (salt) obtained by copolymerizing a monomer component comprising at least one monomer selected from the group of monomers and (b) a monomer having a nitrogen atom. Cleaning agent for semiconductor parts. 2. The cleaning for semiconductor components according to claim 1, further comprising at least one surfactant selected from the group consisting of an anionic surfactant, a cationic surfactant and a nonionic surfactant. Agent. 3. The cleaning agent for semiconductor parts according to claim 1, which is used for cleaning semiconductor parts before and after chemical mechanical polishing. 4. A method for cleaning a semiconductor component, comprising cleaning the semiconductor component using the cleaning agent for a semiconductor component according to claim 1. 5. A polishing composition comprising at least an abrasive and a polishing aid comprising the semiconductor component cleaning agent according to claim 1 or 2. 6. The polishing composition according to claim 5, further comprising a solvent. 7. The polishing composition according to claim 5, which is used for chemical mechanical polishing. 8. A polishing method characterized by polishing an object to be polished using the polishing composition according to claim 5 or 6.