JP2017224643A - Composition for semiconductor surface treatment, surface treatment method, and method for manufacturing semiconductor device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: a composition for semiconductor surface treatment, which can suppress a polishing body from damaging a metal wiring line or the like, and which enables the effective elimination of pollution from a surface of a polished object; and a semiconductor surface treatment method by use of the composition for semiconductor surface treatment.SOLUTION: A composition for semiconductor surface treatment according to the present invention comprises: at least one polymer (A) selected from a group consisting of polyamic acid, a polyamic acid derivative and salts thereof; and a liquid medium (B). The composition for semiconductor surface treatment according to the present invention comprises potassium and sodium, and satisfies M/M=5×10-1×10, where M(ppm) is a content of the potassium and M(ppm) is a content of the sodium.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a semiconductor surface treatment composition, a surface treatment method, and a semiconductor device manufacturing method for treating a surface of a semiconductor substrate including metal wiring.

  CMP (Chemical Mechanical Polishing) utilized in the manufacture of semiconductor devices is a method in which the object to be polished and the polishing pad are slid against each other while the object to be polished is pressure-bonded to the polishing pad and a semiconductor surface treatment method is supplied onto the polishing pad. This is a technique for polishing the object to be polished chemically and mechanically. The chemical mechanical polishing dispersion used in such CMP contains chemicals such as an etching agent in addition to the abrasive grains. In addition, a process of cleaning the abrasive body with a cleaning composition after CMP is essential.

  On the surface of the object to be polished, a metal wiring material such as copper, tungsten and cobalt, an insulating material such as silicon oxide, a barrier metal material such as tantalum nitride and titanium nitride, and the like are exposed. When such dissimilar materials coexist on the surface to be polished, it is necessary to perform flat polishing with a constant polishing rate of various materials. In addition, it is necessary to remove only contamination from the polished surface after polishing, and clean the surface to be polished without damaging it. For example, Patent Document 1 describes a technique for suppressing corrosion of a surface to be polished where a wiring material and a barrier metal material are exposed using an acidic cleaning agent. For example, Patent Documents 2 and 3 disclose techniques for cleaning a surface to be polished from which a wiring material and a barrier metal material such as cobalt are exposed using a neutral to alkaline cleaning agent.

JP 2010-258014 A JP 2009-055020 A JP2013-157516A

  A semiconductor surface treatment composition and a semiconductor capable of further suppressing damage to the metal wiring and the like of the object to be polished and effectively removing contamination from the surface of the object to be polished with the further miniaturization of the circuit structure in recent years. A semiconductor surface treatment method using the surface treatment composition is required.

The semiconductor surface treatment composition according to the present invention comprises:
At least one polymer (A) selected from the group consisting of polyamic acid, polyamic acid derivatives and salts thereof;
A liquid medium (B).

[Application Example 2]
The semiconductor surface treatment composition of Application Example 1 contains potassium and sodium,
When the potassium content is M _K (ppm) and the sodium content is M _Na (ppm), M _K / M _Na = 5 × 10 ³ to 1 × 10 ⁵ can be obtained.

[Application Example 3]
The semiconductor surface treatment composition of Application Example 1 or Application Example 2 is
3 × 10 ^{1 to} 1.5 × 10 ³ particles / mL of particles having a particle size of 0.1 to 0.3 μm can be contained.

[Application Example 4]
The chemical mechanical polishing composition according to the present invention comprises:
A composition for semiconductor surface treatment according to any one of Application Examples 1 to 3, and
Contains abrasive grains.

[Application Example 5]
One aspect of the method for cleaning a semiconductor surface according to the present invention is:
The semiconductor surface treatment composition described in any one of Application Examples 1 to 3 can be used.

[Application Example 6]
One aspect of the method for polishing a semiconductor surface according to the present invention is as follows.
The chemical mechanical polishing composition described in Application Example 4 can be used.

  According to the semiconductor surface treatment composition of the present invention, the surface of the object to be polished can be polished without damaging the metal wiring or the like of the object to be polished. Moreover, according to the composition for semiconductor surface treatment of this invention, the surface of a to-be-polished body can be wash | cleaned, without damaging the metal wiring etc. of a to-be-polished body. Furthermore, according to the semiconductor surface treatment method of the present invention, it is possible to obtain an object to be polished that is clean and excellent in flatness.

It is sectional drawing which shows typically the preparation process of the wiring board used for the semiconductor surface treatment method concerning this embodiment. It is a figure which shows typically the apparatus used for the semiconductor surface treatment method which concerns on this embodiment.

Hereinafter, preferred embodiments according to the present invention will be described in detail. It should be understood that the present invention is not limited only to the embodiments described below, and includes various modifications that are implemented within a scope that does not change the gist of the present invention. In addition, “˜ (meth) acrylate” in the present specification is a concept encompassing both “˜acrylate” and “˜methacrylate”. Further, “(meth) acrylic acid˜” is a concept encompassing both “acrylic acid˜” and “methacrylic acid˜”. Further, “for semiconductor surface treatment” in this specification is a concept encompassing “for surface treatment for treating a surface of a semiconductor substrate including a metal wiring”.
1. Semiconductor surface treatment composition The semiconductor surface treatment composition of the present invention,
At least one polymer (A) selected from the group consisting of polyamic acid, polyamic acid derivatives and salts thereof;
A liquid medium (B).

Hereinafter, preferred embodiments of the present invention will be described in detail.
1.1. Polymer (A)
The polymer (A) contained in the composition for semiconductor surface treatment of the present invention is at least one polymer selected from the group consisting of polyamic acid, polyamic acid derivatives, and salts thereof.

When the polymer (A) contained in the composition for semiconductor surface treatment of the present invention contains an imidized polymer of polyamic acid, the imidization rate of the imidized polymer is preferably 50% or less. . In addition, this imidation rate represents the ratio for which the number of the imide ring structure with respect to the sum total of the number of the amic acid structures of a polyamic acid and the number of imide ring structures is represented by the percentage. The imidation ratio of the polyamic acid can be determined using ¹ H-NMR.

  The polyamic acid and its imidized polymer can be used in combination. If the imidization rate of the imidized polymer is in the above preferred range, the use ratio of the polyamic acid and its imidized polymer is an arbitrary ratio. can do.

  A polyamic acid can be obtained by reacting a tetracarboxylic dianhydride and a diamine. The imidized polymer of polyamic acid can be obtained by dehydrating and ring-closing a part of the amic acid structure of the polyamic acid to imidize it.

  The polymer (A) is preferably water-soluble. When the polymer (A) is water-soluble, the polymer (A) is adsorbed on the semiconductor surface, and corrosion can be more effectively suppressed. In the present invention, “water-soluble” means that the mass dissolved in 100 g of water at 20 ° C. is 0.1 g or more.

  Examples of the tetracarboxylic dianhydride used for synthesizing the polyamic acid in the present invention include an aliphatic tetracarboxylic dianhydride, an alicyclic tetracarboxylic dianhydride, an aromatic tetracarboxylic dianhydride, and the like. Can be mentioned. Specific examples of these include aliphatic tetracarboxylic dianhydrides such as butanetetracarboxylic dianhydride; alicyclic tetracarboxylic dianhydrides such as 1,2,3,4-cyclobutanetetra Carboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl)- Naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl)- Naphtho [1,2-c] furan-1,3-dione, 3-oxabicyclo [3.2.1] octane-2,4-dione-6-spiro-3 ′-(tetrahydrofuran-2 ′, 5 ′ -Dione 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxymethylnorbornane-2 : 3,5: 6-dianhydride, 2,4,6,8-tetracarboxybicyclo [3.3.0] octane-2: 4,6: 8-dianhydride, 4,9-dioxatri Cyclo [5.3.1.02,6] undecane-3,5,8,10-tetraone and the like; aromatic tetracarboxylic dianhydrides such as pyromellitic dianhydride, 3,3 ′, 4 , 4′-benzophenone tetracarboxylic dianhydride, 3,3′4,4′-diphenylsulfone tetracarboxylic dianhydride, and the like, respectively, and Patent Document 4 (Japanese Patent Laid-Open No. 2010-97188). ) It can be used tetracarboxylic acid dianhydride of the mounting.

  Among these, the tetracarboxylic dianhydride used for synthesizing the polyamic acid preferably includes an aromatic tetracarboxylic dianhydride. The tetracarboxylic dianhydride in the present invention consists of only an aromatic tetracarboxylic dianhydride or a mixture of an aromatic tetracarboxylic dianhydride and an alicyclic tetracarboxylic dianhydride. It is preferable from the viewpoint of stability of the composition for semiconductor surface treatment of the present invention. In the latter case, the use ratio of the alicyclic tetracarboxylic dianhydride is preferably 30 mol% or less, more preferably 20 mol% or less, based on the total tetracarboxylic dianhydride.

Examples of the diamine used for synthesizing the polyamic acid in the present invention include aliphatic diamine, alicyclic diamine, aromatic diamine, diaminoorganosiloxane and the like. Specific examples thereof include aliphatic diamines such as 1,1-metaxylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine and the like;
Examples of alicyclic diamines include 1,4-diaminocyclohexane, 4,4′-methylenebis (cyclohexylamine), 1,3-bis (aminomethyl) cyclohexane and the like;
Examples of aromatic diamines include p-phenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl sulfide, 1,5-diaminonaphthalene, 2,2′-dimethyl-4,4′-diaminobiphenyl, 4,4′-diamino-2,2′-bis (trifluoromethyl) biphenyl, 2,7-diaminofluorene, 4,4′-diaminodiphenyl ether, 2,2-bis [4- (4-aminophenoxy) phenyl ] Propane, 9,9-bis (4-aminophenyl) fluorene, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane 4,4 ′-(p-phenylenediisopropylidene) bisaniline, 4,4 ′-(m-phenylenediisopropylene Riden) bisaniline, 1,4-bis (4-aminophenoxy) benzene, 4,4′-bis (4-aminophenoxy) biphenyl, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diamino Pyrimidine, 3,6-diaminoacridine, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, N-ethyl-3,6-diaminocarbazole, N-phenyl-3,6-diaminocarbazole, N , N′-bis (4-aminophenyl) -benzidine, N, N′-bis (4-aminophenyl) -N, N′-dimethylbenzidine, 1,4-bis- (4-aminophenyl) -piperazine, 3,5-diaminobenzoic acid and the like;
Examples of the diaminoorganosiloxane include 1,3-bis (3-aminopropyl) -tetramethyldisiloxane, and the diamine described in Patent Document 4 (Japanese Patent Laid-Open No. 2010-97188). be able to.

  The diamine used for synthesizing the polyamic acid in the present invention preferably contains 30% by mole or more, more preferably 50% by mole or more, especially 80 moles of the aromatic diamine with respect to the total diamine. % Or more is preferable.

  When synthesizing the polyamic acid, a terminal-modified polymer may be synthesized using an appropriate molecular weight regulator together with the tetracarboxylic dianhydride and dimian as described above.

Examples of the molecular weight regulator include acid monoanhydrides, monoamine compounds, monoisocyanate compounds, and the like. Specific examples thereof include acid monoanhydrides such as maleic anhydride, phthalic anhydride, itaconic anhydride, n-decyl succinic anhydride, n-dodecyl succinic anhydride, n-tetradecyl succinic anhydride, n-hexadecyl succinic anhydride and the like;
Examples of monoamine compounds include aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, and n-octylamine;
Examples of the monoisocyanate compound include phenyl isocyanate and naphthyl isocyanate.

  The use ratio of the molecular weight regulator is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, with respect to 100 parts by mass in total of the tetracarboxylic dianhydride and diamine used.

  The ratio of the tetracarboxylic dianhydride and the diamine used for the polyamic acid synthesis reaction is 0.9 to 1 for the tetracarboxylic dianhydride acid anhydride group to 1 equivalent of the amino group of the diamine. A ratio of 2 equivalents is preferable, and a ratio of 1.0 to 1.1 equivalents is more preferable.

  The polyamic acid synthesis reaction is preferably carried out in an organic solvent, preferably at -20 ° C to 150 ° C, more preferably at 0-100 ° C, preferably 0.1-24 hours, more preferably 0.5-12 hours. Done.

Here, as the organic solvent, for example, an aprotic polar solvent, a phenol and a derivative thereof, an alcohol, a ketone, an ether, an ester, a hydrocarbon, or the like, which can generally be used for a polyamic acid synthesis reaction, can be used. . Specific examples of these organic solvents include the above aprotic polar solvents such as N-methyl-2-pyrrolidone, Nt-butyl-2-pyrrolidone, N-methoxyethyl-2-pyrrolidone, N, N-dimethyl. Acetamide, N, N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, tetramethylurea, hexamethylphosphortriamide and the like;
Examples of the phenol derivative include m-cresol, xylenol, halogenated phenol and the like;
Examples of the alcohol include methanol, ethanol, isopropanol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol, and ethylene glycol monomethyl ether;
Examples of the ketone include acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone;
Examples of the ether include ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol-n-propyl ether, ethylene glycol-i-propyl ether, ethylene glycol-mono-n-butyl ether, ethylene glycol-di-n-butyl ether, ethylene Examples thereof include glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, and tetrahydrofuran.
Examples of the ester include ethyl lactate, butyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, isoamyl propionate, isoamyl isobutyrate, diethyl oxalate, and malonic acid. Diethyl etc .;
Examples of the hydrocarbon include hexane, heptane, octane, benzene, toluene, xylene, and the like.

  The polyamic acid dehydration ring-closing reaction is preferably performed by a method of heating the polyamic acid or a method of adding a dehydrating agent and a dehydrating ring-closing catalyst to a solution obtained by dissolving the polyamic acid in an organic solvent and heating as necessary.

  In the method of adding a dehydrating agent and a dehydrating ring-closing catalyst to the polyamic acid solution, for example, an acid anhydride such as acetic anhydride, propionic anhydride, or trifluoroacetic anhydride can be used as the dehydrating agent. The use ratio of the dehydrating agent is preferably 0.01 to 1.0 mol with respect to 1 mol of the amic acid structure of the polyamic acid. As the dehydration ring closure catalyst, for example, tertiary amines such as pyridine, collidine, lutidine, and triethylamine can be used. The use ratio of the dehydration ring closure catalyst is preferably 0.01 to 10 mol per 1 mol of the dehydrating agent to be used. Examples of the organic solvent used in the dehydration ring-closing reaction include the organic solvents exemplified as those used for the synthesis of polyamic acid. The reaction temperature of the dehydration ring closure reaction is preferably 0 to 180 ° C, more preferably 10 to 150 ° C. The reaction time is preferably 1 to 10 hours, more preferably 2 to 5 hours.

  The polyamic acid, polyamic acid derivative, and salts thereof obtained as described above have a solution viscosity of 2,000 to 100,000 mPa · s when this is made into a solution having a concentration of 10% by weight. Is preferred. The solution viscosity (mPa · s) of this polymer is about 10% by weight of the polymer solution prepared using a good solvent for these polymers (for example, γ-butyrolactone, N-methyl-2-pyrrolidone, etc.). It is a value measured at 25 ° C. using an E-type rotational viscometer.

  Moreover, about the polyamic acid obtained as mentioned above, a polyamic acid derivative, and those salts, the polystyrene conversion weight average molecular weight (Mw) measured by the gel permeation chromatography (GPC) is 1,000-500,000. Preferably there is. Furthermore, the ratio (Mw / Mn) between the Mw and the polystyrene-equivalent number average molecular weight (Mn) measured by gel permeation chromatography (GPC) is preferably 15 or less.

  The polyamic acid or its imidized product obtained as described above is used as it is or after purification by a known method as necessary, for preparation of a semiconductor surface treatment composition described later.

  As the polyamic acid in the present invention, a commercially available polyamic acid solution may be used. As a commercially available polyamic acid solution, U-varnish A (made by Ube Industries, Ltd.) etc. can be mentioned, for example.

The content ratio of the polymer (A) is preferably 0.0001% by mass to 1% by mass, more preferably 0.0005% by mass to 0.5% by mass with respect to the total mass of the semiconductor surface treatment composition. Hereinafter, it is particularly preferably 0.001% by mass or more and 0.1% by mass or less. When the content ratio of the polymer (A) is within the above range, the polymer (A) is adsorbed on the surface of the wiring material, and excessive etching can be more effectively suppressed.
1.2. Liquid medium (B)
The composition for semiconductor surface treatment of the present invention contains a liquid medium (B). As a liquid medium (B), it is preferable that the boiling point under 1 atmosphere is 50-300 degreeC. A liquid medium having such a boiling point is easily removed by spin drying or heating after the surface treatment.

  Examples of the liquid medium (B) include water, alcohols, esters, ethers, and hydrocarbons. Especially, it is more preferable in the point of the impure metal ion removal performance on the metal wiring that the said liquid medium (B) is water. The liquid medium (B) preferably contains 90% by mass or more of water.

  Specific examples of the alcohols, the esters, the ethers, and the hydrocarbons include monohydric alcohols such as isopropanol and butanol; ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, and tripropylene. Dihydric alcohols such as glycol, butanediol, pentanediol and hexanediol; ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate; propylene glycol monomethyl ether, propylene glycol monoethyl ether; Propylene such as propylene glycol monopropyl ether and propylene glycol monobutyl ether Glycol monoalkyl ethers; propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl Propylene glycol monoalkyl ether acetates such as ether acetate and propylene glycol monobutyl ether acetate; cellosolves such as ethyl cellosolve and butyl cellosolve; carbitols such as butyl carbitol; methyl lactate, ethyl lactate, n-propyl lactate, isopropyl lactate, etc. Lactic acid esters; , Aliphatic carboxylic acid esters such as n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, isopropyl propionate, n-butyl propionate, isobutyl propionate; Other esters such as methyl methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl pyruvate and ethyl pyruvate; aromatic hydrocarbons such as toluene and xylene Ketones such as 2-heptanone, 3-heptanone, 4-heptanone and cyclohexanone; amides such as N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide and N-methylpyrrolidone; and γ-butyrolactone Examples include lactonesThese solvents may be used alone or in combination of two or more.

The content ratio of the liquid medium (B) is preferably 0.0001% by mass to 1% by mass, more preferably 0.0005% by mass to 0.5% by mass with respect to the total mass of the semiconductor surface treatment composition. Hereinafter, it is particularly preferably 0.001% by mass or more and 0.1% by mass or less. When the content rate of a liquid medium (B) is the said range, the wettability of the semiconductor surface and the composition for semiconductor surface treatment can be improved more.
1.3. Other Components The semiconductor surface treatment composition of the present invention can contain other components in addition to the polymer (A) and the liquid medium (B). Examples of other components include abrasive particles, a surfactant, a water-soluble (co) polymer (salt), a surfactant, a pH adjuster, and the like. These may be used alone or in combination of two or more.

  As the abrasive particles, known materials can be used, but inorganic oxide particles and organic particles are preferable.

  Examples of the inorganic oxide particles include inorganic particles such as silica, ceria, alumina, zirconia, and titania. Moreover, colloidal silica is more preferable from the viewpoint of suppressing generation of scratches on the surface of the wiring metal film.

  The content of the inorganic oxide particles is preferably 0.2 parts by mass or more and 10 parts by mass or less, more preferably 0.3 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the total mass of the semiconductor surface treatment composition. It is below mass parts. When the content of the inorganic oxide particles is within the above range, a sufficient polishing rate for the wiring metal film can be obtained, and a stable semiconductor surface treatment composition that hardly causes sedimentation / separation of the particles can be easily obtained.

  Examples of the surfactant include amines, amine salts of hydrochloric acid, amine salts of hydrobromic acid, and carboxylic acids and amine salts thereof. Specific examples of the surfactant include primary amines such as methylamine, ethylamine, n-propylamine, isopropylamine and n-butylamine; dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, diisopropylamine Secondary amines such as n-butylamine; tertiary amines such as trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine; alkanolamines such as monoethanolamine, diethanolamine, triethanolamine; and , Oxalic acid, malonic acid, succinic acid, adipic acid, glutaric acid, diethyl glutaric acid, pimelic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, diglycolic acid, capric acid, lauric acid, myristic acid, palmitic acid , Linole Aliphatic carboxylic acids such as oleic acid, stearic acid, arachidic acid, behenic acid, linolenic acid; aromatic acids such as benzoic acid; hydroxypivalic acid, dimethylolpropionic acid, citric acid, malic acid, glyceric acid, lactic acid, etc. Hydroxy acids and amine salts of these carboxylic acids. These may be used alone or in combination of two or more. By using the surfactant, the polymer (A) is coordinated and stabilized to a metal ion solubilized by the action of the semiconductor surface treatment composition, and the formed complex can be reliably removed. In addition, the composition for semiconductor surface treatment of the present invention can exhibit the desired effect more effectively.

  The blending amount of the surfactant is not particularly limited, but is preferably 0.01 to 1.00 parts by mass when the total amount of the composition for semiconductor surface treatment is 100 parts by mass, 0.05 to 0 More preferably, it is 50 parts by mass.

  Examples of the water-soluble (co) polymer (salt) include polymers of unsaturated carboxylic acids such as poly (meth) acrylic acid and acrylic acid-methacrylic acid copolymers and salts thereof; polyvinyl alcohol, polyvinyl pyrrolidone, Water-soluble polymers such as hydroxyethyl cellulose can be mentioned. These may be used alone or in combination of two or more.

  By using the water-soluble (co) polymer (salt), it can be adsorbed to foreign matters remaining on the surface of the substrate after chemical mechanical polishing, and these can be dispersed and removed in the liquid, which is more effective. In particular, the desired effect of the composition for semiconductor surface treatment can be exhibited.

  Although the compounding quantity of the said water-soluble (co) polymer (salt) is not specifically limited, When the whole quantity of the composition for semiconductor surface treatment is 100 mass parts, it is 0.01-1.00 mass parts. Preferably, it is 0.05-0.50 mass part.

  Examples of the surfactant include an anionic surfactant and a nonionic surfactant.

  Specific examples of the anionic surfactant include alkylbenzene sulfonic acid such as dodecylbenzene sulfonic acid; alkyl naphthalene sulfonic acid; alkyl sulfate such as lauryl sulfate; sulfate of polyoxyethylene alkyl ether such as polyoxyethylene lauryl sulfate. Naphthalene sulfonic acid condensate; lignin sulfonic acid and the like. These anionic surfactants may be used in the form of a salt.

  Specific examples of the nonionic surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether; polyoxyethylene octyl phenyl ether, Polyoxyethylene aryl ethers such as polyoxyethylene nonylphenyl ether; sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate; polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, And polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monostearate.

  The said surfactant may be used individually by 1 type, and may use 2 or more types together. By using the surfactant, foreign matters remaining on the surface of the substrate can be dispersed and removed when the surface of the semiconductor substrate including the metal wiring is processed using the composition of the present invention. And the desired effect of the composition for semiconductor surface treatment can be exhibited more effectively.

  Although the compounding quantity of the said surfactant is not specifically limited, When the whole quantity of the composition for semiconductor surface treatment is 100 mass parts, it is preferable that it is 0.001-1.00 mass part, 0.001-0 More preferably, it is 10 parts by mass.

  The semiconductor surface treatment composition of the present invention may have the concentration of each component in the above range at the time of use. That is, the composition for semiconductor surface treatment of the present invention may be used by directly blending each component so as to be in the above concentration range, or by preparing a composition in a state concentrated from the above concentration range. Before use, a solvent may be added and diluted so that the concentration of each component is in the above range.

  The composition in a concentrated state can be prepared by increasing the concentration of each component other than the solvent by removing the solvent while maintaining the ratio of the amount of each component other than the solvent. Moreover, it can also prepare by reducing the addition amount of a solvent previously.

  The composition for semiconductor surface treatment of the present invention may further contain a pH adjuster as necessary.

  Examples of the pH adjuster include inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid, and phosphoric acid; alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, rubidium hydroxide, and cesium hydroxide; tetramethylammonium hydroxy And basic substances such as ammonia (TMAH) and ammonia. The said pH adjuster may be used individually by 1 type, and may use 2 or more types together. You may adjust the pH of the composition for semiconductor surface treatment in the following ranges using the said pH adjuster.

  The composition for semiconductor surface treatment of the present invention has a pH of 4 to 11, preferably 4.5 to 10. PH in this invention is a value measured based on 25 degreeC and JISK0400-12-10: 2000.

  The composition for semiconductor surface treatment of the present invention can be prepared by mixing the respective components described above.

2. Method for Preparing Semiconductor Surface Treatment Composition The method for preparing the semiconductor surface treatment composition according to the present embodiment is not particularly limited, and a known method can be used.

When the composition for semiconductor surface treatment is used as a cleaning agent used after the CMP step, it contains 3 × 10 ^{1 to} 1.5 × 10 ³ particles / mL of particles having a particle size of 0.1 to 0.3 μm. preferable. By containing particles having a particle diameter of 0.1 to 0.3 μm in the semiconductor cleaning body composition in the above-mentioned range, it is considered that the polishing scraps remaining on the surface to be polished can be effectively scraped off and removed in the cleaning process. . On the other hand, when particles having a particle size of 0.1 to 0.3 μm contained in the composition for semiconductor surface treatment exceed the above range, the particles remain on the polished surface after cleaning, This is not preferable because a decrease in yield due to deterioration of electrical characteristics of a certain semiconductor circuit is induced.

  Generally, as described in WO 1999/049997 and the like, it is recognized that particles are a foreign substance to be removed as much as possible in the manufacturing process of a semiconductor device. However, in the invention of the present application, it has been found that if the content is within a certain range, the semiconductor properties are not significantly deteriorated, and conversely, the cleaning properties are improved.

  Here, the particle size of the particles and the content in the composition for semiconductor surface treatment are measured when the particle size distribution is measured using a particle size distribution measuring apparatus based on a laser diffraction method, and the particles are accumulated from small particles. This is the value of the particle diameter (D50) at which the cumulative frequency of the number of particles is 50%. Examples of such a laser diffraction particle size distribution measuring apparatus include HORIBA LA-300 series, HORIBA LA-920 series (manufactured by Horiba, Ltd.) and the like. This particle size distribution measuring apparatus does not only evaluate the primary particles of the particles, but also evaluates the secondary particles formed by aggregation of the primary particles. Therefore, the particle diameter obtained by this particle size distribution measuring apparatus can be used as an index of the dispersion state of the particles contained in the semiconductor surface treatment composition.

  In the method for producing a semiconductor surface treatment composition according to the present embodiment, it is preferable to control the amount of particles by filtering with a depth type or pleat type filter, if necessary. Here, the depth type filter is a high-precision filtration filter that is also referred to as a depth filtration or volume filtration type filter. Such depth type filters include those having a laminated structure in which filtration membranes having a large number of pores are laminated, and those in which fiber bundles are wound up. Specific examples of depth type filters include Profile II, Nexis NXA, Nexis NXT, Polyfine XLD, Ultiplez Profile, etc. (all manufactured by Nippon Pole), depth cartridge filters, wind cartridge filters, etc. (all, Advantech) Co., Ltd.), CP filter, BM filter, etc. (all manufactured by Chisso Corporation), slope pure, diamond, micro-Syria, etc. (all manufactured by Loki Techno Co.), and the like.

  As a pleated type filter, a microfiltration membrane sheet made of non-woven fabric, filter paper, metal mesh, etc. is fold-folded and then molded into a cylindrical shape, and the seam of the pleats of the sheet is sealed in a liquid-tight manner. It is a cylindrical high-precision filtration filter obtained by sealing both ends of the liquid-tight. Specifically, HDCII, Polyfine II, etc. (all manufactured by Nihon Pall), PP pleated cartridge filter (manufactured by Advantech), Porous Fine (manufactured by Chisso), Sirton Pore, Micropure, etc. (all, manufactured by Loki Techno) Etc.

  A filtration process can be performed using the filtration apparatus 101 as shown in FIG. 1, for example. The filtration apparatus 101 includes a supply tank 1 for storing and supplying a semiconductor surface treatment composition before removing foreign substances, a metering pump 2 for flowing the semiconductor surface treatment composition before removing foreign substances at a constant flow rate, and a cartridge filter. (Not shown) and a filter 4 having a housing in which the cartridge filter is housed (mounted), a pulsation preventer 3 located in the middle of the metering pump 2 and the filter 4, a pulsation preventer 3 and a filter 4 The 1st pressure gauge 7a arrange | positioned between these, and the 2nd pressure gauge 7b arrange | positioned downstream of the filter 4 are provided. The filtration apparatus 101 includes a return conduit 6 that returns the binder from the filter 4 to the supply tank 1 and a discharge conduit 5 that discharges the semiconductor surface treatment composition filtered by the filter 4.

  In the filtration device 101, the reaction liquid obtained in the polymerization step is supplied from the supply tank 1 to the pulsation preventer 3 whose pressure has been increased by the metering pump 2. When there is a pulsation by the metering pump 2, the pulsation is reduced by the pulsation preventer 3. The reaction liquid discharged from the pulsation preventer 3 is supplied to the filter 4 and removed through the discharge conduit 5 after removing foreign substances. This recovered liquid is a semiconductor surface treatment composition. Here, in this specification, “foreign matter” means particles having a particle diameter of 20 μm or more.

  When the removal of foreign substances in the liquid recovered through the discharge conduit 5 is not sufficient, the recovered liquid is returned to the supply tank 1 through the return conduit 6 without being used as the semiconductor surface treatment composition, and again into the filter 4. Can also be filtered. Moreover, when the pulsation by the metering pump 2 does not occur, the pulsation preventer 3 may not be disposed. Furthermore, when the viscosity of the reaction solution is high, the viscosity of the reaction solution can be lowered by heating the supply tank, the conduit, or both of them. That is, you may further provide the heating means which can heat a supply tank, a conduit | pipe, or both.

  Although the filtration device 101 includes the first pressure gauge 7a and the second pressure gauge 7b, a filtration device that does not include a pressure gauge may be used. However, by providing the first pressure gauge 7a and the second pressure gauge 7b, the differential pressure generated in the filter can be managed so that the filter functions normally. Moreover, it may replace with the supply tank 1 and may supply the composition for semiconductor surface treatment before a foreign material removal directly from the container for conveyance. And although the filtration apparatus 101 is an example using the single filter 4, a several filter can also be used. When using a some filter, a some filter may be connected in series and you may arrange | position in parallel.

3. Surface treatment method The surface treatment method of the present invention is characterized in that the semiconductor surface treatment composition is brought into contact with a surface of a semiconductor substrate containing metal wiring, and the surface of the semiconductor substrate containing metal wiring is treated. Hereinafter, a specific example of the cleaning method according to the present embodiment will be described in detail with reference to the drawings.

3.1. Polishing Step FIG. 2 is a cross-sectional view schematically showing a manufacturing process of a wiring board used in the semiconductor surface treatment method according to this embodiment. Such a wiring board is formed through the following process.

  FIG. 2A is a cross-sectional view schematically showing an object to be processed before the CMP process. As illustrated in FIG. 2A, the target object 100 includes a substrate 10. The substrate 10 may be composed of, for example, a silicon substrate and a silicon oxide film formed thereon. Further, although not shown in the figure, a functional device such as a transistor may be formed on the base 10.

  An object 100 to be processed includes an insulating film 12 provided with a wiring recess 20 on a substrate 10, and a barrier metal film provided so as to cover the surface of the insulating film 12 and the bottom and inner wall surfaces of the wiring recess 20. 14 and a metal film 16 filling the wiring recess 20 and formed on the barrier metal film 14 are sequentially laminated.

  As the insulating film 12, for example, a silicon oxide film (for example, a PETEOS film (Plasma Enhanced-TEOS film), a HDP film (High Density Plasma Enhanced-TEOS film)) formed by a vacuum process, or a thermal chemical vapor deposition method is used. And an insulating film called FSG (Fluorine-doped silicate glass), a boron phosphorous silicate film (BPSG film), an insulating film called SiON (Silicon Oxide Nitride), and silicon nitride.

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

  As shown in FIG. 2A, the metal film 16 needs to completely fill the wiring recess 20. For this purpose, a metal film of 10,000 to 15000 angstroms is deposited usually by chemical vapor deposition or electroplating. Examples of the material of the metal film 20 include copper or tungsten. In the case of copper, not only high-purity copper but also an alloy containing copper can be used. The copper content in the alloy containing copper is preferably 95% by mass or more.

  2A, the metal film 16 other than the portion buried in the wiring recess 20 is polished at high speed by CMP until the barrier metal film 14 is exposed (first polishing step). Further, the barrier metal film 14 exposed on the surface is polished by CMP using the above-described semiconductor surface treatment composition (second polishing step). In this way, a wiring substrate 200 as shown in FIG. 2B is obtained. In addition, when polishing a wiring board where wiring material and barrier metal material coexist on the surface, corrosion of the wiring material and barrier metal material is suppressed, and oxide films and organic residues on the wiring board are efficiently removed. Can do. Since the semiconductor surface treatment method according to the present embodiment uses a composition for semiconductor surface treatment that can reduce the corrosion potential difference between copper / cobalt and copper / tantalum nitride, copper is used as the wiring material, cobalt and / or the barrier metal material is used. When a polishing process is performed on a wiring substrate in which tantalum nitride coexists, a particularly excellent effect is exhibited.

4.2. Cleaning Step Next, the surface (surface to be cleaned) of the wiring substrate 200 shown in FIG. 2B is cleaned using the above-described semiconductor surface treatment composition. According to the semiconductor surface treatment method according to the present embodiment, when cleaning the wiring substrate in which the wiring material and the barrier metal material after the CMP coexist on the surface, the corrosion of the wiring material and the barrier metal material is suppressed, and the wiring An oxide film and organic residues on the substrate can be efficiently removed. Since the semiconductor surface treatment method according to the present embodiment uses a composition for semiconductor surface treatment that can reduce the corrosion potential difference between copper / cobalt and copper / tantalum nitride, copper is used as the wiring material, cobalt and / or the barrier metal material is used. When a cleaning process is performed on a wiring board in which tantalum nitride coexists, a particularly excellent effect is exhibited.

  The semiconductor surface treatment method is not particularly limited, but is performed by a method in which the above-described semiconductor surface treatment composition is directly brought into contact with the wiring substrate 200. As a method for bringing the semiconductor surface treatment composition into direct contact with the wiring substrate 200, a dip type in which the cleaning substrate is filled with the semiconductor surface treatment composition and the wiring substrate is immersed; the composition for semiconductor surface treatment from the nozzle onto the wiring substrate. Examples include a spin method in which the wiring substrate is rotated at a high speed while flowing down; a spray method in which the semiconductor surface treatment composition is sprayed on the wiring substrate and washed. In addition, as an apparatus for performing such a method, a batch type cleaning apparatus that simultaneously cleans a plurality of wiring boards accommodated in a cassette, a single wafer cleaning that attaches and cleans one wiring board to a holder Examples thereof include an apparatus.

  In the semiconductor surface treatment method according to the present embodiment, the temperature of the semiconductor surface treatment composition is usually room temperature, but may be heated within a range not impairing the performance, for example, about 40 to 70 ° C. can do.

  In addition to the above-described method for directly contacting the semiconductor surface treatment composition with the wiring substrate 200, it is also preferable to use a semiconductor surface treatment method based on physical force in combination. Thereby, the removal property of the contamination by the particles adhering to the wiring board 200 is improved, and the cleaning time can be shortened. Examples of the cleaning method using physical force include scrub cleaning using a cleaning brush and ultrasonic cleaning.

  Furthermore, cleaning with ultrapure water or pure water may be performed before and after the cleaning by the semiconductor surface treatment method according to the present embodiment.

4). Examples Hereinafter, the present invention will be described by way of examples. However, the present invention is not limited to these examples. In the examples, “parts” and “%” are based on mass unless otherwise specified.

4.1 Synthesis of polymer (A) After removing the residual moisture inside the container by heating with a heat gun while reducing the pressure inside the 3 L flask equipped with a stirrer, thermometer and condenser, dry nitrogen gas was added. Satisfied. In this flask, 1,170 g of N-methyl-2-pyrrolidone (NMP) subjected to dehydration by a dehydration distillation method using calcium hydride in advance as a solvent, pyromellitic dianhydride 54 as tetracarboxylic dianhydride .53 g (0.250 mol) and 50.06 g (0.250 mol) of 4,4′-diaminodiphenyl ether as a diamine were charged and reacted at 25 ° C. with stirring for 3 hours to obtain 10 mass of polyamic acid A1. % NMP solution was obtained.

  100 g of the solution containing the prepared polyamic acid A1 was dropped little by little into about 1 L of water and solidified. The coagulated product was thoroughly washed in running water to sufficiently remove NMP, and then dried under reduced pressure overnight at room temperature to obtain a solid polyamic acid. Next, 10 g of the solid polyamic acid was placed in 90 g of a 2% by mass aqueous ammonia solution (pH 11) and stirred at room temperature for 3 hours to obtain an aqueous solution containing 10% by mass of polyamic acid A1.

  NMP solution containing 10% by mass of polyamic acids A2 to A20, respectively, in the same manner as polyamic acid A1, except that the types of tetracarboxylic dianhydride and diamine used were those shown in Table 1, respectively. Got.

  Regarding these polyamic acids, an aqueous solution containing 10% by mass of polyamic acids A2 to A20 was obtained in the same manner as the polyamic acid A1.

4.2. Example 1
4.2.1. Preparation of semiconductor surface treatment composition Each component and potassium hydroxide or tetramethylammonium hydroxide were added to polyethylene containers at appropriate times so as to have the concentrations and pH shown in Table 2 as semiconductor surface treatment compositions, and ion exchange was performed. An appropriate amount of water was added and stirred for 15 minutes.

  After adding 0.01 parts by mass of colloidal silica (trade name “PL-1”, manufactured by Fuso Chemical Industries, Ltd., primary particle size 15 nm) to the composition thus obtained, FIG. Filtration was performed using the filtration device 101 shown (filtration step). A filtration apparatus 101 shown in FIG. 1 includes a supply tank 1 for storing and supplying a composition before removing foreign matter, a metering pump 2 for flowing the composition before removing foreign matter at a constant flow rate, and a cartridge filter (not shown). ) And a filter 4 having a housing in which this cartridge filter is housed (mounted), a pulsation preventer 3 located in the middle of the metering pump 2 and the filter 4, and disposed between the pulsation preventer 3 and the filter 4. The first pressure gauge 7a and the second pressure gauge 7b disposed downstream of the filter 4 are provided. The filtration device 101 includes a return conduit 6 that returns the semiconductor surface treatment composition from the filter 4 to the supply tank 1, and a discharge conduit 5 that discharges the semiconductor surface treatment composition filtered by the filter 4. I have.

  In this experimental example, the filter 4 has a membrane type cartridge filter “Water Fine” (manufactured by Nippon Pole Co., Ltd., rated filtration accuracy 0.05 μm, length 10 inches) mounted in the housing. As the metering pump 2, an air-driven diaphragm pump was used.

  The composition was sampled in a timely manner, and when the number of particles of 0.1 to 0.3 μm contained in the composition became as shown in Table 1, filtration was stopped to prepare a semiconductor surface treatment composition. The number of particles per 1 mL of the composition was measured as follows.

  As the particle counter, an in-liquid particle counter “KS-42AF” manufactured by Rion Co., Ltd. was used. Specifically, until the number of particles to be measured reaches “300 particles / mL (0.1 μm)” (that is, “300 particles having a particle diameter larger than 0.1 μm in 1 mL or less”). Blank measurement was repeated with ultrapure water. Thereafter, 100 mL of a semiconductor surface treatment composition (sample) was prepared, and this sample was set in the particle size distribution analyzer. Thereafter, the number of particles per 1 mL of the sample is measured twice by the particle counter, and an average value is calculated. This average value was defined as the number of particles per 1 mL of the semiconductor surface treatment composition.

4.2.2. Treatment of semiconductor surface 4.2.2.1. Chemical mechanical polishing An 8-inch wafer for evaluation (manufactured by Advance Materials Technology, cobalt film formed by CVD with a thickness of 200 nm) was chemically treated using a chemical mechanical polishing apparatus “EPO112” (manufactured by Ebara Corporation) under the following conditions. Mechanical polishing was performed.
-Chemical mechanical polishing aqueous dispersion: "CMS8501 / CMS8552" manufactured by JSR Corporation
・ Polishing pad: “IC1000 / SUBA400” manufactured by Rodel Nitta Co., Ltd.
・ Surface rotation speed: 70rpm
-Head rotation speed: 70 rpm
Head load: 250 g / cm ²
-Chemical mechanical polishing aqueous dispersion supply rate: 200 mL / min-Polishing time: 60 seconds 4.2.2.2. Corrosion evaluation by AFM A substrate having undergone the above-mentioned chemical mechanical polishing treatment was cut to prepare a 2 × 2 cm test piece, and a frame size of 10 μm using a Dimension FastScan, a scanning atomic force microscope (AFM) manufactured by Bluker Corporation. A wafer that was observed with no unevenness at 12 locations and was confirmed to have a flat surface with an average value of arithmetic average roughness at 12 locations of 0.1 nm or less was used for defect evaluation. The test piece was immersed in the semiconductor surface treatment composition according to the present embodiment whose temperature was adjusted to 18 ° C. for 1 hour. After the immersion, it was rinsed with ultrapure water for 30 seconds and allowed to dry naturally. The dried test specimens were observed at arbitrary three locations with a frame size of 10 μm using a scanning atomic force microscope.

  If the average value of the arithmetic average roughness at three locations is 0.2 nm or more, the composition for semiconductor surface treatment causes corrosion to be judged as defective, and if it is less than “×”, less than 0.2 nm, the semiconductor surface treatment Table 2 shows that it was judged as good without corrosion due to the composition for use.

4.2.2.3. Corrosion evaluation by EIS The polished substrate obtained above was cut to prepare two 1 × 3 cm test pieces, and the central 1 × 1 cm portion was covered with an insulating tape. Thereafter, using the electrochemical impedance measurement device (Electrochemical interface (SI1287) and Frequency Response Analyzer (1252A) manufactured by Solartron), the two test pieces are used as a working electrode and a counter electrode, respectively, and the semiconductor surface treatment composition according to this embodiment is used. A two-electrode cell using the product as an electrolyte was assembled. An AC voltage having an amplitude of 5 mV and a frequency of 1500 to 0.07 Hz was applied from a high frequency to a low frequency, and the values of the real part and the imaginary part of the resistance value were measured. A semicircular plot obtained by taking the measurement result with the imaginary part on the vertical axis and the real part on the horizontal axis was analyzed with AC impedance analysis software “Z view” to calculate the charge transfer resistance (Ω).

  If the calculated charge transfer resistance value is 40 kΩ or less, it is judged that the corrosion resistance is insufficient.

4.3. Examples 2-20, Comparative Examples 1-7
A composition for semiconductor surface treatment was prepared and evaluated in the same manner as in Example 1 except that the compositions shown in Tables 2 and 3 were changed and adjusted to the compositions shown in Tables 2 and 3. The results are shown in Table 2 and Table 3.

4.4. Example 21
4.4.1. Preparation of composition for semiconductor surface treatment 4.4.2. Measurement of Polishing Rate The 8-inch wafer for evaluation shown below was chemically processed using the chemical mechanical polishing apparatus “EPO112” (manufactured by Ebara Corporation) under the following conditions. Mechanical polishing was performed.

(1) Polishing speed measurement substrate: 8-inch thermal oxide film silicon substrate on which a 2,000 Å-thick cobalt film is laminated.
A silicon substrate with an 8-inch thermal oxide film on which a titanium nitride film having a thickness of 2,000 angstroms is laminated.
An 8-inch silicon substrate on which a 10,000 Å thick PETEOS film is laminated.

(2) Polishing conditions and head rotation speed: 70 rpm
Head load: 200 gf / cm ²
・ Table rotation speed: 70rpm
-Supply rate of chemical mechanical polishing aqueous dispersion: 200 mL / min-Polishing time: 60 seconds (3) Calculation method of polishing rate For cobalt film and titanium nitride film, an electroconductive film thickness meter (manufactured by KLA Tencor) Using the format “Omnimap RS75”), the film thickness after the polishing treatment was measured, and the polishing rate was calculated from the film thickness decreased by chemical mechanical polishing and the polishing time.

  For PETEOS film and low dielectric constant insulating film, the film thickness after polishing is measured using an optical interference film thickness measuring instrument (Nanometrics Japan, model “Nanospec6100”) and reduced by chemical mechanical polishing. The polishing rate was calculated from the obtained film thickness and polishing time.

4.4.3. Corrosion evaluation by AFM The polished cobalt substrate obtained above was cut to prepare a 2 × 2 cm test piece, and immersed for 1 hour in the semiconductor surface treatment composition according to the present embodiment, which was temperature-controlled at 18 ° C. . After immersing, the surface of the test piece was thoroughly polished by a hand wearing a nitrile glove while being rinsed with ultrapure water for 30 seconds, and then naturally dried. The dried test specimens were observed at arbitrary three locations at a frame size of 10 μm using a scanning atomic force microscope (AFM, manufactured by Bluker Corporation, apparatus name “Dimension FastScan”).

  If the average value of arithmetic average roughness at three locations on the cobalt substrate test piece is 0.2 nm or more, it is judged that corrosion has occurred and it is judged as “x”, and if it is less than 0.2 nm, it is good without corrosion. It was judged as “◯” and shown in Table 4.

4.4.4. Corrosion evaluation by EIS All the polished substrates obtained above were cut to prepare two 1 × 3 cm test pieces, and the central 1 × 1 cm portion was covered with an insulating tape. Thereafter, using the electrochemical impedance measurement device (Electrochemical interface (SI1287) and Frequency Response Analyzer (1252A) manufactured by Solartron), the two test pieces are used as a working electrode and a counter electrode, respectively, and the semiconductor surface treatment composition according to this embodiment is used. A two-electrode cell using the product as an electrolyte was assembled. An AC voltage having an amplitude of 5 mV and a frequency of 1500 to 0.07 Hz was applied from a high frequency to a low frequency, and the values of the real part and the imaginary part of the resistance value were measured. A semicircular plot obtained by taking the measurement result with the imaginary part on the vertical axis and the real part on the horizontal axis was analyzed with AC impedance analysis software “Z view” to calculate the charge transfer resistance (Ω).

  If the calculated charge transfer resistance value is 40 kΩ or less, it is judged that the corrosion resistance is insufficient.

4.4. Examples 22-40, Comparative Examples 8-14
A composition for semiconductor surface treatment was prepared and evaluated in the same manner as in Example 21 except that the composition was changed to the composition shown in Table 4 and adjusted to the composition shown in Table 4. The evaluation results are shown in Table 4.

  4.5. Evaluation results

  As is clear from Tables 2 to 4, when the semiconductor surface treatment compositions according to Examples 1 to 40 were used, the corrosion state of the substrate surface was good.

  The present invention is not limited to the above-described embodiments, and various modifications can be made. For example, the present invention includes substantially the same configuration (for example, a configuration having the same function, method, and result, or a configuration having the same purpose and effect) as the configuration described in the embodiment. In addition, the invention includes a configuration in which a non-essential part of the configuration described in the embodiment is replaced. In addition, the present invention includes a configuration that achieves the same effect as the configuration described in the embodiment or a configuration that can achieve the same object. In addition, the invention includes a configuration in which a known technique is added to the configuration described in the embodiment.

DESCRIPTION OF SYMBOLS 1 ... Supply tank, 2 ... Metering pump, 3 ... Anti-pulsation device, 4 ... Filter, 5 ... Discharge conduit, 6 ... Return conduit, 7a ... First pressure gauge, 7b ... Second pressure gauge, 101 ... Filtration device,
DESCRIPTION OF SYMBOLS 10 ... Base | substrate, 12 ... Insulating film, 14 ... Barrier metal film, 16 ... Metal film, 20 ... Recess for wiring, 100 ... To-be-processed object, 200 ... Wiring board

Claims (6)

At least one polymer (A) selected from the group consisting of polyamic acid, polyamic acid derivatives and salts thereof;
A liquid medium (B);
A composition for semiconductor surface treatment, comprising: A semiconductor surface treatment composition containing potassium and sodium,
The content of the potassium _M K (ppm), the content of the sodium is taken _{as M} Na (ppm), a _{M K / M Na = 5 ×} 10 3 ~1 × 10 5, in claim 1 The composition for semiconductor surface treatment as described. ^{3. The} composition for semiconductor surface treatment according to claim ^1, comprising 3 × 10 ^{1 to} 1.5 × 10 ³ particles / mL of particles having a particle diameter of 0.1 to 0.3 μm. The composition for semiconductor surface treatment according to claims 1 to 3,
Containing abrasive grains,
Chemical mechanical polishing composition.   The method to wash | clean a semiconductor surface using the composition for semiconductor surface treatments of Claims 1-3. A method for polishing a semiconductor surface using the chemical mechanical polishing composition according to claim 4.