POLISHING LIQUID COMPOSITION FOR SILICON OXIDE FILM

Abstract

A polishing liquid composition for a silicon oxide film according to the present invention includes cerium oxide particles, a water-soluble macromolecular compound, and an aqueous medium, and the water-soluble macromolecular compound is a water-soluble macromolecular compound including a betaine structure, excluding carbobetaine homopolymers and sulfobetaine homopolymers. The water-soluble macromolecular compound is preferably a water-soluble macromolecular compound containing a constitutional unit A including a betaine structure, and a constitutional unit B that is a constitutional unit other than the constitutional unit A and contains at least one group of a primary amino group, a secondary amino group, a tertiary amino group, a quaternary ammonium group, and salts thereof.

Claims

1. A polishing liquid composition for a silicon oxide film, comprising: cerium oxide particles; a water-soluble macromolecular compound; and an aqueous medium, wherein the water-soluble macromolecular compound is a water-soluble macromolecular compound including a betaine structure, excluding carbobetaine homopolymers and sulfobetaine homopolymers.

2. The polishing liquid composition for a silicon oxide film according to claim 1, wherein the water-soluble macromolecular compound is a water-soluble macromolecular compound containing a constitutional unit A including a betaine structure, and a constitutional unit B that is a constitutional unit other than the constitutional unit A and contains at least one group of a primary amino group, a secondary amino group, a tertiary amino group, a quaternary ammonium group, and salts thereof.

3. The polishing liquid composition for a silicon oxide film according to claim 1, wherein the water-soluble macromolecular compound is a water-soluble macromolecular compound containing a constitutional unit a represented by Formula (1): ##STR00005## where R.sup.1 to R.sup.3 are the same as or different from each other and represent a hydrogen atom, a methyl group, or an ethyl group, R.sup.4 represents an alkylene group having 1 to 4 carbon atoms or YOPO.sub.3.sup.Y.sup.2, Y.sup.1 and Y.sup.2 are the same as or different from each other and represent an alkylene group having 1 to 4 carbon atoms, R.sup.5 and R.sup.6 are the same as or different from each other and represent a hydrocarbon group having 1 to 4 carbon atoms, X.sup.1 represents O or NR.sup.7, R.sup.7 represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, X.sup.2 represents a hydrocarbon group having 1 to 4 carbon atoms, R.sup.17SO.sub.3.sup., or R.sup.18COO.sup., and R.sup.17 and R.sup.18 are the same as or different from each other and represent an alkylene group having 1 to 4 carbon atoms, and when R.sup.4 is an alkylene group having 1 to 4 carbon atoms, X.sup.2 is R.sup.17SO.sub.3.sup. or R.sup.18COO.sup., and when R.sup.4 is Y.sup.1OPO.sub.3.sup.Y.sup.2, X.sup.2 is a hydrocarbon group having 1 to 4 carbon atoms.

4. The polishing liquid composition for a silicon oxide film according to claim 2, wherein the water-soluble macromolecular compound is a water-soluble macromolecular compound containing a constitutional unit b represented by Formula (2): ##STR00006## where R.sup.8 to R.sup.10 are the same as or different from each other and represent a hydrogen atom, a methyl group, or an ethyl group, X.sup.3 represents O or NR.sup.19, R.sup.19 represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, R.sup.11 represents an alkylene group having 1 to 22 carbon atoms, where a hydrogen atom of the alkylene group is optionally substituted by a hydroxy group, X.sup.4 represents N.sup.+R.sup.12R.sup.13R.sup.14 or NR.sup.15R.sup.16, R.sup.12 to R.sup.14 are the same as or different from each other and represent a hydrocarbon group having 1 to 4 carbon atoms, and R.sup.15 and R.sup.16 are the same as or different from each other and represent a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms.

5. The polishing liquid composition for a silicon oxide film according to claim 1, wherein the water-soluble macromolecular compound is a water-soluble macromolecular compound including a phosphobetaine structure.

6. The polishing liquid composition for a silicon oxide film according to claim 1, further comprising an anionic macromolecular compound.

7. A polishing liquid kit for preparing a polishing liquid composition for a silicon oxide film, comprising: a first liquid obtained by dispersing cerium oxide particles in an aqueous medium; and a second liquid that is contained in a container separate from a container containing the first liquid and contains an aqueous medium, wherein one or both of the first liquid and the second liquid further contains a water-soluble macromolecular compound, and the water-soluble macromolecular compound is a water-soluble macromolecular compound including a betaine structure, excluding other than carbobetaine homopolymers and sulfobetaine homopolymers.

8. An additive composition for silicon oxide film polishing to be used together with a dispersion liquid obtained by dispersing cerium oxide particles in an aqueous medium, comprising: an aqueous medium; and a water-soluble macromolecular compound dissolved in the aqueous medium, wherein the water-soluble macromolecular compound is a water-soluble macromolecular compound including a betaine structure, excluding other than carbobetaine homopolymers and sulfobetaine homopolymers.

9. A method for manufacturing a semiconductor device, comprising a step of polishing a silicon oxide film using the polishing liquid composition for a silicon oxide film according to claim 1.

10. A method for polishing a silicon oxide film, comprising a step of polishing a silicon oxide film using the polishing liquid composition for a silicon oxide film according to claim 1, wherein the silicon oxide film is an insulating film formed in a process for manufacturing a semiconductor device.

Description

EXAMPLES

[0177] 1. Preparation of Polishing Liquid Composition

Preparation of Polishing Liquid Compositions of Examples 1 to 12 and Comparative Examples 1 to 8

[0178] Polishing liquid compositions of Examples 1 to 12 and Comparative Examples 1 to 8 were each prepared by mixing a slurry of cerium oxide particles obtained by dispersing cerium oxide particles in an aqueous medium with a macromolecule solution obtained by dissolving the macromolecule X or a comparison substance thereof in an aqueous medium and adding a pH adjuster to the resulting solution as needed. However, comparison substances of the macromolecules X were not added to the polishing liquid compositions of Comparative Examples 1 and 2. As the pH adjuster, a 1 N aqueous solution of hydrochloric acid or a 1 N aqueous solution of ammonium was used. The pH values of the polishing liquid compositions of Examples 1 to 12 and Comparative Examples 1 to 8 at 25 C. were as shown in Table 2. The contents of the cerium oxide particles, the macromolecules X, and the comparison substances in the polishing liquid compositions were as shown in Table 2.

Preparation of Polishing Liquid Compositions of Examples 13 to 29 and Comparative Examples 9 to 16

[0179] Polishing liquid compositions of Examples 13 to 29 and Comparative Examples 9 to 16 were each prepared by mixing a slurry of cerium oxide particles obtained by dispersing cerium oxide particles in an aqueous medium with a macromolecule solution (additive composition) obtained by dissolving the macromolecule X or a comparison substance thereof and an anionic macromolecular compound (macromolecule Y) in an aqueous medium and adding a pH adjuster to the resulting solution as needed. However, comparison substances of the macromolecules X were not added to the polishing liquid compositions of Comparative Examples 9 and 11, and a comparison substance of the macromolecules X and the macromolecule Y were not added to the polishing liquid composition of Comparative Example 10. As the pH adjuster, a 1 N aqueous solution of hydrochloric acid or a 1 N aqueous solution of ammonium was used. The pH values of the polishing liquid compositions of Examples 13 to 29 and Comparative Examples 9 to 16 at 25 C. were as shown in Table 3. The contents of the cerium oxide particles, the macromolecules X, the comparison substances thereof, and the macromolecules Y in the polishing liquid compositions were as shown in Table 3.

[0180] The details of the cerium oxide particles used to prepare the polishing liquid compositions of Examples 1 to 29 and Comparative Examples 1 to 16 were as follows.

[0181] Pulverized ceria A (pulverized ceria; average primary particle diameter=37.9 nm, D50=165 nm, average crystallite diameter=23.2 nm)

[0182] HC-60 (colloidal ceria manufactured by Solvay Special Chem Japan, Ltd., product name: ZENUS HC-60; average primary particle diameter=67.7 nm, D50=137 nm, average crystallite diameter=37.6 nm)

[0183] The details of constitutional monomers of the macromolecules X and the comparison substances thereof used to prepare the polishing liquid compositions of Examples 1 to 29 were as listed below and as shown in Table 1. [0184] MPC: 2-methacryloyloxyethyl phosphorylcholine [0185] SBMA: [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfopropyl) ammonium hydroxide [0186] CBMA: N-(2-carboxyethyl)-N-methacryloxyethyl-N,N-dimethylammonium betaine [0187] THMPA: N,N,N-trimethyl-N-(2-hydroxy-3-methacryloyloxypropyl)-ammonium chloride [0188] MOEA: 2-aminoethyl methacrylate hydrochloride [0189] MOEDEA: 2-(diethylamino)ethyl methacrylate

TABLE-US-00001 TABLE 1 Constitutional Structures in monomer Structures in Formula (1) Formula (2) SBMA R.sup.1 = R.sup.2 = H, R.sup.3 = CH.sub.3, R.sup.4 = C.sub.2H.sub.4, R.sup.5 = R.sup.6 = CH.sup.3, X.sup.1 = O, X.sup.2 = R.sup.17SO.sub.3.sup., R.sup.17 = C.sub.3H.sub.6 MPC R.sup.1 = R.sup.2 = H, R.sup.3 = CH.sub.3, R.sup.4 = Y.sup.1OPO.sub.3.sup.Y.sup.2, Y.sup.1 = Y.sup.2 = C.sub.2H.sub.4, R.sup.5 = R.sup.6 = CH.sub.3, X.sup.1 = O, X.sup.2 = C.sub.3 THMPA R.sup.8 = R.sup.9 = H, R.sup.10 = CH.sub.3, X.sub.3 = O R.sup.11 = CH.sub.2CH(OH)CH.sub.2 X.sup.4 = N.sup.+R.sup.12R.sup.13R.sup.14, R.sup.12 = R.sup.13 = R.sup.14 = CH.sub.3 CBMA R.sup.1 = R.sup.2 = H, R.sup.3 = CH.sub.3, R.sup.4 = C.sub.2H.sub.4, R.sup.5 = R.sup.6 = CH.sub.3, X.sup.1 = O, X.sup.2 = R.sup.18COO.sup., R.sup.18 = CH.sub.2 MOEA R.sup.8 = R.sup.9 = H, R.sup.10 = CH.sub.3, X.sub.3 = O R.sup.11 = C.sub.2H.sub.4 X.sup.4 = NR.sup.15R.sup.16 R.sup.15 = R.sup.16 = H MOEDEA R.sup.8 = R.sup.9 = H, R.sup.10 = CH.sub.3, X.sub.3 = O R.sup.11 = C.sub.2H.sub.4 X.sup.4 = NR.sup.15R.sup.16 R.sup.15 = R.sup.16 = CH.sub.2CH.sub.3

[0190] Manufacturing of Macromolecule X1

[0191] In a 500-mL four-neck flask, 60 g of ultrapure water was placed and heated to 65 C. A solution obtained by mixing 5.0 g of 2-methacryloyloxyethyl phosphorylcholine (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.0 g of BLEMMER QA (manufactured by NOF Corporation), and 40 g of ultrapure water together and a solution obtained by mixing 0.057 g of V-50 (manufactured by Wako Pure Chemical Industries, Ltd.) and 20 g of ultrapure water together were separately dropped into the water in the flask over a 2-hour period, and polymerization was carried out. After having been matured for 6 hours, the resulting solution was allowed to cool to room temperature, and thus an aqueous polymer solution containing a macromolecule X1 was obtained. The molar ratio between the constitutional units (THMPA/MPC) in the macromolecule X1 was 20/80, and the weight average molecular weight of the macromolecule X1 was 500,000.

[0192] Manufacturing of Macromolecule X2

[0193] In a 500-mL four-neck flask, 52 g of ultrapure water was placed and heated to 65 C. A solution obtained by mixing 5.0 g of 2-methacryloyloxyethyl phosphorylcholine (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.42 g of BLEMMER QA (manufactured by NOF Corporation), and 35 g of ultrapure water together and a solution obtained by mixing 0.048 g of V-50 (manufactured by Wako Pure Chemical Industries, Ltd.) and 17 g of ultrapure water together were separately dropped into the water in the flask over a 2-hour period, and polymerization was carried out. After having been matured for 6 hours, the resulting solution was allowed to cool to room temperature, and thus an aqueous polymer solution containing a macromolecule X2 was obtained. The molar ratio between the constitutional units (THMPA/MPC) in the macromolecule X2 was 5/95, and the weight average molecular weight of the macromolecule X2 was 300,000.

[0194] Manufacturing of Macromolecule X3

[0195] In a 500-mL four-neck flask, 90 g of ultrapure water was placed and heated to 65 C. A solution obtained by mixing 5.0 g of 2-methacryloyloxyethyl phosphorylcholine (manufactured by Tokyo Chemical Industry Co., Ltd.), 8.1 g of BLEMMER QA (manufactured by NOF Corporation), and 60 g of ultrapure water together and a solution obtained by mixing 0.092 g of V-50 (manufactured by Wako Pure Chemical Industries, Ltd.) and 30 g of ultrapure water together were separately dropped into the water in the flask over a 2-hour period, and polymerization was carried out. After having been matured for 6 hours, the resulting solution was allowed to cool to room temperature, and thus an aqueous polymer solution containing a macromolecule X3 was obtained. The molar ratio between the constitutional units (THMPA/MPC) in the macromolecule X3 was 50/50, and the weight average molecular weight of the macromolecule X3 was 520,000.

[0196] Manufacturing of Macromolecule X4

[0197] In a 1000-mL four-neck flask, 210 g of ultrapure water was placed and heated to 65 C. A solution obtained by mixing 5.0 g of 2-methacryloyloxyethyl phosphorylcholine (manufactured by Tokyo Chemical Industry Co., Ltd.), 32.2 g of BLEMMER QA (manufactured by NOF Corporation), and 140 g of ultrapure water together and a solution obtained by mixing 0.23 g of V-50 (manufactured by Wako Pure Chemical Industries, Ltd.) and 70 g of ultrapure water together were separately dropped into the water in the flask over a 2-hour period, and polymerization was carried out. After having been matured for 6 hours, the resulting solution was allowed to cool to room temperature, and thus an aqueous polymer solution containing a macromolecule X4 was obtained. The molar ratio between the constitutional units (THMPA/MPC) in the macromolecule X4 was 80/20, and the weight average molecular weight of the macromolecule X4 was 150,000.

[0198] Manufacturing of Macromolecule X5

[0199] In a 500-mL four-neck flask, 64 g of ultrapure water was placed and heated to 65 C. A solution obtained by mixing 5.0 g of N-(2-carboxyethyl)-N-methacryloxyethyl-N,N-dimethylammonium betaine (manufactured by Osaka

[0200] Organic Chemical Industry Ltd.), 2.76 g of BLEMMER QA (manufactured by NOF Corporation), and 43 g of ultrapure water together and a solution obtained by mixing 0.079 g of V-50 (manufactured by Wako Pure Chemical Industries, Ltd.) and 21 g of ultrapure water together were separately dropped into the water in the flask over a 2-hour period, and polymerization was carried out. After having been matured for 6 hours, the resulting solution was allowed to cool to room temperature, and thus an aqueous polymer solution containing a macromolecule X5 was obtained. The molar ratio between the constitutional units (THMPA/CBMA) in the macromolecule X5 was 20/80, and the weight average molecular weight of the macromolecule X5 was 310,000.

[0201] Manufacturing of Macromolecule X6

[0202] In a 500-mL four-neck flask, 61 g of ultrapure water was placed and heated to 65 C. A solution obtained by mixing 5.0 g of [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfopropyl) ammonium hydroxide (manufactured by SIGMA-ALDRICH), 2.12 g of BLEMMER QA (manufactured by NOF Corporation), and 40 g of ultrapure water together and a solution obtained by mixing 0.061 g of V-50 (manufactured by Wako Pure Chemical Industries, Ltd.) and 20 g of ultrapure water together were separately dropped into the water in the flask over a 2-hour period, and polymerization was carried out. After having been matured for 6 hours, the resulting solution was allowed to cool to room temperature, and thus an aqueous polymer solution containing a macromolecule X6 was obtained. The molar ratio between the constitutional units (THMPA/SBMA) in the macromolecule X6 was 20/80, and the weight average molecular weight of the macromolecule X6 was 460,000.

[0203] Manufacturing of Macromolecule X7

[0204] In a 500-mL four-neck flask, 57 g of ultrapure water was placed and heated to 65 C. A solution obtained by mixing 5.0 g of 2-methacryloyloxyethyl phosphorylcholine (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.70 g of 2-aminoethyl methacrylate hydrochloride (manufactured by SIGMA-ALDRICH), and 38 g of ultrapure water together and a solution obtained by mixing 0.057 g of V-50 (manufactured by Wako Pure Chemical Industries, Ltd.) and 19 g of ultrapure water together were separately dropped into the water in the flask over a 2-hour period, and polymerization was carried out. After having been matured for 6 hours, the resulting solution was allowed to cool to room temperature, and thus an aqueous polymer solution containing a macromolecule X7 was obtained. The molar ratio between the constitutional units (MOEA/MPC) in the macromolecule X7 was 20/80, and the weight average molecular weight of the macromolecule X7 was 330,000.

[0205] Manufacturing of Macromolecule X8

[0206] In a 500-mL four-neck flask, 58 g of ultrapure water was placed and heated to 65 C. A solution obtained by mixing 5.0 g of 2-methacryloyloxyethyl phosphorylcholine (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.78 g of 2-(diethylamino)ethyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), and 39 g of ultrapure water together and a solution obtained by mixing 0.057 g of V-50 (manufactured by Wako Pure Chemical Industries, Ltd.) and 19 g of ultrapure water together were separately dropped into the water in the flask over a 2-hour period, and polymerization was carried out. After having been matured for 6 hours, the resulting solution was allowed to cool to room temperature, and thus an aqueous polymer solution containing a macromolecule X8 was obtained. The molar ratio between the constitutional units (MOEDEA/MPC) in the macromolecule X8 was 20/80, and the weight average molecular weight of the macromolecule X8 was 250,000.

[0207] Macromolecule X9

[0208] MPC (2-methacryloyloxyethyl phosphorylcholine) homopolymer (Lipidure-HM; manufactured by NOF Corporation)

[0209] The details of the comparison substances of the macromolecules X used to prepare the polishing agent compositions of Comparative Examples 1 to 16 were as follows.

[0210] Comparison Substance X11

[0211] Carbobetaine monomer (N-(2-carboxyethyl)-N-methacryloxyethyl-N,N-dimethylammonium betaine; manufactured by Osaka Organic Chemical Industry Ltd.)

[0212] Manufacturing of Comparison Substance X12

[0213] In a 500-mL four-neck flask, 50 g of ultrapure water was placed and heated to 65 C. A solution obtained by mixing 5.0 g of N-(2-carboxyethyl)-N-methacryloxyethyl-N,N-dimethylammonium betaine (manufactured by Osaka Organic Chemical Industry Ltd.) and 33 g of ultrapure water together and a solution obtained by mixing 0.063 g of V-50 (manufactured by Wako Pure Chemical Industries, Ltd.) and 17 g of ultrapure water together were separately dropped into the water in the flask over a 2-hour period, and polymerization was carried out. After having been matured for 6 hours, the resulting solution was allowed to cool to room temperature, and thus an aqueous polymer solution containing a comparison substance X12 (CBMA homopolymer) was obtained. The weight average molecular weight of the comparison substance X12 was 360,000.

[0214] Manufacturing of Comparison Substance X13

[0215] In a 500-mL four-neck flask, 50 g of ultrapure water was placed and heated to 65 C. A solution obtained by mixing 5.0 g of [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfopropyl) ammonium hydroxide (manufactured by SIGMA-ALDRICH) and 33 g of ultrapure water together and a solution obtained by mixing 0.049 g of V-50 (manufactured by Wako Pure Chemical Industries, Ltd.) and 17 g of ultrapure water together were separately dropped into the water in the flask over a 2-hour period, and polymerization was carried out. After having been matured for 6 hours, the resulting solution was allowed to cool to room temperature, and thus an aqueous polymer solution containing a comparison substance X13 (SBMA homopolymer) was obtained. The weight average molecular weight of the comparison substance X13 was 440,000.

[0216] Comparison Substance X14

[0217] Betaine (trimethylglycine; manufactured by Wako Pure Chemical Industries, Ltd.)

[0218] Manufacturing of Comparison Substance X15

[0219] In a 500-mL four-neck flask, 50 g of ultrapure water was placed and heated to 65 C. A solution obtained by mixing 10.0 g of BLEMMER QA (manufactured by NOF Corporation) and 33 g of ultrapure water together and a solution obtained by mixing 0.057 g of V-50 (manufactured by Wako Pure Chemical Industries, Ltd.) and 17 g of ultrapure water together were separately dropped into the water in the flask over a 2-hour period, and polymerization was carried out. After having been matured for 6 hours, the resulting solution was allowed to cool to room temperature, and thus an aqueous polymer solution containing a comparison substance X15 (THMPA homopolymer) was obtained. The weight average molecular weight of the comparison substance X15 was 220,000.

[0220] Manufacturing of Comparison Substance X16

[0221] In a 500-mL four-neck flask, 75 g of ultrapure water was placed and heated to 65 C. A solution obtained by mixing 2.0 g of methacrylic acid (MAA; manufactured by Tokyo Chemical Industry Co., Ltd.), 11.0 g of BLEMMER QA (manufactured by NOF Corporation), and 50 g of ultrapure water together and a solution obtained by mixing 0.13 g of V-50 (manufactured by Wako Pure Chemical Industries, Ltd.) and 25 g of ultrapure water together were separately dropped into the water in the flask over a 2-hour period, and polymerization was carried out. After having been matured for 6 hours, the resulting solution was allowed to cool to room temperature, and thus an aqueous polymer solution containing a comparison substance X16 was obtained. The molar ratio between the constitutional units (THMPA/MAA) in the comparison substance X16 was 50/50, and the weight average molecular weight of the comparison substance X16 was 280,000.

[0222] The details of the macromolecules Y used to prepare the polishing agent compositions of Examples 14 to 29 and Comparative Examples 9, 11, and 12 to 16 were as follows.

[0223] Preparation of PAA

[0224] In a separable flask equipped with a reflux tube, a stirring device, a thermometer, and a nitrogen introduction tube, 796.75 g of deionized water was placed and heated to 98 C. A solution obtained by dissolving 875.3 g of acrylic acid (manufactured by Wako Pure Chemical Industries, Ltd., special grade, 98% purity) and 116 g of ammonium persulfate (manufactured by Wako Pure Chemical Industries, Ltd., special grade, 98% purity) serving as an initiator was dropped into the water in the flask over a 2-hour period, and polymerization was carried out while the temperature was kept at 98 C. Then, the resulting solution was matured for 1 hour while the temperature was kept at 98 C., and thus polyacrylic acid with an average molecular weight of 23,000 was obtained. The obtained polyacrylic acid was cooled to 40 C., and 721.2 g of a 28 mass % aqueous solution of ammonia (manufactured by Wako Pure Chemical Industries, Ltd., special grade) was dropped thereinto over a 1-hour period while the temperature was kept at 40 C. Thus, ammonium polyacrylate with a neutralization degree of 100% was prepared. [0225] Polyvinyl phosphonic acid; manufactured by Maruzen Petrochemical, weight average molecular weight of 9,100 [0226] Polyvinyl sulfonic acid (poly(vinyl sulfonic acid, sodium salt) solution; manufactured by Wako Pure Chemical Industries, Ltd., weight average molecular weight of 4,000 to 6,000) [0227] P(AA/AMPS): (molar ratio (AA/AMPS)=80/20, copolymer of acrylic acid/acrylamide-2-methylpropane sulfonic acid; manufactured by TOAGOSEI Co., Ltd., weight average molecular weight of 24,000)

[0228] 2. Measurement Methods for Various Parameters

[0229] Weight Average Molecular Weight of Macromolecules X and Comparison Substances Thereof

[0230] The weight average molecular weights of the macromolecules X and the comparison substances thereof used to prepare the polishing liquid compositions were calculated based on the peaks in chromatograms obtained by performing gel permeation chromatography (GPC) under the conditions listed below.

[0231] Apparatus: HLC-8320 GPC (TOSOH Corporation, detector-integrated type)

[0232] Column: Two columns (TSKge1 a-M; manufactured by TOSOH Corporation) coupled in series

[0233] Eluent: 0.15 mol Na.sub.2SO.sub.4/1% CH.sub.3COOH/water

[0234] Flow rate: 1.0 mL/min

[0235] Column temperature: 40 C.

[0236] Detector: RI detector

[0237] Standard substance: Pullulan

[0238] Weight Average Molecular Weights of Macromolecules Y etc.

[0239] The weight average molecular weights of the macromolecules Y used to prepare the polishing liquid compositions were calculated based on the peaks in chromatograms obtained by performing gel permeation chromatography (GPC) under the conditions listed below.

[0240] Apparatus: HLC-8320 GPC (TOSOH Corporation, detector-integrated type)

[0241] Column: G4000PWXL and G2500PWXL (manufactured by TOSOH Corporation) coupled in series

[0242] Eluent: 0.2 M MPB/CH.sub.3CN=90/10

[0243] Flow rate: 1.0 mL/min

[0244] Column temperature: 40 C.

[0245] Detector: RI, UV detector

[0246] Standard substance: Polyethylene glycol

[0247] pH Values of Polishing Liquid Compositions

[0248] The pH values of the polishing liquid compositions at 25 C. were obtained through measurement using a pH meter (HM-30G; manufactured by TOA Electronics Ltd.) performed 1 minute after an electrode was immersed in the polishing liquid compositions.

[0249] Average Primary Particle Diameter of Cerium Oxide Particles

[0250] The average primary particle diameter (nm) of the cerium oxide particles means a particle diameter (on a spherical shape basis) calculated based on the equation below using a specific surface area S (m.sup.2/g) calculated using a BET (nitrogen adsorption) method, and was calculated based on the equation below.

[0251] The specific surface area S in the equation below was determined as follows. That is, 10 g of a slurry of cerium oxide particles was dried under reduced pressure at 110 C. to remove moisture and then the thus-obtained dry matter was pulverized in an agate mortar. The resulting powder was subjected to measurement using a fluid-type automatic specific surface area measurement apparatus FlowSorb 2300 (manufactured by Shimadzu Corporation).

[0252] Average primary particle diameter (nm)=820/S

[0253] Average Crystallite Diameter of Cerium Oxide Particles

[0254] The average crystallite diameter was determined through powder X-ray diffraction. That is, a slurry of the cerium oxide particles was dried in a dryer at 120 C. and then the thus-obtained dry matter was pulverized on a mortar to produce CeO.sub.2 powder. This powder was subjected to measurement using an X-ray diffraction apparatus (RINT2500 manufactured by Rigaku Corporation; CuK rays; =1.5418 ) in which the measurement angle was set to 10 to 70, and the average crystallite diameter was calculated based on Scherrer's equation (the equation below) using the peak value of the main peak (1,1,1) plane of CeO.sub.2 observed near 28 to 30.

[0255] Average crystallite diameter=C/B/cos

[0256] : Wavelength of CuK rays (1.5418 )

[0257] : Half-value width ()

[0258] : Diffraction angle ()

[0259] C.: Constant=0.9

[0260] Volume Based Average Particle Size (D50) of Cerium Oxide Particles

[0261] The volume based average particle size (D50) of the cerium oxide particles was measured under the following conditions. Ion-exchanged water serving as a dispersion medium was injected into a measurement tank, and the polishing liquid composition was dropped into the dispersion medium while the dispersion medium was stirred and circulated. The polishing liquid composition was gradually added such that the laser beam transmittance of the mixed solution of the polishing liquid composition and the dispersion medium was 80 to 90%. Once the transmittance had reached the above-mentioned value, the particle size distribution was measured without performing ultrasonic dispersion treatment, and the volume based average particle size (D50) was determined.

[0262] Measurement apparatus: Laser diffraction/scattering particle size distribution analyzer LA-920 manufactured by HORIBA, Ltd.

[0263] Stirring speed: 4

[0264] Circulating speed: 4

[0265] Dispersion medium: Ion-exchanged water

[0266] Relative refractive index: 1.65

[0267] 3. Evaluation of Polishing Liquid Compositions (Examples 1 to 29 and Comparative Examples 1 to 16)

[0268] Evaluation Sample

[0269] A silicon oxide film test piece was obtained by cutting a square piece with a size of 40 mm40 mm from a silicon wafer provided with a silicon oxide film with a thickness of 2000 nm on one side thereof using a TEOS-plasma CVD method.

[0270] Polishing Conditions

[0271] Polishing testing machine: One-side polishing machine (TR15M-TRK1 manufactured by Techno Rise Corporation; surface plate diameter: 38 cm) Polishing Pad: Product No. IC-1000/Suba400 (manufactured by Nitta Haas Incorporated.)

[0272] Surface plate rotation number: 100 rpm

[0273] Head rotation number: 110 rpm (the rotation direction was the same as that of the surface plate)

[0274] Polishing load: 300 g-weight/cm.sup.2

[0275] Supply amount of polishing liquid: 50 mL/min (3.125 g/(cm.sup.2.Math.min))

[0276] Polishing time: 1 minute

[0277] Measurement of Silicon Oxide Film Polishing Speed

[0278] The evaluation samples were polished under the above-mentioned polishing conditions using the polishing liquid composition shown in Table 1. After the polishing, the silicon oxide film test pieces were washed using ultrapure water and dried, and were used as measurement targets of measurement using an optical interferometric film thickness measurement apparatus, which will be described later. The polished evaluation samples were subjected to measurement of the thickness of a protruding remaining film using an optical interferometric film thickness measurement apparatus (product name: VM-1230; manufactured by SCREEN Semiconductor Solutions Co., Ltd.).

[0279] Before and after the polishing, the thickness of the silicon oxide film was measured using an optical interferometric film thickness measurement apparatus (product name: VM-1230; manufactured by SCREEN Semiconductor Solutions Co., Ltd.). The silicon oxide film polishing speed was calculated based on the equation below.

Silicon Oxide Film Polishing Speed (nm/minute)=[Thickness (nm) of silicon oxide film before polishingthickness (nm) of silicon oxide film after polishing]/polishing time (minute)

[0280] Measurement of Silicon Nitride Film (Oxidation Stopper Film) Polishing Speed

[0281] Polishing of a silicon nitride film, measurement of the thickness thereof, and calculation of the polishing speed were performed in the same manner as in Measurement of Silicon Oxide Film Polishing Speed above, except that a silicon nitride film test piece was used as a test piece instead of the silicon oxide film test pieces, and the rotation time (polishing time) of the surface plate and a holder was set to 20 seconds. The silicon nitride film polishing speed was shown in Table 3 below.

[0282] Polishing Speed Ratio

[0283] The ratio of the silicon oxide film polishing speed to the silicon nitride film polishing speed was taken as a polishing speed ratio. The polishing speed ratio was calculated based on the equation below and is shown in Table 2 below. The greater the value of the polishing speed ratio is, the higher the polishing selectivity is.

Polishing speed ratio=silicon oxide film polishing speed (nm/minute)/silicon nitride film polishing speed (nm/minute)

TABLE-US-00002 TABLE 2 Polishing liquid composition Evaluation Macromolecule X and comparison substance Silicon Cerium oxide Polymer- oxide particles ization Weight film Content Type of ratio of average Content pH polishing Table (mass constituent constituent molecular (mass (25 speed 2 Type %) Type monomer monomer weight %) C.) (nm/min) Comp. Pulverized 0.3 None 6.5 162 Ex. 1 ceria A Ex. 1 Pulverized 0.3 X1 THMPA/MPC 20/80 500,000 0.001 6.5 201 ceria A Ex. 2 Pulverized 0.3 THMPA/MPC 20/80 500,000 0.01 6.5 572 ceria A Ex. 3 Pulverized 0.3 THMPA/MPC 20/80 500,000 0.1 6.5 253 ceria A Ex. 4 Pulverized 0.3 THMPA/MPC 20/80 500,000 0.5 6.5 187 ceria A Ex. 5 Pulverized 0.3 X2 THMPA/MPC 5/95 300,000 0.01 6.5 524 ceria A Ex. 6 Pulverized 0.3 X3 THMPA/MPC 50/50 520,000 0.01 6.5 411 ceria A Ex. 7 Pulverized 0.3 X4 THMPA/MPC 80/20 150,000 0.01 6.5 243 ceria A Ex. 8 Pulverized 0.3 X5 THMPA/ 20/80 310,000 0.01 6.5 361 ceria A CBMA Ex. 9 Pulverized 0.3 X6 THMPA/ 20/80 460,000 0.01 6.5 250 ceria A SBMA Ex. 10 Pulverized 0.3 X7 MOEA/MPC 20/80 330,000 0.01 6.5 428 ceria A Ex. 11 Pulverized 0.3 X8 MOEDEA/ 20/80 250,000 0.01 6.5 455 ceria A MPC Comp. HC-60 0.3 None 6.5 291 Ex. 2 Ex. 12 HC-60 0.3 X1 THMPA/MPC 20/80 500,000 0.01 6.5 412 Comp. Pulverized 0.3 X11 CBMA 0.05 5.1 165 Ex. 3 ceria A monomer Comp. Pulverized 0.3 X12 CBMA 0/100 360,000 0.05 5.1 163 Ex. 4 ceria A homopolymer Comp. Pulverized 0.3 X13 SBMA 0/100 440,000 0.01 6.5 157 Ex. 5 ceria A homopolymer Comp. Pulverized 0.3 X14 Betaine 0.01 6.5 169 Ex. 6 ceria A Comp. Pulverized 0.3 X15+ Mixture 0.01 6.5 131 Ex. 7 ceria A X12.sup.1) of THMPA homopolymer and CBMA homopolymer Comp. Pulverized 0.3 X16 Copolymer of 280,000 0.01 6.5 164 Ex. 8 ceria A monomer containing anionic group and monomer containing cationic group .sup.1)The mixing ratio (mass ratio) between X15 and X12 was 2:8.

[0284] As shown in Table 2, the silicon oxide film polishing speed was faster in the case where the polishing liquid compositions of Examples 1 to 12 were used than in the case where the polishing liquid compositions of Comparative Examples 1 to 8 were used.

TABLE-US-00003 TABLE 3 Polishing liquid composition Evaluation Silicon Silicon Macromolecule X or comparison substance Macromolecule Y oxide nitride Ceria particles Weight film film Content Type of average Content Content pH polishing polishing Polishing (mass constituent molecular (mass (mass (25 speed speed selective Table 3 Type %) Type monomer Ratio weight %) Type %) C.) (nm/min) (nm/min) ratio Comp. Pulverized 0.3 None None 6.5 162 65 2.5 Ex. 1 ceria A Comp. Pulverized 0.3 None PAA 0.4 6.5 143 9.3 15.2 Ex. 9 ceria A Ex. 13 Pulverized 0.3 X9 MPC 100,000 0.01 None 6.5 189 61.3 3.1 ceria A homo- polymer Ex. 14 Pulverized 0.3 MPC 100,000 0.01 PAA 0.4 6.5 181 9 20.1 ceria A homo polymer- Ex. 2 Pulverized 0.3 X1 THMPA/ 20/80 500.000 0.01 None 6.5 572 144 4.0 ceria A MPC Ex. 15 Pulverized 0.3 THMPA/ 20/80 500.000 0.01 PAA 0.4 6.5 740 11.2 66.1 ceria A MPC Ex. 16 Pulverized 0.3 THMPA/ 20/80 500.000 0.001 PAA 0.4 6.5 194 9.6 20.2 ceria A MPC Ex. 17 Pulverized 0.3 THMPA/ 20/80 500,000 0.1 PAA 0.4 6.5 312 14.3 21.8 ceria A MPC Ex. 18 Pulverized 0.3 X2 THMPA/ 5/95 300.000 0.01 PAA 0.4 6.5 702 12.3 57.0 ceria A MPC Ex. 19 Pulverized 0.3 X3 THMPA/ 50/50 520.000 0.01 PAA 0.4 6.5 534 10.1 52.9 ceria A MPC Ex. 20 Pulverized 0.3 X4 THMPA/ 80/20 150.000 0.01 PAA 0.4 6.5 277 13.1 21.1 ceria A MPC Ex. 21 Pulverized 0.3 X7 MOEA/ 20/80 330,000 0.01 PAA 0.4 6.5 592 10.4 56.9 ceria A MPC Ex. 22 Pulverized 0.3 X8 MOEDEA/ 20/80 250,000 0.01 PAA 0.4 6.5 640 10.9 58.7 ceria A MPC Ex. 23 Pulverized 0.3 X1 THMPA/ 20/80 500,000 0.01 PAA 0.01 6.5 611 22.3 27.4 ceria A MPC Ex. 24 Pulverized 0.3 THMPA/ 20/80 500.000 0.01 PAA 0.1 6.5 629 12.8 49.1 ceria A MPC Ex. 25 Pulverized 0.3 THMPA/ 20/80 500,000 0.01 PAA 0.7 6.5 195 8.2 23.8 ceria A MPC Ex. 26 Pulverized 0.3 THMPA/ 20/80 500,000 0.01 Polyvinyl 0.4 6.5 688 10.3 66.8 ceria A MPC phosphonic acid Ex. 27 Pulverized 0.3 THMPA/ 20/80 500,000 0.01 Polyvinyl 0.4 6.5 266 12.5 21.3 ceria A MPC phosphonic acid Ex. 28 Pulverized 0.3 THMPA/ 20/80 500.000 0.01 P(AA/ 0.4 6.5 735 9.9 74.2 ceria A MPC AMPS) Comp. HC-60 0.3 None None 6.5 291 170 1.7 Ex. 10 Comp. HC-60 0.3 None PAA 0.4 6.5 63 4.8 13.1 Ex. 11 Ex. 12 HC-60 0.3 X1 THMPA/ 20/80 500,000 0.01 None 6.5 412 215 1.9 MPC Ex. 29 HC-60 0.3 THMPA/ 20/80 500,000 0.01 PAA 0.4 6.5 373 6.5 57.4 MPC Comp. Pulverized 0.3 X11 CBMA 0.01 PAA 0.4 5.1 87 8.4 10.4 Ex. 12 ceria A monomer Comp. Pulverized 0.3 X12 CBMA 360,000 0.01 PAA 0.4 5.1 79 9.2 8.6 Ex. 13 ceria A homo- polymer Comp. Pulverized 0.3 X13 SBMA 440.000 0.01 PAA 0.4 6.5 142 10.3 13.8 Ex. 14 ceria A homo- polymer Comp. Pulverized 0.3 X14 Betaine 0.01 PAA 0.4 6.5 138 9.3 14.8 Ex. 15 ceria A Comp. Pulverized 0.3 X16 THMPA/ 50/50 280.000 0.01 PAA 0.4 6.5 131 11.3 11.6 Ex. 16 ceria A MAA

[0285] As shown in Table 3, in the case where the polishing liquid compositions of Examples 13 to 29 containing both the macromolecule X and the macromolecule Y were used, the polishing of the silicon nitride film is inhibited while the silicon oxide film is polished at a high speed, and thus high polishing selectivity can be realized.

INDUSTRIAL APPLICABILITY

[0286] As described above, the polishing liquid composition according to the present disclosure is useful in a method for manufacturing a semiconductor device capable of realizing high density and high integration degree.