Abrasive Slurry Composition

Abstract

The present invention relates to an abrasive slurry composition comprising nanoceria abrasive particles; and a water-soluble compound having an intramolecular hydrophilic group; and optionally further comprising at least one of an amphoteric compound having an intramolecular carboxyl group and an amine group, a surface modifier including an organic acid, and a pH adjuster.

Description

[Technical field]

[0001] The present invention relates to an abrasive slurry composition comprising nano-ceria abrasive particles. [Background technology]

[0002] The Chemical Mechanical Polishing (CMP) process is carried out by applying a slurry containing abrasive particles onto a substrate and using a polishing pad attached to a polishing device. At this time, the abrasive particles mechanically polish the surface under pressure from the polishing device, and the chemical components contained in the polishing slurry composition chemically react with the substrate surface to chemically remove the surface portion of the substrate.

[0003] Generally, there are various types of polishing slurry compositions depending on the type and characteristics of the object to be removed. Among them, there are many different types of polishing slurry compositions that selectively remove a specific film to be polished, but recent semiconductor device structures require a slurry composition that can simultaneously polish silicon oxide film, silicon nitride film, and polysilicon film. However, conventional slurry compositions cannot selectively polish silicon oxide film, silicon nitride film, and polysilicon film, and therefore cannot obtain a desired level of polishing speed, or defects and scratches occur, and there is a problem that aggregation occurs due to low dispersion stability. In addition, when ceria particles have an angular crystal grain shape and a wide range of particle size distribution, the occurrence of micro-scratches in the polysilicon film becomes unavoidable. In addition, there is an increasing need for the application of small-sized particles in order to improve defects and scratches in the polishing film quality and improve dishing and erosion values ​​in the pattern.

[0004] When the size of ceria particles is 40nm or less, the polishing rate of the insulating film is very low, and when the particle size is 100nm or more, the sharp crystal planes of the polyhedron structure cause a rapid increase in the number of micro-scratches. This is because as the particle size decreases, the pressure between the abrasive particles and the polishing film decreases, reducing the polishing rate of the polishing film, and when the particle size becomes smaller than a certain size, the polishing mechanism changes and the number of inactive abrasive particles increases. Theoretically, as the particle size decreases, some particles follow the "Hydrodynamical Contact model". This was proposed in a paper in "IEEE TRANSACTIONS ON SEMICONDUCTOR MANUFACTURING, VOL.14, NO.2, MAY 2001". The polishing mechanism changes depending on the distance between the polishing pad and the particles of the CMP device, and between the particles and the polishing surface, and as the particle size decreases, inactive abrasive particles act as the cause of the decrease in the polishing rate. Summary of the Invention [Problem to be solved by the invention]

[0005] In order to solve the above problems, the present invention provides an abrasive slurry composition that provides a suitable dispersion environment for ceria abrasive particles, suppresses the generation of inactive abrasive particles due to a reduction in particle size, and allows the abrasive particles to uniformly participate in the polishing process, thereby improving the polishing rate of the polishing film.

[0006] However, the problems that the present invention is intended to solve are not limited to those mentioned above, and other problems not mentioned will be clearly understood by a person of ordinary skill in the art from the following description. [Means for solving the problem]

[0007] One embodiment of the present invention relates to a polishing slurry composition comprising nanoceria abrasive particles; and a water-soluble compound containing an intramolecular hydrophilic group; and having a resultant value (S) of the following formula 1 of 0.9 to 1.1.

[0008]

number

[0009] According to an embodiment of the present invention, the b may be a primary particle size of 30 nm or less.

[0010] According to an embodiment of the present invention, the abrasive particles may be present in an amount of 0.0001% to 5% by weight of the slurry composition.

[0011] According to an embodiment of the present invention, the water-soluble compound may be 0.001% by weight to 1% by weight of the polishing slurry composition.

[0012] According to one embodiment of the present invention, the molecular weight of the water-soluble compound may be less than 3000.

[0013] According to one embodiment of the present invention, the water-soluble compound may comprise a polymer, copolymer, or both, including at least one monomer selected from the group consisting of alkylene glycols, oxyalkylene alkyl ethers, oxyalkylene alkenyl ethers, oxyalkylene alkyl aryl ethers, and oxyalkylene alkyl ether carboxylic acids.

[0014] According to one embodiment of the present invention, the water-soluble compound may comprise a polymer, copolymer, or both comprising at least one monomer selected from the group consisting of alkyl acrylates; alkyl (meth)acrylates; (meth)acrylates containing an aliphatic ring or an aromatic ring; and acrylates containing an aliphatic ring or an aromatic ring.

[0015] According to one embodiment of the present invention, the composition further includes an amphoteric compound, which may include an amphoteric amino acid, an organic acid containing an amine group and a carboxyl group, or both.

[0016] According to an embodiment of the present invention, the PI value of the amphoteric compound may be 5.5 to 6.5, and the molecular weight of the amphoteric compound may be 1000 or less.

[0017] According to one embodiment of the present invention, the amphoteric amino acid is selected from the group consisting of lysine, methionine, cysteine, tyrosine, glycine, glutamic acid, alanine, serine, asparagine, phenylalanine, threonine, valine, leucine, isoleucine, proline, histidine, lysine, arginine, aspartic acid, tryptophan, glutamine, cysteine, betaine, cocomidopropyl betaine, lauryl betaine, stearyl betaine, The surfactant may include at least one selected from the group consisting of laurylpropylbetaine, cocodimethylcarboxymethylbetaine, lauryldimethylcarboxymethylbetaine, lauryldimethylalpha-carboxyethylbetaine, cetyldimethylcarboxymethylbetaine, aminocarboxylates, imidazolium betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, lauryldimethylamine oxide, and lecithin.

[0018] According to one embodiment of the present invention, the organic acid containing an amine group and a carboxyl group is selected from the group consisting of sarcosine, aminobutyric acid, 4-aminobutyric acid, diaminobutyric acid, laurylpropyl betaine, ornithine, cocomidopropyl betaine, theanine, aminoadipic acid, iminodiacetic acid, nitrilotriacetic acid, anthranilic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 3-amino-1,2,4-triazole-5-carboxylic acid, 1,2,3,4-tetrahydroisoquinoline-3-carboxylic acid, and the like. acid, pipecolic acid, nipecotic acid, isonipecotic acid, 4-amino-3-hydroxybutyric acid, 6-aminohexanoic acid, Aminocaproic acid, 2-amino-2-thiazoline-4-carboxylic acid, 3-amino-3-methylbenzoic acid, 3-aminomethylbutanoic acid, 5-aminopentanoic acid, 2-aminothiopheneacetic acid, aminonaphthoic acid, 3-aminopyrazo 4-carboxylic acid 2-amino-4-pentenoic acid, 3-aminobutyric acid , aminolevulinic acid, and 8-aminocaprylic acid.

[0019] According to an embodiment of the present invention, the amphoteric compound may be present in an amount of 0.001% to 1% by weight of the polishing slurry composition.

[0020] According to an embodiment of the present invention, the coating composition may further include a surface modifier including an organic acid, and the organic acid may include a monocarboxylic acid.

[0021] According to one embodiment of the present invention, the monocarboxylic acid may be formic acid, acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, heptanoic acid, caprylic acid, nonanoic acid, decanoic acid, undecylenic acid, lauric acid, tridecylic acid, myristic acid, pentadecanoic acid, palmitic acid, phenylacetic acid, 2-phenylpropionic acid, triphenylacetic acid, mandelic acid, hydrocinnamic acid, or the like. The acetic acid may include at least one selected from the group consisting of o-, p-, and m-tolylacetic acid, 4-hydroxyphenyl acetic acid, benzoic acid, toluic acid, dimethylbenzoic acid, dichlorophenylacetic acid, naphthoic acid (1-naphthoic acid, 2-naphthoic acid, and the like), and salicylic acid. According to an embodiment of the present invention, the organic acid may be present in an amount of 0.001% by weight to 0.1% by weight of the polishing slurry composition.

[0022] According to an embodiment of the present invention, the pH adjusting agent may further include an acidic substance, a basic substance, or both, and the acidic substance may include at least one selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, perchloric acid, bromic acid, perchloric acid, hydrofluoric acid, iodic acid, nitrous acid, persulfuric acid, sulfurous acid, hyposulfurous acid, boronic acid, iodic acid, phosphoric acid, phosphorous acid, hypophosphorous acid, superphosphoric acid, chlorous acid, hypochlorous acid, perchloric acid, bromous acid, hypobromous acid, perbromic acid, hypoiodous acid, periodic acid, hydrogen fluoride, boron trifluoride, tetrafluoroboric acid, hydrophosphoric acid, and salts thereof. The basic substance may include ammonium methyl propanol (AMP), tetramethylammonium hydroxide (tetramethylammonium hydroxide ... The compound may include at least one selected from the group consisting of trimethylammonium hydroxide (TMAH), ammonium hydroxide, ammonia, potassium hydroxide, sodium hydroxide, magnesium hydroxide, rubidium hydroxide, cesium hydroxide, sodium bicarbonate, sodium carbonate, imidazole, and salts of each. Effect of the Invention

[0023] The present invention provides an abrasive slurry composition that can prevent the increase of inactive abrasive particles due to the change in the polishing mechanism when the size of the abrasive particles is reduced, and can increase the participation rate of the abrasive particles in the polishing composition in the polishing process. That is, when the size of the particles is reduced, polishing is performed by the polishing mechanism according to the "Hydrodynamic Contact Model", and at this time, the amount of inactive particles increases, and the polishing rate decreases, for example, at particle sizes of 30 nm or less. However, the abrasive slurry composition of the present invention provides an appropriate dispersion environment for the abrasive particles in the abrasive slurry composition, and can improve the participation rate of the abrasive particles in the polishing process even when the size of the abrasive particles is reduced, thereby improving the polishing rate of the polishing film quality. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0024] Hereinafter, the embodiments of the present invention will be described in detail. In the description of the present invention, if it is determined that a detailed description of related known functions or configurations may unnecessarily obscure the gist of the present invention, the detailed description will be omitted. In addition, the terms used in this specification are terms used to appropriately express preferred embodiments of the present invention, and may vary depending on the intentions of users and operators, or the practices of the field to which the present invention belongs. Therefore, the definitions of these terms must be based on the overall content of this specification.

[0025] Throughout this specification, when an element is referred to as being "on" another element, this includes not only when the element is in contact with the other element, but also when there is an additional element between the two elements.

[0026] Throughout the specification, when a part "comprises" a certain element, this does not mean to the exclusion of other elements, but may further include other elements.

[0027] Hereinafter, the present invention will be described in detail with reference to examples of the polishing slurry composition, but the present invention is not limited to such examples.

[0028] The present invention relates to an abrasive slurry composition, and according to one embodiment of the present invention, the abrasive slurry composition comprises ceria abrasive particles; and a water-soluble compound; and may optionally further comprise at least one of an amphoteric compound, a surface modifier, and a pH adjuster.

[0029] According to one embodiment of the present invention, the present invention provides an abrasive slurry composition in which all abrasive particles are active in the polishing process, thereby improving the polishing rate and improving dishing, erosion, scratches, etc. The polishing rate is proportional to the contact area between the abrasive particles and the polishing surface, and it can be confirmed by referring to the literature "Journal of the Electrochemical Society, 147(9)3523-3528(2000)" that the polishing rate increases as the specific surface area of ​​the particles increases. However, if the size of the abrasive particles is reduced, the contact area with the polishing surface decreases or the number of abrasive particles that inactively participate in the polishing process increases, which may result in a lower polishing rate. In the polishing slurry composition according to the present invention, when the primary particle size of the nanoceria abrasive particles and the polishing rate are substituted into the following formula 1, the result value (S) of formula 1 is 0.9 to 1.1, and preferably a value close to 1 can be obtained. In other words, the polishing slurry composition according to the present invention provides an appropriate dispersion environment for nanoceria abrasive particles, which prevents an increase in inactive abrasive particles that occurs when the size of the abrasive particles is reduced, and provides an environment in which (almost) all of the nanoceria abrasive particles contained in the polishing slurry composition can uniformly participate in the polishing process. For example, even when nanoceria abrasive particles having a primary particle size of 30 nm or less are used, the polishing rate can be improved.

[0030]

number

[0031] In the formula 1, a is the primary particle size of the standard abrasive particles, b is the primary particle size of the abrasive particles according to the present invention, A is the polishing rate of the target film when the polishing slurry composition contains the ceria abrasive particles of size a, and B is the polishing rate of the target film when the polishing slurry composition contains the ceria abrasive particles of size b. For example, a may be an abrasive particle having a primary particle size of 30 nm (or more) to 40 nm, and b may be an abrasive particle having a primary particle size of 30 nm or less, 20 nm or less, or 10 nm or less. a and b correspond to different primary particle sizes.

[0032] According to one embodiment of the present invention, the ceria abrasive particles may be produced by any method known in the technical field of the present invention, including, but not limited to, hydrothermal synthesis, sol-gel, co-immersion, spray drying, thermal evaporation, etc., using a trivalent cerium precursor. The ceria abrasive particles may have an (average) primary particle size of 30 nm or less, 20 nm or less, or 10 nm or less. When the particle size falls within the above range, the ceria abrasive particles have excellent dispersion stability in the polishing composition, and performance degradation during long-term polishing processes can be prevented.

[0033] In one embodiment of the present invention, the specific surface area of ​​the ceria abrasive particles having the primary particle size is 31 m 2 / g or more; 40m 2 / g or more; 31m 2 / g~200m 2 / g; or 40m 2 / g~150m 2 / g, and when the specific surface area is within the above range, the area of ​​contact with the film to be polished is sufficiently secured, providing a high level of polishing speed and reducing the occurrence of scratches and dishing on the surface of the film to be polished. The specific surface area can be measured by the BET (Brunauer-Emmett-Teller; BET) method. For example, it can be measured by the BET 6-point method using a porosimetry analyzer (Belsorp-II mini, Bell Japan Inc.) and a nitrogen gas adsorption and flow method.

[0034] In one embodiment of the present invention, the ceria abrasive particles may be included in the polishing slurry composition in an amount of 0.01 to 5 wt%, 0.05 to 2 wt%, or 0.05 to 1 wt%. If the content of the abrasive particles is less than 0.01 wt%, it is difficult to ensure a high level of polishing rate, and if it exceeds 5 wt%, the dispersion stability of the abrasive particles is reduced, the occurrence of defects increases, and it is difficult to obtain the effect of reducing the occurrence of dishing.

[0035] According to one embodiment of the present invention, the water-soluble compound may be a water-soluble compound containing a hydrophilic group in the molecule. That is, by controlling the concentration and molecular weight of the water-soluble compound having the hydrophilic group and the amphoteric compound having the following amine group, an environment in which (almost) all of the ceria abrasive particles can uniformly participate in the polishing process is provided, and the slurry composition is designed so that the calculated value of the above formula 1 is close to 1, and the polishing rate can be improved by increasing the participation rate in the polishing process without a sudden change in the contact area with the film to be polished during the polishing process of the nanoceria particles.

[0036] In one embodiment of the present invention, the water-soluble compound includes at least one of a monomolecule, a monomer, a polymer, and a copolymer having a hydrophilic group, for example, the hydrophilic group is a hydroxyl group, a carboxyl group, an ether group, an ester group, an amino group, etc. The water-soluble compound includes an alkylene glycol-based compound, an acrylate-based compound, or both, and the alkylene glycol-based compound and the acrylate-based compound respectively refer to intramolecular moieties, a monomolecule, a monomer, a polymer, and a copolymer.

[0037] In one embodiment of the present invention, the alkylene glycol-based compound includes at least one of a monomer, a polymer, a copolymer, and a salt thereof, which includes at least one selected from alkylene glycol, oxyalkylene alkyl ether, oxyalkylene alkenyl ether, oxyalkylene alkylaryl ether, and oxyalkylene alkyl ether carboxylic acid. For example, polyalkylene glycol, polyoxyalkylene alkyl ether, polyoxyalkylene alkyl ether, polyoxyalkylene alkyl ether carboxylic acid, and the like. ether), polyoxyalkylene alkenyl ether, polyoxyalkylene alkylaryl ether, and polyoxyalkylene alkyl ether carboxylic acid (alkyl and alkylene are selected from those having 1 to 20 carbon atoms; 1 to 10 carbon atoms; or 2 to 5 carbon atoms, alkenyl is selected from those having 2 to 20 carbon atoms, and aryl is selected from those having 5 to 30 carbon atoms. More specifically, the water-soluble compound is polyethylene glycol, polypropylene glycol, poly(isopropylene glycol), polybutylene glycol polyoxyethylene methyl ether, polyethylene glycol sulfonic acid, polyvinyl alcohol, polyethylene oxide-propylene oxide copolymer, poly(ethylene glycol)-end-capped poly(propylene glycol) (PEG-PPG-PEG block copolymer), etc.

[0038] As one example of the present invention, the acrylate-based compound includes at least one or more of a monomer, polymer, copolymer, and salt thereof, which includes at least one or more selected from the group consisting of alkyl acrylate, alkyl (meth)acrylate, and (meth)acrylate containing an aliphatic ring or an aromatic ring; and acrylate containing an aliphatic ring or an aromatic ring; wherein the alkyl is selected from those having 1 to 30 carbon atoms, the aliphatic ring is selected from those having 4 to 30 carbon atoms, and the aromatic ring is selected from those having 6 to 30 carbon atoms. More specifically, the acrylate may be acrylate, methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, isobutyl acrylate, pentyl acrylate, isopentyl acrylate, hexyl acrylate, isohexyl acrylate, heptyl acrylate, octyl acrylate, isooctyl acrylate, nonyl acrylate, lauryl acrylate, carboxyethyl acrylate, carboxyethyl acrylate oligomer, carboxyethyl acrylate ... oligomers), (methacryloyloxy)ethyl maleate, (methacryloyloxy)ethyl succinate, and at least one of ammonium acrylate, cyclopentyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, cyclohexyl acrylate, and 2-phenoxyethyl acrylate. and copolymers of maleic acid / acrylate, copolymer of fumaric acid / acrylate, copolymer of itaconic acid / acrylate, copolymer of citraconic acid / acrylate, copolymer of acrylic acid / acrylate, copolymer of methacrylic acid / acrylate, copolymer of crotonic acid / acrylate, copolymer of vinylacetic ... polyacrylic acid / acrylate), polyacrylamide / acrylic acid copolymer, polyacrylic acid / sulfonic acid copolymer, polysulfonic acid / acrylamide copolymer, polyacrylamidomethylpropanesulfonic acid, polyacrylic acid / styrene copolymer, polyacrylic acid-malonic acid copolymer, carboxymethylsulfoethylcellulose polyacrylic acid, polyacrylmaleic acid, polymethacrylic acid, and polymethacrylic acid ammonium salt.

[0039] As one example of the present invention, the water-soluble compound is 0.001 wt % to 1 wt %; 0.01 wt % to 1 wt %; or 0.1 wt % to 1 wt % of the polishing slurry composition, and when it is within the above range, the participation rate of the abrasive particles in the polishing process can be increased, and the polishing rate can be improved.

[0040] In one embodiment of the present invention, the molecular weight of the water-soluble compound is less than 3000, for example, within the above molecular weight range, and thus it is possible to prevent a decrease in the polishing rate due to a cushioning effect between the abrasive particles and the film to be polished caused by an increase in molecular weight, thereby ensuring a good polishing rate and reducing defects such as dishing and scratches.

[0041] According to one embodiment of the present invention, the amphoteric compound is for improving the dispersion stability and polishing rate of the polishing slurry composition, and the amphoteric compound means a compound that acts as a base with respect to an acidic substance and acts as an acid with respect to a basic substance. The amphoteric compound in the present invention is a compound containing an amine group and a carboxyl group, and may include an amino acid having an amphoteric charge; and an organic acid containing an amine group and a carboxyl group; or both of them.

[0042] As an example of the present invention, amino acids have both a carboxyl group (-COOH) that shows acidity and an amino group (-NH2) that shows basicity in one molecule. When dissolved in water, they act as an acid or a base depending on the pH, so they are called amphoteric compounds. Depending on the pH of the solution, hydrogen ions (H + ) is accepted as a (base) cation (-NH2+H + >>>-NH3 + ) and hydrogen ions (H + ) released (acid) anion (-COOH>>>-COO - +H +) together, forming a zwitterion. For example, the surfactant may include at least one selected from the group consisting of lysine, methionine, cysteine, tyrosine, glycine, glutamic acid, alanine, serine, asparagine, phenylalanine, threonine, valine, leucine, isoleucine, proline, histidine, lysine, arginine, aspartic acid, tryptophan, glutamine, cysteine, betaine, cocomidopropyl betaine, lauryl betaine, stearyl betaine, lauryl propyl betaine, cocodimethyl carboxymethyl betaine, lauryl dimethyl carboxymethyl betaine, lauryl dimethyl alpha-carboxyethyl betaine, cetyl dimethyl carboxymethyl betaine, amino carboxylate, imidazolium betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethyl imidazolinium betaine, lauryl dimethyl amine oxide, and lecithin.

[0043] In one embodiment of the present invention, the amine group- and carboxyl group-containing organic acid may be sarcosine, aminobutyric acid, 4-aminobutyric acid, diaminobutyric acid, laurylpropyl betaine, ornithine, cocomidopropyl betaine, theanine, aminoadipic acid, iminodiacetic acid, nitrilotriacetic acid, anthranilic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 3-amino-1,2,4-triazole-5-carboxylic acid, 1,2,3,4-tetrahydroisoquinoline-3-carboxylic acid, pipecolic acid, acid, nipecotic acid, isonipecotic acid, 4-amino-3-hydroxybutyric acid, 6-aminohexanoic acid, Aminocaproic acid, 2-amino-2-thiazoline-4-carboxylic acid, 3-amino-3-methylbenzoic acid, 3-aminomethylbutanoic acid, 5-aminopentanoic acid, 2-aminothiopheneacetic acid, aminonaphthoic acid, 3-aminopyrazo 4-carboxylic acid, 2-amino-4-pentenoic acid 3-aminobutyric acid, amine It contains at least one selected from the group consisting of aminolevulinic acid, and 8-aminocaprylic acid.

[0044] In one embodiment of the present invention, the amphoteric compound may have a PI value of 5.5 to 6.5 and a molecular weight of not more than 1000. When the PI value is within the above range, the participation rate of the abrasive particles in the polishing process is increased, which is advantageous in improving the polishing rate of the film to be polished and reducing defects such as dishing and erosion.

[0045] In one embodiment of the present invention, the amphoteric compound may be 0.001% by weight to 1% by weight, or 0.01% by weight to 0.5% by weight of the polishing slurry composition. When the amphoteric compound is contained within the above range, the contact area of ​​the nano-abrasive particles with the target film to be polished is prevented from decreasing, thereby improving the polishing rate of the target film to be polished.

[0046] According to an embodiment of the present invention, the surface modifier may include an organic acid, the organic acid including a monocarboxylic acid having one carboxyl group, the monocarboxylic acid including at least one of an aliphatic monocarboxylic acid and an aromatic monocarboxylic acid, the aliphatic monocarboxylic acid including at least one selected from the group consisting of formic acid, acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, heptanoic acid, caprylic acid, nonanoic acid, decanoic acid, undecylenic acid, lauric acid, tridecylic acid, myristic acid, pentadecanoic acid, and palmitic acid. The aromatic monocarboxylic acid includes at least one selected from the group consisting of phenylacetic acid, 2-phenylpropionic acid, triphenylacetic acid, mandelic acid, hydrocinnamic acid, o-, p-, and m-tolylacetic acid, 4-hydroxyphenylacetic acid, benzoic acid, toluic acid, dimethylbenzoic acid, dichlorophenylacetic acid, naphthoic acid (e.g., 1-naphthoic acid, 2-naphthoic acid, and the like), and salicylic acid.

[0047] In one example of the present invention, the organic acid is 0.001 wt % to 0.1 wt % of the polishing slurry composition; or 0.005 wt % to 0.1 wt %, and when included within the above range, aggregation of particles is prevented, which is advantageous in maintaining a constant specific surface area of ​​the particles and thereby ensuring a constant polishing rate of film quality.

[0048] According to one embodiment of the present invention, the pH adjuster includes an acidic substance, a basic substance, or both, and the acidic substance includes at least one selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, perchloric acid, bromic acid, perchloric acid, hydrofluoric acid, iodic acid, nitrous acid, persulfuric acid, sulfurous acid, hyposulfurous acid, boronic acid, iodic acid, phosphoric acid, phosphorous acid, hypophosphorous acid, superphosphoric acid, chlorous acid, hypochlorous acid, perchloric acid, bromous acid, hypobromous acid, perbromic acid, hypoiodous acid, periodic acid, hydrogen fluoride, boron trifluoride, tetrafluoroboric acid, hydrophosphoric acid, and salts thereof. The basic substance includes at least one selected from the group consisting of ammonium methyl propanol (AMP), tetramethylammonium hydroxide (tetramethylammonium hydroxide ... hydroxide;TMAH), ammonium hydroxide, ammonia (anhydrous or aqueous solution), potassium hydroxide, sodium hydroxide, magnesium hydroxide, rubidium hydroxide, cesium hydroxide, sodium bicarbonate, sodium carbonate, imidazole, and at least one selected from the group consisting of salts of each. For example, the pH adjuster may be used in an amount appropriate for adjusting the pH of the polishing slurry composition to a range of 2 to 11, preferably 5 to 7.

[0049] According to an embodiment of the present invention, the polishing slurry composition may be used in a CMP polishing process of a semiconductor wafer including at least one of a silicon nitride film, a silicon oxide film, a polysilicon film, and a silicon film. The polishing slurry composition may be used in a process of removing a silicon oxide film at a high polishing rate, or a process of removing a silicon oxide film at a high polishing rate and stopping polishing at a polysilicon film. The polishing rate of the silicon oxide film in the polishing process is 2,000 Å / min to 6,000 Å / min.

[0050] The present invention will now be described in more detail with reference to the following examples. However, the following examples are merely for illustrative purposes and are not intended to limit the scope of the present invention.

[0051] Reference Example 1 According to Table 1, ceria particles (primary particle size, 32 nm, 0.1 wt%), polyethylene glycol (molecular weight: 600, 0.5 wt%), L-alanine (PI Value 6.11, 0.1 wt%), formic acid (0.02 wt%), and a pH adjuster (ammonia) were mixed to prepare a polishing slurry composition with a pH of 6.

[0052] Example 1 According to Table 1, ceria particles (primary particle size, 18 nm, 0.1 wt%), polyethylene glycol (molecular weight: 600, 0.5 wt%), L-alanine (PI Value 6.11, 0.1 wt%), formic acid (0.02 wt%), and a pH adjuster (ammonia) were mixed to prepare a polishing slurry composition with a pH of 6.

[0053] Example 2 According to Table 1, ceria particles (primary particle size, 7 nm, 0.1 wt%), polyethylene glycol (molecular weight: 600, 0.5 wt%), L-alanine (PI Value 6.11, 0.1 wt%), formic acid (0.02 wt%), and a pH adjuster (ammonia) were mixed to prepare a polishing slurry composition with a pH of 6.

[0054] Example 3 According to Table 1, ceria particles (primary particle size, 4 nm, 0.1 wt%), polyethylene glycol (molecular weight: 600, 0.5 wt%), L-alanine (PI Value 6.11, 0.1 wt%), formic acid (0.02 wt%), and a pH adjuster (ammonia) were mixed to prepare a polishing slurry composition with a pH of 6.

[0055] Example 4 According to Table 1, ceria particles (primary particle size: 7 nm, 0.1 wt%), polyoxyethylene polyglyceryl ethers (molecular weight: 1000, 0.5 wt%), L-vanillin (PI Value 5.97, 0.1 wt%), acetic acid (0.02 wt%), and a pH adjuster (ammonia) were mixed to prepare a polishing slurry composition with a pH of 6.

[0056] Example 5 According to Table 1, ceria particles (primary particle size: 7 nm, 0.1 wt%), polyoxyethylene polyglyceryl ethers (molecular weight: 1000, 0.5 wt%), L-(-)-proline (PI Value 6.30, 0.1 wt%), acetic acid (0.02 wt%), and pH adjuster ammonia were mixed to prepare a polishing slurry composition with pH=6.

[0057] Example 6 According to Table 1, ceria particles (primary particle size: 7 nm, 0.1 wt%), polyoxyethylene polyglyceryl ethers (molecular weight: 1000, 0.5 wt%), L-(-)-proline (PI Value 6.30, 0.1 wt%), butyric acid (0.02 wt%), and pH adjuster ammonia were mixed to prepare a polishing slurry composition with pH=6.

[0058] Comparative Example 1 According to Table 1, ceria particles (primary particle size, 52 nm, 0.1 wt%), polyethylene glycol (molecular weight: 600, 0.5 wt%), L-alanine (PI Value 6.11, 0.1 wt%), formic acid (0.02 wt%), and a pH adjuster (ammonia) were mixed to prepare a polishing slurry composition with a pH of 6.

[0059] Comparative Example 2 According to Table 1, wet ceria particles (primary particle size, 61 nm, 0.1 wt%), polyethylene glycol (molecular weight: 600, 0.5 wt%), L-alanine (PI Value 6.11, 0.1 wt%), formic acid (0.02 wt%), and a pH adjuster (ammonia) were mixed to prepare a polishing slurry composition with a pH of 6.

[0060] Comparative Example 3 According to Table 1, ceria particles (primary particle size, 7 nm, 0.1 wt%), polyethylene glycol (molecular weight: 600, 0.5 wt%), formic acid (0.02 wt%), and a pH adjuster (ammonia) were mixed to prepare a polishing slurry composition with a pH of 6.

[0061] Comparative Example 4 According to Table 1, ceria particles (primary particle size, 7 nm, 0.1 wt%), polyethylene glycol (molecular weight: 600, 0.5 wt%), L-vanillin (PI Value 5.97, 0.1 wt%), and a pH adjuster (ammonia) were mixed to prepare a polishing slurry composition with a pH of 6.

[0062] Comparative Example 5 According to Table 1, ceria particles (primary particle size: 7 nm, 0.1 wt%), polyoxyethylene polyglyceryl ethers (molecular weight: 1000, 0.5 wt%), butyric acid (0.02 wt%), and a pH adjuster (ammonia) were mixed to prepare a polishing slurry composition with a pH of 6.

[0063] Comparative Example 6 According to Table 1, wet ceria particles (primary particle size, 7 nm, 0.1 wt%), polyethylene glycol (molecular weight: 4000, 0.5 wt%), L-alanine (PI Value 6.11, 0.1 wt%), formic acid (0.02 wt%), and a pH adjuster (ammonia) were mixed to prepare a polishing slurry composition with a pH of 6.

[0064] Polishing characteristics evaluation Using the polishing slurry compositions of the Reference Example, Examples, and Comparative Examples, PETEOS-containing substrates were polished under the polishing conditions described below. [Polishing conditions] (1) Polishing equipment: ST#01 (KCT) (2) Carrier rpm: 60 / 63 (3) Wafer Pressure: 2 psi (4) Flow rate (ml / min): 200 (5) Pad: IC 1000 (6) Time: 60 seconds (7) R-ring pressure: 4.5 psi

[0065] In order to evaluate the polishing characteristics, the polishing rate after polishing a PETEOS wafer substrate was measured using the polishing slurry compositions of the Examples and Comparative Examples, and the results are shown in Table 1. The specific surface area of ​​the polishing particles of the Examples and Comparative Examples was measured by the BET (Brunauer-Emmett-Teller; BET) method and is shown in Table 2.

[0066] [Table 1] A-1: PEG 600 (weight average molecular weight 600) A-2:POE(20)polyglyceryl ether (weight average molecular weight 1,000) A-3: PEG 4000 (weight average molecular weight 4,000) B-1: L-Alanine (PI Value 6.11) B-2: L-Valine (PI Value 5.97) B-3:L-(-)-Proline(PI Value 6.30) C-1:Formic acid C-2: Acetic acid C-3: Butyric acid *Primary grain size was confirmed by TEM.

[0067] The grain size and polishing rate in Table 1 were substituted into the Real Contact / Theoretical Contact formula below for calculation. TIFF0007612048000004.tif2549 a: Primary particle size of ceria nanoparticles of Reference Example 1 A: PETEOS polishing rate of ceria nanoparticles with a primary particle size of a b: Primary particle size of ceria nanoparticles (particle size for which percentage calculation is desired) B: PETEOS polishing rate of ceria nanoparticles with primary particle size of b

[0068] [Table 2]

[0069] As shown in Table 1, when nano-sized ceria particles, for example, 30 nm or less, are used, the polishing slurry composition according to the present invention can improve the dispersibility of the particles and reduce the proportion of inactive abrasive particles in the polishing process, thereby preventing a decrease in the contact area with the film to be polished. That is, even when various ranges of nano-sized particles are used in the polishing slurry compositions of Examples 1 to 6 shown in Table 1, when comparing the contact area according to the polishing rate by substituting Reference Example 1 as a reference according to Formula 1, the values ​​are close to 1. That is, the polishing slurry composition according to the present invention can reduce the generation of inactive particles in the polishing process of nano-sized ceria particles and can improve the polishing rate by allowing all particles to participate in the polishing process uniformly.

[0070] Although the embodiments have been described above by way of limited examples, those skilled in the art may make various modifications and variations from the above description. For example, the described techniques may be performed in a different order than described, and / or the described components may be combined or combined in a different manner than described, and may be replaced or substituted by other components or equivalents, while still achieving the appropriate results. Therefore, other implementations, other embodiments, and equivalents to the claims are also within the scope of the following claims.

Claims

1. Nanoceria abrasive particles; and a water-soluble compound containing an intramolecular hydrophilic group; Including, A polishing slurry composition having a result value (S) of the following formula 1 of 0.9 to 1.1: [0010] (In formula 1, a: The primary particle size of the standard ceria abrasive particles is 30 nm to 40 nm. b: The nanoceria abrasive particles have a primary particle size of 30 nm or less. A: The polishing rate of a silicon oxide film of a polishing slurry composition containing a-size ceria abrasive particles B: The polishing rate of a silicon oxide film of a polishing slurry composition containing ceria abrasive particles of size b The polishing rate is measured under the following polishing conditions. [Polishing conditions] Carrier rpm: 60 / 63 Wafer Pressure: 2psi Flow rate (ml / min): 200)

2. 2. The abrasive slurry composition of claim 1, wherein the abrasive particles comprise from 0.0001% to 5% by weight of the slurry composition.

3. 2. The polishing slurry composition of claim 1, wherein the water soluble compound is 0.001% to 1% by weight of the polishing slurry composition.

4. The abrasive slurry composition of claim 1 , wherein the water-soluble compound has a molecular weight of less than 3,000.

5. 2. The polishing slurry composition of claim 1, wherein the water-soluble compound comprises a polymer, copolymer, or both containing at least one monomer selected from the group consisting of alkylene glycol, oxyalkylene alkyl ether, oxyalkylene alkenyl ether, oxyalkylene alkyl aryl ether, and oxyalkylene alkyl ether carboxylic acid.

6. 2. The polishing slurry composition of claim 1, wherein the water-soluble compound comprises a polymer, copolymer, or both containing at least one monomer selected from the group consisting of alkyl acrylates; alkyl (meth)acrylates; (meth)acrylates containing an aliphatic or aromatic ring; and acrylates containing an aliphatic or aromatic ring.

7. further comprising an amphoteric compound, The polishing slurry composition of claim 1 , wherein the amphoteric compound comprises an amphoteric amino acid, an organic acid containing an amine group and a carboxyl group, or both.

8. The PI value of the amphoteric compound is 5.5 to 6.5; 8. The polishing slurry composition according to claim 7, wherein the amphoteric compound has a molecular weight of 1,000 or less.

9. The amphoteric amino acids include lysine, methionine, cysteine, tyrosine, glycine, glutamic acid, alanine, serine, asparagine, phenylalanine, threonine, valine, leucine, isoleucine, proline, histidine, lysine, arginine, aspartic acid, tryptophan, glutamine, cysteine, betaine, cocomidopropyl betaine, lauryl betaine, stearyl betaine, lauryl propyl betaine, and the like.

8. The polishing slurry composition according to claim 7, comprising at least one selected from the group consisting of laurylpropylbetaine, cocodimethylcarboxymethylbetaine, lauryldimethylcarboxymethylbetaine, lauryldimethylalpha-carboxyethylbetaine, cetyldimethylcarboxymethylbetaine, aminocarboxylates, imidazolium betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, lauryldimethylamine oxide and lecithin.

10. The amine group- and carboxyl group-containing organic acids include sarcosine, aminobutyric acid, 4-aminobutyric acid, diaminobutyric acid, laurylpropyl betaine, ornithine, cocomidopropyl betaine, theanine, aminoadipic acid, iminodiacetic acid, nitrilotriacetic acid, anthranilic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, and the like. acid), 3-amino-1,2,4-triazole-5-carboxylic acid (3-amino-1,2,4-triazole-5-carboxylic acid), 1,2,3,4-tetrahydroisoquinoline-3-carboxylic acid (1,2,3,4-tetrahydroisoquinolin-3-carboxylic acid, pipecolic acid, nipecotic acid, isonipecotic acid, 4-amino-3-hydroxybutyric acid, 6-aminohexanoic acid, 2-amino-2-thiazoline-4-carboxylic acid, 3-amino-3-methylbenzoic acid Benzoic acid, 3-aminomethylbutanoic acid, 5-aminopentanoic acid, 2-aminothiopheneacetic acid, aminonaphthoic acid, 3-aminopyrazo 4-carboxylic acid, 2-amino-4-pentenoic acid, 3-aminobutyric acid, aminolevulinic acid 8. The polishing slurry composition according to claim 7, comprising at least one selected from the group consisting of 8-aminocaprylic acid and 8-aminocaprylic acid.

11. 8. The polishing slurry composition of claim 7, wherein the amphoteric compound is 0.001% to 1% by weight of the polishing slurry composition.

12. Further comprising a surface modifier comprising an organic acid; The abrasive slurry composition of claim 1 , wherein the organic acid comprises a monocarboxylic acid.

13. The monocarboxylic acids include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, heptanoic acid, caprylic acid, nonanoic acid, decanoic acid, undecylic acid, lauric acid, tridecylic acid, myristic acid, and pentadecanoic acid. acid), palmitic acid, phenylacetic acid, 2-phenylpropionic acid, triphenylacetic acid, mandelic acid, hydrocinnamic acid, tolylacetic acid (o-, p-, m-tolylacetic acid), 4-hydroxyphenylacetic acid, benzoic acid, toluic acid, dimethylbenzoic acid 13. The polishing slurry composition according to claim 12, comprising at least one selected from the group consisting of dichlorophenylacetic acid, naphthoic acid (1-naphthoic acid, 2-naphthoic acid, etc.), and salicylic acid.

14. 13. The polishing slurry composition of claim 12, wherein the organic acid is 0.001% to 0.1% by weight of the polishing slurry composition.

15. Further comprising a pH adjuster, The pH adjuster comprises an acidic substance, a basic substance, or both; The acidic substance includes at least one selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, perchloric acid, bromic acid, perchloric acid, hydrofluoric acid, iodic acid, nitrous acid, persulfuric acid, sulfurous acid, hyposulfurous acid, boronic acid, iodic acid, phosphoric acid, phosphorous acid, hypophosphorous acid, superphosphoric acid, chlorous acid, hypochlorous acid, perchloric acid, bromous acid, hypobromous acid, perbromic acid, hypoiodous acid, periodic acid, hydrogen fluoride, boron trifluoride, tetrafluoroboric acid, hydrophosphoric acid, and salts thereof; The polishing slurry composition according to claim 1, wherein the basic substance comprises at least one selected from the group consisting of ammonium methyl propanol (AMP), tetramethyl ammonium hydroxide (TMAH), ammonium hydroxide, ammonia, potassium hydroxide, sodium hydroxide, magnesium hydroxide, rubidium hydroxide, cesium hydroxide, sodium bicarbonate, sodium carbonate, imidazole, and salts thereof.

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