KR102638342B1 - Polishing slurry composition - Google Patents

Abstract

The present invention relates to a polishing slurry composition, and more specifically, to a polishing slurry composition comprising colloidal silica abrasive particles; quaternary ammonium cationic polymer; and an acidic substance. It relates to a polishing slurry composition for polishing polycrystalline silicon.

Description

Polishing slurry composition {POLISHING SLURRY COMPOSITION}

The present invention relates to a polishing slurry composition for chemical mechanical polishing (CMP) processes of polycrystalline silicon films.

The chemical mechanical polishing (CMP) process refers to a process of polishing the surface of a semiconductor wafer flat using a slurry containing abrasives and various compounds while rotating the surface of a semiconductor wafer in contact with a polishing pad. It is generally known that the metal polishing process involves repeatedly forming metal oxide (MO _x ) by an oxidizing agent and removing the formed metal oxide with abrasive particles.

As semiconductor devices become more diverse and highly integrated, finer pattern formation technologies are being used, and as a result, the surface structures of semiconductor devices are becoming more complex and the steps between surface films are becoming larger. In manufacturing semiconductor devices, a CMP (chemical mechanical polishing) process is used as a planarization technology to remove steps in a specific film formed on a wafer. CMP compositions are selective in removing one type of integrated circuit component relative to another component. Compositions and methods for CMP of wafer surfaces are well known in the art. CMP slurry compositions for polishing the surface of a semiconductor wafer typically include abrasive particles and various additive compounds. Flash memory devices with three-dimensional transistor stacking (3D flash memory) are increasingly popular. Polishing slurries for 3D flash applications must generally provide high removal rates of polycrystalline silicon, high polishing selectivity of silicon oxide, as well as good surface topography and low defect levels. In addition, it is necessary to overcome the limitations of the polishing slurry composition to ensure a high polishing rate of polycrystalline silicon film, which is only possible in an alkaline region.

In order to solve the above-mentioned problems, the present invention relates to a polishing slurry composition for polishing polycrystalline silicon films, which can realize high polishing performance of polycrystalline silicon, for example, high polishing performance in an acidic region.

However, the problems to be solved by the present invention are not limited to those mentioned above, and other problems not mentioned will be clearly understood by those skilled in the art from the description below.

According to one embodiment of the present invention, colloidal silica abrasive particles; quaternary ammonium cationic polymer; and an acidic substance. It relates to a polishing slurry composition for polishing polycrystalline silicon.

According to one embodiment of the present invention, the colloidal silica abrasive particles have a cationic surface charge, and the colloidal silica abrasive particles are a single size particle of 10 nm to 200 nm or two types of particles of 10 nm to 200 nm. It may include mixed particles having different sizes.

According to one embodiment of the present invention, the abrasive particles may be 0.0001% by weight to 10% by weight of the slurry composition.

According to one embodiment of the present invention, the quaternary ammonium cationic polymer may include at least one of the compounds represented by Formula 1 and Formula 2 below.

[Formula 1]

(Here, R ¹ and R ² are each selected from a straight-chain or branched alkyl group having 1 to 50 carbon atoms, a straight-chain or branched alkenyl group having 2 to 50 carbon atoms, and a straight-chain or branched alkoxyl group having 1 to 50 carbon atoms, n is ^an integer ^of 10 or ^{more ,} _and HSO ₄ ^- ), methyl methanesulfonate (CH ₃ SO ₃ ^- ), perchlorateClO ₄ ^- ) and hexafluorophosphate (PF ₆ ^- ).

[Formula 2]

(Here, R is hydrogen, a straight-chain or branched alkyl group with 1 to 50 carbon atoms, a straight-chain or branched alkenyl group with 2 to 50 carbon atoms, a straight-chain or branched alkoxyl group with 1 to 50 carbon atoms, and an aromatic group with 6 to 30 carbon atoms. selected from a ring, and R ¹ is a straight-chain or branched alkylene group having 1 to 50 carbon atoms and (R ⁵ and R ⁷ are each a straight-chain or branched alkylene group having 1 to 50 carbon atoms, and R ⁶ is hydrogen, a straight-chain or branched alkyl group having 1 to 50 carbon atoms; or a straight-chain or branched alkyl group having 2 to 50 carbon atoms) is an alkenyl group, and n is 0 or 1), and R ² to R ⁴ are each hydrogen, a straight-chain or branched alkyl group with 1 to 50 carbon atoms, or a straight-chain or branched alkenyl group with 2 to 50 carbon atoms. and an aromatic ring having 6 ^to 30 carbon atoms, n is an integer of 10 or ^more , ^and nitrate (NO ₃ ^- ), hydrogensulfate (HSO ₄ ^- ) or methyl methanesulfonate (CH ₃ SO ₃ ^- ), perchlorateClO ₄ ^- ) and hexafluorophosphate (PF ₆ ^- ).

According to one embodiment of the present invention, the molecular weight of the compound of Formula 1 may be 100,000 or more.

According to one embodiment of the present invention, the molecular weight of the compound of Formula 2 may be 50,000 or more, and may be lower than the molecular weight of the compound of Formula 1.

According to one embodiment of the present invention, the quaternary ammonium cationic polymer may be 0.0001% to 0.5% by weight of the composition.

According to one embodiment of the present invention, the quaternary ammonium cationic polymer is poly[bis(2-chloroethyl)ether-alt-1,3-bis[3 (dimethylamino)propyl]urea](Poly[bis (2-chloroethyl)ether-alt-1,3-bis[3-(dimethylamino)propyl]urea]); 2,2',2''-nitrilotris ethanol polymer with 1,4-dichloro-2-butene and N,N,N',N'-tetramethyl-2-butene-1,4-diamine (Ethanol , 2,2',2''-nitrilotris-, polymer with 1,4-dichloro-2-butene and N,N,N',N'-tetramethyl-2-butene-1,4-diamine); Hydroxyethyl cellulose dimethyl diallylammonium chloride copolymer; Copolymer of acrylamide and diallyldimethylammonium chloride; Copolymer of acrylamide and quaternized dimethylammoniumethyl methacrylate; Copolymer of acrylic acid and diallyldimethylammonium Chloride; Acrylamide-dimethylaminoethyl methacrylate methyl chloride copolymer; Quaternized hydroxyethyl cellulose; Copolymer of vinylpyrrolidone and quaternized dimethylaminoethyl methacrylate; Copolymer of vinylpyrrolidone and quaternized vinylimidazole; Copolymer of vinylpyrrolidone and methacrylamidopropyl trimethylammonium; Poly[oxyethylene(dimethylimino)ethylene (dimethylimino)ethylene dichloride]); Terpolymer of acrylic acid, acrylamide and diallyldimethylammonium Chloride; Terpolymer of acrylic acid, methacrylamidopropyl trimethylammonium chloride, and methyl acrylate; Terpolymer of vinylcaprolactam, vinylpyrrolidone, and quaternized vinylimidazole; Poly(2-methacryloxyethylphosphorylcholine-co-n-butyl methacrylate); poly[(dimethylamino)ethylacrylate benzyl chloride quaternary salt] (PDMAEA BCQ) and poly[(dimethylamino)ethylacrylate methyl chloride quaternary salt] (PDMAEA MCQ); Poly(acrylamide 2-methacryloxyethyltrimethyl ammonium chloride); poly[3-acrylamidopropyl trimethylammonium chloride] (poly[3-acrylamidopropyl trimethylammonium chloride]); poly[ 3-methacrylamidopropyl trimethylammonium chloride] (poly[3-methacrylamidopropyl trimethylammonium chloride]); and polydiallyldimethyl ammonium chloride (Poly(diallyldimethylammonium chloride)). there is.

According to one embodiment of the present invention, the acidic material includes an inorganic acid, an organic acid, or both, and the acidic material may be 0.0001% by weight to 1% by weight of the polishing slurry composition.

According to one embodiment of the present invention, the inorganic acid may include at least one selected from the group consisting of sulfuric acid, nitric acid, phosphoric acid, silicic acid, hydrofluoric acid, boric acid, hydrobromic acid, iodic acid, hydrochloric acid, and perchloric acid.

According to one embodiment of the present invention, the organic acid includes monocarboxylic acid, dicarboxylic acid, or both, and the organic acid includes citric acid, oxalic acid, and propionic acid. , Stearic acid, Pyruvic acid, Acetic acid, Acetoacetic acid, Glyoxylic acid, Malic acid, Malonic acid, dimethylmalonic acid. , Maleic acid, Glutaric acid, Adipic acid, 2-methyladipic acid, trimethyladipic acid, pimelic acid, Phthalic acid, Trimellitic acid, Tartaric acid, Glycollic acid, 2,2-dimethylglutaric acid, Lactic acid, Isoleucine, Glutaric acid, It may contain at least one selected from the group consisting of butyric acid, succinic acid, 3,3-diethylsuccinic acid, and ascorbic acid.

According to one embodiment of the present invention, when two or more types of acidic substances are applied, the mass ratio of the first acidic substance to the remaining acidic substances may be 9:1 to 1:9.

According to one embodiment of the present invention, the polishing slurry composition further includes a basic compound, and the basic compound is ammonia, ammonium methyl propanol (AMP), and tetramethyl ammonium hydroxide. hydroxide; TMAH), ammonium hydroxide, potassium hydroxide, sodium hydroxide, magnesium hydroxide, rubidium hydroxide, cesium hydroxide, sodium bicarbonate, sodium carbonate, imidazole, monoethanolamine (MEA), diethanol amine (DEA) , triethanolamine (TEA), 1,5-diamino-3-pentanol, 2-dimethylamino-2-methyl-1-propanol, 1-amino-2-propanol, 1-dimethylamino-2-propanol, 1 ,3-diamino-2-propanol, 3-dimethylamino-1-propanol, 2-amino-1-propanol, 2-dimethylamino-1-propanol, 2-diethylamino-1-propanol, 2-(2 -Aminoethylamino)ethanol, 2-diethylamino-1-ethanol, 2-ethylamino-1-ethanol, 1-(dimethylamino)2-propanol, N-methyldiethanolamine, N-propyldiethanolamine, N-isopropyldiethanolamine, N-(2-methylpropyl)diethanolamine, N-n-butyldiethanolamine, N-t-butylethanolamine, N-cyclohexyldiethanolamine, 2-(dimethylamino)ethanol, 2-diethylaminoethanol, 2-dipropylaminoethanol, 2-butylaminoethanol, 2-t-butylaminoethanol, 2-cycloaminoethanol, 2-amino-2-pentanol, 2-[bis(2- Hydroxyethyl)amino]-2-methyl-1-propanol, 2-[bis(2-hydroxyethyl)amino]-2-propanol, N,N-bis(2-hydroxypropyl)ethanolamine, 2- Amino-2-methyl-1-propanol, tris(hydroxymethyl)aminomethane, triisopropanolamine, tetraethyl ammonium hydroxide (TEAH), tetrapropylammonium hydroxide (TPAH), Tetrabutylammonium hydroxide, Tetrapentylammonium hydroxide (TBAH), Methyl(trishydroxyethyl)ammonium hydroxide, Tributylethylammonium hydroxide hydroxide), (2-hydroxyethyl)triethylammonium hydroxide, (2-hydroxyethyl)tripropylammonium hydroxide, and It may include at least one selected from the group consisting of (1-hydroxypropyl)triethylammonium hydroxide.

According to one embodiment of the present invention, the pH of the slurry composition may be 2 to 11.

According to one embodiment of the present invention, the polishing rate for the polycrystalline silicon film may be 2000 Å/min or more.

According to one embodiment of the present invention, the selectivity ratio of the polycrystalline silicon film to the silicon nitride film, silicon oxide film, or film containing both at pH 3 to 5 or pH 9 to 11 of the polishing slurry composition is 10:1 to 1000: It may be 1.

The present invention provides a polishing slurry composition that can secure a high polishing rate for a polycrystalline silicon film and improve polishing performance. For example, it is possible to secure a high polishing rate of a polycrystalline silicon film not only in a basic region but also in an acidic region. And, a good polishing selectivity with respect to other films such as nitride film and oxide film can be realized.

Hereinafter, embodiments of the present invention will be described in detail. In describing the present invention, if a detailed description of a related known function or configuration is judged to 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 intention of the user or operator or the customs of the field to which the present invention belongs. Therefore, definitions of these terms should be made based on the content throughout this specification.

Throughout the specification, when a member is said to be located “on” another member, this includes not only cases where a member is in contact with another member, but also cases where another member exists between the two members.

Throughout the specification, when a part “includes” a certain component, this does not mean excluding other components, but rather means that it can further include other components.

Hereinafter, the present invention will be described in detail with reference to examples with respect to the polishing slurry composition. However, the present invention is not limited to these examples.

The present invention relates to a polishing slurry composition, and according to one embodiment of the present invention, the polishing slurry composition includes colloidal silica abrasive particles; quaternary ammonium cationic polymer; and acidic substances;

According to one embodiment of the present invention, the colloidal silica abrasive particles have a particle size of 10 nm to 200 nm; Alternatively, it may include particles with a size of 20 nm to 200 nm. If the abrasive particles are within the size range, the desired polishing rate can be secured and over-polishing due to size increase can be prevented. For example, the abrasive particles may be single-sized particles of 10 nm to 200 nm or may include mixed particles having two or more different sizes of 10 nm to 200 nm. For example, the abrasive particles include first particles with a size of 10 nm to 50 nm and second particles with a size of greater than 50 nm to 100 nm, and the mixing ratio (mass ratio) of the first particles to the second particles is 1:0.1. It can be from 10 to 10. The size may mean diameter, length, thickness, etc. depending on the shape of the particle.

As an example of the present invention, the colloidal silica abrasive particles are a single particle with a specific surface area of 30 to 150 (m ² /g) or a mixed particle having two or more different specific surface areas of 30 to 150 (m ² /g). may include. For example, the abrasive particles include first particles having a specific surface area of 30 to 80 (m ² /g) and second particles having a specific surface area of greater than 80 to 150 (m ² /g), and the ratio of the first particles to the first particle is The mixing ratio (mass ratio) of the two particles may be 1:0.1 to 10. The specific surface area can be measured, for example, by the BET 6 point method using a pore distribution analyzer (Bell Japan Inc, Belsorp-II mini) using a nitrogen gas adsorption flow method.

As an example of the present invention, the colloidal silica abrasive particles may include at least one selected from the group consisting of spherical shape, square shape, needle shape, and plate shape.

As an example of the present invention, the colloidal silica abrasive particles may exhibit a cationic surface charge by coating with an organic material and/or an inorganic material, surface substitution, or both. In addition, the colloidal silica abrasive particles can control the silica surface charge through the type of substituent on the surface of the silica particle, for example, substitution with cations such as NH ₃ ⁺ and control of substituent density (or number). You can. For example, the cationic surface charge of the colloidal silica abrasive particles is greater than or equal to 8 mV at pH 1 to 6 in a liquid carrier; 10 mV or more; 15 mV or more; Alternatively, it may exhibit a positive zeta potential of 40 mV or more.

In one example of the present invention, the colloidal silica abrasive particles are contained in an amount of 0.0001% by weight to 10% by weight in the slurry composition; 0.001% to 10% by weight; Alternatively, it may be included from 0.1% by weight to 10% by weight. If it is within the above range, it is possible to implement a desired polishing rate and/or adjust the polishing rate according to the polishing target film (e.g., polycrystalline silicon film) to achieve a desired selectivity, and polishing according to an increase in the content of abrasive particles. It can reduce the number of abrasive particles remaining on the surface of the target film (e.g., polycrystalline silicon film), reduce the polishing speed due to low content, and prevent secondary defects such as dishing or erosion in the pattern due to over-polishing. there is.

According to one embodiment of the present invention, the quaternary ammonium cationic polymer may be a polymer containing at least one of the compounds represented by Formula 1 and Formula 2 below. For example, it may be a homopolymer consisting of one type of the above-mentioned compound, a mixed polymer of two or more types, or a copolymer containing a block unit containing at least one or more of the above-mentioned compounds. The quaternary ammonium cationic polymer is composed of a hydrophobic group and a hydrophilic group formed by an aliphatic hydrocarbon chain (C-Chain) and can help achieve a high polishing rate when polishing polycrystalline silicon.

[Formula 1]

As an example of the present invention, in Formula 1, R ¹ and R ² are each a straight-chain or branched alkyl group having 1 to 50 carbon atoms, a straight-chain or branched alkenyl group having 2 to 50 carbon atoms, and a straight-chain or branched carbon number 1 to 50 group. It may be selected from an alkoxyl group.

n is 10 or more; over 50; Or it may be an integer of 100 or more.

^{The _ _} _{_} ^_ _{_} ^_ It may be selected from insulfonate (CH ₃ SO ₃ ^- ), perchlorateClO ₄ ^- ) and hexafluorophosphate (PF ₆ ^- ). The alkoxyl group is represented by -O-R', and R' may be selected from a straight-chain or branched alkyl group having 1 to 50 carbon atoms and a straight-chain or branched alkenyl group having 2 to 50 carbon atoms, respectively.

In Formula 2, the “carbon number” of alkyl is 1 to 50, respectively; 1 to 30; 1 to 20; Or it may be selected from 1 to 10.

As an example of the present invention, the molecular weight (weight average molecular weight or number average molecular weight) of the quaternary ammonium cationic polymer comprising Formula 1 may be 100,000 or more, for example, 100,000 to 400,000. If it is within the above molecular weight range, it can help improve the high polishing speed and polishing performance of the polycrystalline silicon film.

[Formula 2]

As an example of the present invention, in Formula 2, R is hydrogen, a straight-chain or branched alkyl group with 1 to 50 carbon atoms, a straight-chain or branched alkenyl group with 2 to 50 carbon atoms, and a straight-chain or branched alkoxyl group with 1 to 50 carbon atoms. and an aromatic ring having 6 to 30 carbon atoms, wherein the alkoxyl group is represented by -O-R', where R' is a straight-chain or branched alkyl group with 1 to 50 carbon atoms and a straight-chain or branched alkyl group with 2 to 50 carbon atoms. It may be selected from alkenyl groups.

As an example of the present invention, in Formula 2, R ¹ is a straight-chain or branched alkylene group having 1 to 50 carbon atoms and (R ⁵ and R ⁷ are each a straight-chain or branched alkylene group having 1 to 50 carbon atoms, and R ⁶ is hydrogen, a straight-chain or branched alkyl group having 1 to 50 carbon atoms; or a straight-chain or branched alkyl group having 2 to 50 carbon atoms) alkenyl group; and n is 0 or 1).

As an example of the present invention, in Formula 2, R ² to R ⁴ are each hydrogen, a straight-chain or branched alkyl group with 1 to 50 carbon atoms, a straight-chain or branched alkenyl group with 2 to 50 carbon atoms, and 6 to 30 carbon atoms. It may be selected from an aromatic ring.

n is 10 or more; over 50; Or it may be an integer of 100 or more.

^{The _ _} _{_} ^_ _{_} ^_ It may be selected from insulfonate (CH ₃ SO ₃ ^- ), perchlorateClO ₄ ^- ) and hexafluorophosphate (PF ₆ ^- ).

In Formula 2, the “carbon number” of alkyl is 1 to 50, respectively; 1 to 30; 1 to 20; Or it may be selected from 1 to 10.

As an example of the present invention, the molecular weight (weight average molecular weight or number average molecular weight) of the quaternary ammonium cationic polymer containing the compound of Formula 2 is 50,000 or more, for example, more than the compound represented by Formula 1. It may be of low molecular weight. If it is within the above molecular weight range, it can help improve the high polishing speed and polishing performance of the polycrystalline silicon film.

As an example of the present invention, the quaternary ammonium cationic polymer is poly[bis(2-chloroethyl)ether-alt-1,3-bis[3-(dimethylamino)propyl]urea](Poly[bis(2 -chloroethyl) ether-alt-1,3-bis[3-(dimethylamino)propyl]urea]); 2,2',2''-nitrilotris ethanol polymer with 1,4-dichloro-2-butene and N,N,N',N'-tetramethyl-2-butene-1,4-diamine (Ethanol , 2,2',2''-nitrilotris-, polymer with 1,4-dichloro-2-butene and N,N,N',N'-tetramethyl-2-butene-1,4-diamine); Hydroxyethyl cellulose dimethyl diallylammonium chloride copolymer; Copolymer of acrylamide and diallyldimethylammonium chloride; Copolymer of acrylamide and quaternized dimethylammoniumethyl methacrylate; Copolymer of acrylic acid and diallyldimethylammonium Chloride; Acrylamide-dimethylaminoethyl methacrylate methyl chloride copolymer; Quaternized hydroxyethyl cellulose; Copolymer of vinylpyrrolidone and quaternized dimethylaminoethyl methacrylate; Copolymer of vinylpyrrolidone and quaternized vinylimidazole; Copolymer of vinylpyrrolidone and methacrylamidopropyl trimethylammonium; Poly[oxyethylene(dimethylimino)ethylene (Dimethylimino)ethylene dichloride]); Terpolymer of acrylic acid, acrylamide and diallyldimethylammonium Chloride; Terpolymer of acrylic acid, methacrylamidopropyl trimethylammonium chloride, and methyl acrylate; Terpolymer of vinylcaprolactam, vinylpyrrolidone, and quaternized vinylimidazole; Poly(2-methacryloxyethylphosphorylcholine-co-n-butyl methacrylate); poly[(dimethylamino)ethylacrylate benzyl chloride quaternary salt] (PDMAEA BCQ) and poly[(dimethylamino)ethylacrylate methyl chloride quaternary salt] (PDMAEA MCQ); Poly(acrylamide 2-methacryloxyethyltrimethyl ammonium chloride); Poly[3-acrylamidopropyl trimethylammonium chloride]); Poly[ 3-methacrylamidopropyl trimethylammonium chloride] (Poly[3-methacrylamidopropyl trimethylammonium chloride]); and polydiallyldimethyl ammonium chloride (Poly(diallyldimethylammonium chloride)). It may further include at least one selected from the group consisting of .

As an example of the present invention, the quaternary ammonium cationic polymer is 0.0001% by weight to 0.5% by weight in the polishing slurry composition, and when contained within the above range, a high polishing rate is realized when polishing a polycrystalline silicon film, for example, acid In this area, it is possible to achieve a high polishing rate for polycrystalline silicon films.

According to one embodiment of the present invention, the acidic material may help improve the function of the pH regulator of the polishing slurry composition, the dispersion stability of colloidal silica particles, and the polishing performance of polycrystalline silicon. For example, inorganic acid , organic acids, or both.

As an example of the present invention, the inorganic acid may include at least one selected from the group consisting of sulfuric acid, nitric acid, phosphoric acid, silicic acid, hydrofluoric acid, boric acid, hydrobromic acid, iodic acid, hydrochloric acid, and perchloric acid.

As an example of the present invention, the organic acid includes monocarboxylic acid, dicarboxylic acid, or both, and the organic acid includes citric acid, oxalic acid, propionic acid, and stearic acid ( stearic acid, pyruvic acid, acetic acid, acetoacetic acid, glyoxylic acid, malic acid, malonic acid, dimethylmalonic acid, maleic acid (maleic acid), glutaric acid, adipic acid, 2-methyladipic acid, trimethyladipic acid, pimelic acid, phthalic acid, trimellitic acid (trimellitic acid), tartaric acid, glycolic acid, 2,2-dimethylglutaric acid, lactic acid, isoleucine, glutaric acid It may include at least one selected from the group consisting of glutaric acid, butyric acid, succinic acid, 3,3-diethylsuccinic acid, and ascorbic acid.

In one example of the present invention, the acidic material is present in an amount of 0.0001% by weight to 3% by weight in the polishing slurry composition; 0.001% to 1% by weight; Or 0.01% by weight to 1% by weight, and if it is included within the above range, it is advantageous to obtain an effect of increasing the amount of CMP polishing of polycrystalline silicon due to an increase in the content of the acidic material, and the acidic material is used when two or more types of acidic materials are applied. The mass ratio of the first acidic material to the remaining acidic material is 9:1 to 1:9, which can help improve the polishing selectivity of polycrystalline silicon.

According to one embodiment of the present invention, the polishing slurry composition may further include a basic compound. As an example of the present invention, the basic compound can help improve the function of a pH adjuster, the dispersion stability of colloidal silica particles, and the polishing performance of polycrystalline silicon, and the basic compound is ammonia, ammonium methyl propanol (Ammonium methyl propanol; AMP), tetramethyl ammonium hydroxide (TMAH), ammonium hydroxide, potassium hydroxide, sodium hydroxide, magnesium hydroxide, rubidium hydroxide, cesium hydroxide, sodium bicarbonate, sodium carbonate, imidazole, monoethanolamine (Monoethanolamine, MEA), Diethanol amine (DEA), Triethanolamine (TEA), 1,5-diamino-3-pentanol, 2-dimethylamino-2-methyl-1-propanol, 1-amino -2-propanol, 1-dimethylamino-2-propanol, 1,3-diamino-2-propanol, 3-dimethylamino-1-propanol, 2-amino-1-propanol, 2-dimethylamino-1-propanol , 2-diethylamino-1-propanol, 2-(2-aminoethylamino)ethanol, 2-diethylamino-1-ethanol, 2-ethylamino-1-ethanol, 1-(dimethylamino)2-propanol , N-methyldiethanolamine, N-propyldiethanolamine, N-isopropyldiethanolamine, N-(2-methylpropyl)diethanolamine, N-n-butyldiethanolamine, N-t-butylethanolamine, N- Cyclohexyldiethanolamine, 2-(dimethylamino)ethanol, 2-diethylaminoethanol, 2-dipropylaminoethanol, 2-butylaminoethanol, 2-t-butylaminoethanol, 2-cycloaminoethanol, 2 -Amino-2-pentanol, 2-[bis(2-hydroxyethyl)amino]-2-methyl-1-propanol, 2-[bis(2-hydroxyethyl)amino]-2-propanol, N, N-bis(2-hydroxypropyl)ethanolamine, 2-amino-2-methyl-1-propanol, tris(hydroxymethyl)aminomethane, triisopropanolamine, tetraethyl ammonium hydroxide, TEAH ), Tetrapropylammonium hydroxide (TPAH), Tetrabutylammonium hydroxide, Tetrapentylammonium hydroxide (TBAH), Methyl (trihydroxyethyl) ammonium hydroxide (Methyl ( trishydroxyethyl)ammonium hydroxide), (Tributylethylammonium hydroxide), (2-hydroxyethyl)triethylammonium hydroxide ((2-hydroxyethyl),triethylammonium hydroxide), (2-hydroxyethyl)tri It may include at least one selected from the group consisting of propylammonium hydroxide ((2-hydroxyethyl) tripropylammonium hydroxide) and (1-hydroxypropyl) triethylammonium hydroxide. .

In one example of the present invention, the basic compound is 0.0001% by weight to 3% by weight in the polishing slurry composition; It is 0.001% by weight to 1% by weight or 0.01% by weight to 1.0% by weight, and if it is included within the above range, it may be advantageous to obtain an increase in the CMP polishing amount of polycrystalline silicon.

According to one embodiment of the present invention, the pH of the polishing slurry composition may be 2 to 11, for example, pH 3 to 5 or pH 9 to 11. The polishing slurry composition can achieve dispersion stability and high polishing performance of polycrystalline silicon films in an acidic range of pH 3 to 5. In addition, when a highly basic region is formed outside the pH range, significant separation of the semiconductor material may occur after polishing, and the roughness of the surface of the substrate to be polished, for example, a wafer, is not constant. It can cause defects such as dishing, erosion, erosion, corrosion and surface imbalance.

According to one embodiment of the present invention, the polishing slurry composition can be applied to polishing a substrate comprising a polycrystalline silicon film, for example, in a chemical-mechanical polishing process (CMP) of a substrate comprising a polycrystalline silicon film. .

According to one embodiment of the present invention, the polishing slurry composition has a positive zeta potential, for example, 1 mV to 100 mV; 10 mV to 80 mV; Alternatively, it may have a zeta potential of 20 mV to 60 mV. If the zeta potential is within the range, the polishing rate of the hydrophobic polycrystalline silicon film can be improved.

According to one embodiment of the present invention, the polishing slurry composition may exhibit a negative zeta potential in an alkaline region, -1 mV or less; -10 mV or less; -30 mV or less; Or it may be -30 mV to -100 mV.

According to one embodiment of the present invention, when a polishing process is performed on a substrate including the polycrystalline silicon film with the polishing slurry composition, the polishing rate for the polycrystalline silicon film is 2000 Å/min or more; It may be 3000 Å/min or more, for example, 2000 Å/min to 5000 Å/min.

According to one embodiment of the present invention, when performing a polishing process with the polishing slurry composition on a substrate including the polycrystalline silicon film, silicon nitride film, silicon oxide film, or a film containing both, high polishing selection of the polycrystalline silicon film For example, at pH 3 to 5 or pH 9 to 11 of the polishing slurry composition, the selection ratio of the polycrystalline silicon film to the silicon nitride film, silicon oxide film, or a film containing both is 10:1 to 3000. : It may be 1.

Hereinafter, the present invention will be described in more detail through examples. However, the following examples are for illustrative purposes only and are not intended to limit the scope of the present invention.

Example 1

According to Table 1 below, colloidal silica with a cationic surface charge (size of 60 nm to 80 nm), quaternary ammonium cationic polymer (PDADMAC), and nitric acid as a pH adjuster until pH reaches 4. A polishing slurry composition was prepared by mixing.

Example 2

According to Table 1 below, colloidal silica with a cationic surface charge (size of 60 nm to 80 nm), quaternary ammonium cationic polymer (PDAMAC), and nitric acid as a pH adjuster were mixed until pH reached 4. A polishing slurry composition was prepared by mixing.

Example 3

According to Table 1 below, colloidal silica with a cationic surface charge (size of 60 nm to 80 nm), quaternary ammonium cationic polymer (PDAMAC), and nitric acid as a pH adjuster were mixed until pH reached 4. A polishing slurry composition was prepared by mixing.

Example 4

According to Table 1 below, colloidal silica with a cationic surface charge (size of 60 nm to 80 nm), quaternary ammonium cationic polymer (PDAMAC), and nitric acid as a pH adjuster were mixed until pH reached 4. A polishing slurry composition was prepared by mixing.

Example 5

According to Table 1 below, colloidal silica with a cationic surface charge (size of 60 nm to 80 nm), quaternary ammonium cationic polymer (PMAC), and nitric acid as a pH adjuster were mixed until pH reached 4. A polishing slurry composition was prepared by mixing.

Example 6

According to Table 1 below, colloidal silica with a cationic surface charge (size of 60 nm to 80 nm), quaternary ammonium cationic polymer (PDAMAC), and nitric acid as a pH adjuster were mixed until pH reached 4. A polishing slurry composition was prepared by mixing.

Example 7

According to Table 1 below, colloidal silica with a cationic surface charge (size of 30 nm to 40 nm), quaternary ammonium cationic polymer (PDAMAC), and nitric acid as a pH adjuster until pH reaches 4. A polishing slurry composition was prepared by mixing.

Example 8

According to Table 1 below, colloidal silica with a cationic surface charge (size of 10 nm to 20 nm), quaternary ammonium cationic polymer (PDAMAC), and nitric acid as a pH adjuster were mixed until pH reached 4. A polishing slurry composition was prepared by mixing.

Example 9

According to Table 1 below, colloidal silica with a cationic surface charge (size of 10 nm to 20 nm), quaternary ammonium cationic polymer (PDAMAC), and potassium hydroxide (KOH) as a pH adjuster were mixed until pH reached 11. A polishing slurry composition was prepared by mixing.

Comparative Example 1

According to Table 1 below, colloidal silica with a cationic surface charge (size of 60 nm to 80 nm), a cationic polymer (P2VP, Poly(2-vinylpyridine), and nitric acid as a pH adjuster were used at pH 4. A polishing slurry composition was prepared by mixing until smooth.

Comparative Example 2

According to Table 1 below, colloidal silica with a cationic surface charge (size of 60 nm to 80 nm), a cationic polymer (PEI, polyethyleneimine), and nitric acid as a pH adjuster are mixed until pH is 4. A polishing slurry composition was prepared.

Comparative Example 3

According to Table 1 below, colloidal silica with a cationic surface charge (size of 60 nm to 80 nm), a cationic polymer (Mirapol WT), and nitric acid as a pH adjuster were mixed until pH reached 4. A polishing slurry composition was prepared.

Comparative Example 4

According to Table 1 below, colloidal silica (size of 60 nm to 80 nm) with a cationic surface charge, an anionic polymer (PAA, polyacrylic acid), and nitric acid as a pH adjuster were mixed until pH reached 4. A polishing slurry composition was prepared by mixing.

Comparative Example 5

According to Table 1 below, colloidal silica with a cationic surface charge (size of 60 nm to 80 nm), a nonionic polymer (PEG, Polyethylene glycol), and nitric acid as a pH adjuster are used when the pH is 4. A polishing slurry composition was prepared by mixing until.

Comparative Example 6

According to Table 1 below, colloidal silica (size of 30 nm to 40 nm) with a cationic surface charge, a nonionic polymer (PEG, polyethylene glycol), and nitric acid as a pH adjuster are used when the pH is 4. A polishing slurry composition was prepared by mixing until.

Comparative Example 7

According to Table 1 below, colloidal silica with a cationic surface charge (size of 30 nm to 40 nm), a quaternized nonionic polymer (QHEC, Quanternized Hydroxyethylcelluse), and nitric acid as a pH adjuster are used to adjust the pH to 4. A polishing slurry composition was prepared by mixing until mixed.

Evaluation of polishing properties

A polysilicon film-containing substrate was polished using the polishing slurry compositions of Examples and Comparative Examples under the following polishing conditions.

[Polishing conditions]

(1) Polishing equipment: ST#01 (KCT)

(2) Carrier rpm/Platen rpm: 87/93

(3) Wafer Pressure: 3 psi

(4) Surry Flow rate (ml/min): 250 ml/min

(5) Pad: IC 1000

(6) Time: 60s

(7) R-ring pressure: 6 psi

In order to evaluate the polishing characteristics, the polishing speed and the recess of the pattern surface after polishing the polysilicon wafer substrate were measured using the polishing slurry composition according to the examples and comparative examples, and the results are shown in Table 1.

colloidal silica particles Additive-1 pH Poly-Si polishing amount
(Å/min) Nitride polishing amount
(Å/min) Oxide
Polishing amount
(Å/min) type Wt% type Wt% Example 1 F-1 One A-1 0.3 4 2892 8.2 1.5 Example 2 F-1 One A-1 0.1 4 4011 7 4 Example 3 F-1 One A-1 0.03 4 4411 6.2 8.3 Example 4 F-1 One A-1 0.01 4 3387 5.9 9 Example 5 F-1 One A-2 0.01 4 2366 5.8 5.2 Example 6 F-1 2 A-1 0.03 4 4652 10.8 14.2 Example 7 F-2 One A-1 0.03 4 5349 7.3 3 Example 8 G-1 One A-1 0.03 4 4635 6.1 4.2 Example 9 G-1 One A-1 0.01 11 4989 8.4 6.8 Comparative Example 1 F-1 One B-1 0.01 4 1038 4.7 1.8 Comparative Example 2 F-1 One B-2 0.01 4 1108 4.5 2.1 Comparative Example 3 F-1 One B-3 0.01 4 45 4.9 2 Comparative Example 4 F-1 One C 0.1 4 12 5.2 2 Comparative Example 5 F-1 One D 0.1 4 6 4.8 2.1 Comparative Example 6 F-2 One D 0.1 4 7 5.6 4 Comparative Example 7 F-2 One E 0.1 4 10 5.6 4

A-1: Quaternary Ammonium Cation polymer, PDADMAC (Polydiallyldimethylammonium chloride), molecular weight: 100 K~200 K

A-2: Quaternary Ammonium Cation polymer, PMAC (Poly(2-methacryloxyethyltrimethylammonium chloride)), molecular weight: 50 K

B-1: Cation polymer, P2VP(Poly(2-vinylpyridine))

B-2: Cation polymer, PEI (Polyethyleneimine)

B-3: Cation polymer, Mirapol WT

C: Anion polymer, PAA (Polyacrylic acid)

D: Nonion polymer, PEG (Polyethylene glycol)

E: Quanternized nonion polymer, QHEC (Quanternized Hydroxyethylcelluse)

F-1: PL-3C (FUSO, cation type)

F-2: PL-1C (FUSO, cation type)

G-1 : BS-1 LC(FUSO)

pH adjuster: Select from nitric acid, KOH, and TEA (Triethanolamine) and add 0.03 to 0.1% by weight of each.

Looking at Table 1, the polishing slurry composition according to the present invention can secure a high polishing rate polishing performance for a polycrystalline silicon film in an acidic region when adding the quaternary ammonium cationic polymer represented by Formula 1 and Formula 2. . That is, the polishing slurry composition according to the present invention has a high polishing rate for polycrystalline silicon films and a high polishing selectivity for silicon oxide and silicon nitride films compared to the application of nonionic polymers, anionic polymers, and cationic polymers in comparative examples. We can confirm that it can be implemented.

As described above, although the embodiments have been described with limited examples and drawings, various modifications and variations can be made by those skilled in the art from the above description. For example, even if the described techniques are performed in a different order than the described method, and/or the described components are combined or combined in a different form than the described method, or are replaced or substituted by other components or equivalents. Adequate results can be achieved. Therefore, other implementations, other embodiments, and equivalents of the claims also fall within the scope of the claims described below.

Claims (16)

colloidal silica abrasive particles;
quaternary ammonium cationic polymer; and
acidic substances;
Including,
The quaternary ammonium cationic polymer is at least one selected from the group consisting of poly(diallyldimethylammonium chloride) and poly(2-methacryloxyethyltrimethylammonium chloride). It includes more than
The polishing slurry composition further includes a basic compound,
The basic compounds include ammonia, ammonium methyl propanol (AMP), tetramethyl ammonium hydroxide (TMAH), ammonium hydroxide, potassium hydroxide, sodium hydroxide, magnesium hydroxide, rubidium hydroxide, and cesium hydroxide. , sodium bicarbonate, sodium carbonate, imidazole, monoethanolamine (MEA), diethanol amine (DEA), triethanolamine (TEA), 1,5-diamino-3-pentanol, 2-dimethyl Amino-2-methyl-1-propanol, 1-amino-2-propanol, 1-dimethylamino-2-propanol, 1,3-diamino-2-propanol, 3-dimethylamino-1-propanol, 2-amino -1-propanol, 2-dimethylamino-1-propanol, 2-diethylamino-1-propanol, 2-(2-aminoethylamino)ethanol, 2-diethylamino-1-ethanol, 2-ethylamino- 1-ethanol, 1-(dimethylamino)2-propanol, N-methyldiethanolamine, N-propyldiethanolamine, N-isopropyldiethanolamine, N-(2-methylpropyl)diethanolamine, Nn- Butyldiethanolamine, Nt-butylethanolamine, N-cyclohexyldiethanolamine, 2-(dimethylamino)ethanol, 2-diethylaminoethanol, 2-dipropylaminoethanol, 2-butylaminoethanol, 2- t-butylaminoethanol, 2-cycloaminoethanol, 2-amino-2-pentanol, 2-[bis(2-hydroxyethyl)amino]-2-methyl-1-propanol, 2-[bis(2- Hydroxyethyl)amino]-2-propanol, N,N-bis(2-hydroxypropyl)ethanolamine, 2-amino-2-methyl-1-propanol, tris(hydroxymethyl)aminomethane, triisopropanolamine , Tetraethyl ammonium hydroxide (TEAH), Tetrapropylammonium hydroxide (TPAH), Tetrabutylammonium hydroxide, Tetrapentylammonium hydroxide (TBAH), methyl (Methyl(trishydroxyethyl)ammonium hydroxide), Tributylethylammonium hydroxide, (2-hydroxyethyl)triethylammonium hydroxide ((2-hydroxyethyl) , triethylammonium hydroxide), (2-hydroxyethyl) tripropylammonium hydroxide and (1-hydroxypropyl) triethylammonium hydroxide ((1- hydroxypropyl) trimethylammonium hydroxide) It contains at least one selected from the group consisting of,
The basic compound is 0.0001% to 3% by weight of the polishing slurry composition,
It is for polishing polycrystalline silicon,
The polishing rate for the polycrystalline silicon film is 2000 Å/min or more,
Polishing slurry composition.
According to paragraph 1,
The colloidal silica abrasive particles have a cationic surface charge,
The colloidal silica abrasive particles are single-sized particles of 10 nm to 200 nm or contain mixed particles having two or more different sizes of 10 nm to 200 nm,
Polishing slurry composition.
According to paragraph 1,
The abrasive particles are,
0.0001% to 10% by weight of the slurry composition,
Polishing slurry composition.
delete delete delete According to paragraph 1,
The quaternary ammonium cationic polymer is,
0.0001% to 0.5% by weight of the composition,
Polishing slurry composition.
delete According to paragraph 1,
The acidic substance includes an inorganic acid, an organic acid, or both,
The acidic substance is 0.0001% to 1% by weight of the polishing slurry composition,
Polishing slurry composition.
According to clause 9,
The inorganic acid is,
Containing at least one selected from the group consisting of sulfuric acid, nitric acid, phosphoric acid, silicic acid, hydrofluoric acid, boric acid, hydrobromic acid, iodic acid, hydrochloric acid, and perchloric acid,
Polishing slurry composition.
According to clause 9,
The organic acid includes monocarboxylic acid, dicarboxylic acid, or both,
The organic acids include citric acid, oxalic acid, propionic acid, stearic acid, pyruvic acid, acetic acid, acetoacetic acid, and glyoxylic acid. (glyoxylic acid), malic acid, malonic acid, dimethylmalonic acid, maleic acid, glutaric acid, adipic acid, 2-methyladip Acids, trimethyladipic acid, pimelic acid, phthalic acid, trimellitic acid, tartaric acid, glycolic acid, 2,2-dimethylglutaric acid , lactic acid, isoleucine, glutaric acid, butyric acid, succinic acid, 3,3-diethylsuccinic acid, and ascorbic acid. Containing at least one selected from the group consisting of,
Polishing slurry composition.
According to clause 9,
The acidic substance is,
When applying two or more types of acidic substances, the mass ratio of the first acidic substance to the remaining acidic substances is 9:1 to 1:9,
Polishing slurry composition.
delete According to paragraph 1,
The pH of the slurry composition is 2 to 11,
Polishing slurry composition.
delete According to paragraph 1,
At pH 3 to 5 or pH 9 to 11 of the polishing slurry composition, the selectivity ratio of the polycrystalline silicon film to the silicon nitride film, silicon oxide film, or film containing both is,
10:1 to 1000:1,
Polishing slurry composition.