KR20170048513A - Slurry composition, rinse composition, substrate polishing method and rinsing method - Google Patents

Abstract

A slurry composition for chemical mechanical polishing, a rinse composition, a substrate polishing method, and a rinsing method are disclosed. The slurry composition of the present invention is a slurry composition for chemical mechanical polishing comprising water, abrasive particles, and at least one water-soluble polymer containing polyvinyl alcohol structural units. When one such water-soluble polymer is present in the slurry composition, its polyoxyalkylene oxide structural unit and polyvinyl alcohol structural unit can form the main skeleton or side chain of the water-soluble polymer. The slurry composition of the present invention may contain a water-soluble polymer selected from a pH adjuster, a cellulosic polymer and a polyalkylene oxide polymer, and a haze improving agent. The water soluble polymer may be present in the slurry composition at 1 ppm to 5000 ppm.

Description

TECHNICAL FIELD [0001] The present invention relates to a slurry composition, a rinse composition, a substrate polishing method, and a rinse method,

More particularly, the present invention relates to a slurry composition, a rinse composition, a substrate polishing method, and a rinsing method used for chemical mechanical polishing (CMP) or the like.

A semiconductor substrate in the form of a silicon wafer used for producing a semiconductor device is used for supplying semiconductor devices after being subjected to various photolithography, deposition, polishing and the like. Since many processing steps are applied to a silicon wafer to manufacture a semiconductor device and it is necessary to improve the yield of the semiconductor device, the surface quality of the silicon wafer is subject to strict requirements. Conventionally, chemical mechanical polishing (CMP) has been used to ensure surface quality through mirror polishing of silicon wafers.

When the silicon wafer is polished by CMP, the silicon wafer is generally held on a carrier for holding the silicon wafer, and the silicon wafer has a top surface with a polishing cloth having a synthetic resin foam or suede- (Hereinafter referred to as a slurry composition) containing silica, alumina, ceria, zirconia, or other colloid particles, and then the silicon wafer is polished while being compressed and rotated.

As CMP is performed on silicon wafers, demand for improvement in productivity and surface quality has increased sharply with increasing demand in recent years, improvement in semiconductor device performance, and higher integration density, so that the polishing rate, surface roughness, haze (Including surface blur), flatness (including roll-off (end surface deflection), SFQR, ESFQR), and scratch reduction.

Conventionally, a technique for improving the surface properties of a semiconductor substrate has been proposed. For example, Japanese Laid-Open Patent Publication No. 2014-38906 (Patent Document 1) discloses a technique for preventing particles from adhering to a polished surface of a polishing target A polishing composition containing polyvinyl alcohol as the main skeleton structure is disclosed. Japanese Patent Application Laid-Open No. H11-140427 (Patent Document 2) discloses a polishing liquid containing a long hydrocarbon chain main skeleton and a linear hydrocarbon polymer having a hydroxy-lower alkylene group as a side chain thereof, and a polishing method using the same .

While such techniques are known, there is a need to further improve the surface state of the semiconductor substrate in order to improve the yield and other parameters of the integrated circuit product as the size of the device is required to be further reduced, along with the demand for higher levels of semiconductor device integration. Needs to be.

Japanese Patent Laid-Open No. 2014-38906 Japanese Patent Application Laid-Open No. H11-140427

In view of the foregoing, it is an object of the present invention to provide a slurry composition, a rinse composition, a substrate polishing method, and a rinsing method which make it possible to improve the surface condition of a semiconductor substrate.

According to the present invention,

water,

Abrasive particles, and

There is provided a slurry composition for chemical mechanical polishing comprising at least one water-soluble polymer containing polyvinyl alcohol structural units.

In the present invention, the water-soluble polymer may be at least one water-soluble polymer containing a polyoxyalkylene oxide structural unit or a polyvinyl alcohol structural unit, respectively. When one such water-soluble polymer is present in the slurry composition, the polyoxyalkylene oxide structural unit or the polyvinyl alcohol structural unit thereof may form a main skeleton or a side chain of the water-soluble polymer. The water-soluble polymer preferably contains a pH adjuster. Further, the present invention may contain a water-soluble polymer selected from a cellulose-based polymer and a polyalkylene oxide-based polymer. Further, the present invention may contain a haze improving agent. In the present invention, the water-soluble polymer is preferably contained at 1 ppm to 5000 ppm.

Further, according to the second aspect of the present invention,

Water and

There is provided a rinse composition for a polishing substrate comprising at least one water-soluble polymer containing polyvinyl alcohol structural units.

In the present invention, the water-soluble polymer may be at least one water-soluble polymer containing a polyalkylene oxide structural unit or a polyvinyl alcohol structural unit, respectively. In addition, when one water-soluble polymer is present in the slurry composition, the polyalkylene oxide structural unit and the polyvinyl alcohol structural unit thereof may form the main skeleton or the side chain of the water-soluble polymer. Further, the present invention may contain a water-soluble polymer selected from a cellulose-based polymer and a polyalkylene oxide-based polymer. The present invention may further contain a hazing agent. The water-soluble polymer is preferably contained in an amount of 1 ppm to 5000 ppm.

Further, in the third configuration of the present invention,

Attaching the slurry composition to a polishing substrate, and

There is provided a substrate polishing method comprising polishing the polishing substrate with a polishing pad using the slurry composition.

According to a fourth aspect of the present invention, there is provided a rinsing method of a polishing substrate comprising rinsing a polishing substrate with the rinsing composition.

According to the present invention, there is provided a slurry composition which enables to improve nanoscale polishing defects called fine surface irregularities, that is, for example, light point defects (LPD), haze, haze scratches, , A rinse composition, a substrate polishing method, and a rinsing method are provided.

Hereinafter, the present invention will be described with reference to its embodiments, but the present invention is not limited to the following embodiments. In this embodiment, nanoscale polishing defects are referred to as nanoscratches. The slurry composition or rinse composition of the present invention comprises at least one water-soluble polymer containing polyalkylene oxide structural units and polyvinyl alcohol structural units, respectively. As the first embodiment of the water-soluble polymer of the present embodiment, two different polyoxyalkylene oxides and polyvinyl alcohol water-soluble polymers may be contained in each composition. In a second aspect of the present invention, a polyalkylene structural unit or a polyvinyl alcohol structural unit may be present in each composition in the form of a graft polymer constituting a main skeletal chain or a side chain. In the present invention, when the polyvinyl alcohol structural unit is present in the main skeletal chain or the side chain, some of the hydroxyl groups may be substituted with an acyloxy group. As the acyloxy group, an acyloxy group having two or more carbon atoms can be preferably used, and (CH ₃ COO-) group is particularly preferable.

The polyoxyalkylene oxide of the polyalkylene oxide structural unit may be a polyethylene oxide, a polypropylene oxide, or an (ethylene oxide-propylene oxide) copolymer, and the copolymer may be a random copolymer or a block copolymer have. The repeating chain length of the alkylene oxide of the polyalkylene oxide is from 1 to 1000, more preferably from 2 to 300, and still more preferably from about 3 to 200.

When the water-soluble polymer of the present embodiment is composed of a water-soluble polymer which is independent of each other in the form of polyalkylene oxide or polyvinyl alcohol, the abundance ratio thereof is preferably from 5:95 to 40:60 in terms of mol%, and the nanoscale polishing defect Lt; RTI ID = 0.0 > 10:90 to 30:70. ≪ / RTI > In addition, the molecular weight of the polyalkylene oxide and polyvinyl alcohol may be in the range of 1,000 to 10,000,000.

When the polyalkylene oxide and the polyvinyl alcohol form a graft polymer in the present embodiment, the molecular weight of the graft polymer may be about 5,000 to 500,000, and the physical properties of the solution such as the slurry solution The weight average molecular weight may preferably be in the range of 10,000 to 300,000, more preferably in the range of 10,000 to 200,000.

In the graft polymer of the present embodiment, the abundance ratio of the polyalkylene oxide main skeleton to the polyvinyl alcohol main skeleton is preferably from 5:95 to 40:60 in terms of mole%, and from the viewpoint of improving nanoscale abrasion defects, : 90 to 30:70.

The alkylene oxide main skeleton of the present embodiment may be ethylene oxide, propylene oxide, or may form a chain by random polymerization or block polymerization thereof. Of these, the alkylene oxide is most preferably ethylene oxide.

When the water-soluble polymer is added in the form of a graft polymer, specific examples of the water-soluble polymer include water-soluble polymers having the following general formula (1).

[Chemical Formula 1]

In the general formulas (1) and (1 '), R represents a hydroxyl group or an acyloxy group having 2 or more carbon atoms, a represents an integer of 1 to 10,000, M1, M2, N1 and N2 represent a real number of 0 or more (Grating rate). In the general formula (1), R ₁ represents a hydrogen atom or an acyl group. R ₂ and R ₃ may be the same or different and each represents a linear or branched alkyl group having 2 or more carbon atoms, and b represents an integer of 2 to 10,000. R in formulas (1) and (1 ') may have a complex structure in which both a hydroxyl group and an acyloxy group exist, i.e., a structure in which an acyloxy group is saponified with a hydroxy group.

Specific examples of preferred water-soluble polymers of this embodiment include water-soluble polymers having the structural formulas (2) and (3) shown below. In addition, a part or the terminal hydroxyl group of the hydroxy groups of the following general formulas (2) and (3) may be substituted with an acyloxy group.

(2)

(3)

In the present embodiment, the water soluble polymer may be present in the slurry composition in the range of 1 ppm (0.001 wt%) to 5000 ppm (0.5 wt%). Further, it is preferable that the water-soluble polymer is added in the range of 10 ppm to 1000 ppm from the viewpoint of maintaining the polishing rate which enables realistic production throughput.

The slurry composition of the present embodiment may contain a polymer having a tertiary amine structure in its main chain structure for use as a haze improving agent for improving the haze and LPD of the surface of a semiconductor substrate.

The polymer used in the present invention is a polymer obtained by reacting an active hydrogen of a polyamine compound having at least two primary amino groups and / or secondary amino groups in a molecule and containing 4 to 100 N atoms, with an alkylene oxide The seed can be produced by addition polymerization. The weight average molecular weight of the polymer may range from 5,000 to 100,000. In addition, the number of N atoms contained in the polymer of the present embodiment is preferably 2 to 10,000 or less in view of providing water solubility for application to the CMP process, and it is preferable to provide sufficient CMP process suitability while improving haze It is preferable that the number of N atoms is in the range of 2 to 1,000. Hereinafter, in the description of this embodiment, the polymer is referred to as an alkylene polyalkyleneoxide amine polymer (APOA).

Examples of the polyamine compound to which the main chain structure is imparted in the present embodiment include polyamine compounds obtained by polymerization of polyethylene polyamines such as triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, or hexaethyleneheptamine, and ethyleneimine And polyalkyleneimines such as polyethyleneimine. These compounds may be used alone to form the polyamine main chain structure of the present embodiment, or two or more may be used in combination.

Examples of the alkylene oxide added to the main chain structure include ethylene oxide, propylene oxide and butylene oxide, and these alkylene oxides may be used singly or in a mixture of two or more thereof.

The alkylene oxide main skeleton which can be used in the present embodiment is preferably selected from ethylene oxide main skeleton and / or polypropylene main skeleton. The proportion of the ethylene oxide contained in the alkylene oxide added to the polymer of the present embodiment is 5% or more, preferably 10% or more. When the ratio is made 50% to 90%, it is possible to give a preferable CMP process suitability have. When the propylene oxide skeleton is contained in the present embodiment, it is preferable that the propylene oxide skeleton is contained in the range of 10% to 20% in order to widen the process margin.

The polymer of this embodiment can be easily produced by a conventional method. For example, the polymer of the present embodiment can be produced by subjecting an alkylene oxide to the addition polymerization (grafting) to the starting material of the polyamine compound type at an atmospheric pressure of 1 atm to 10 atm at a temperature of 100 ° C to 180 ° C in the presence of an alkali catalyst Followed by polymerization).

The manner of adding the alkylene oxide to the main chain structure of the polyamine compound type is not particularly limited, and in the case of a method in which two or more alkylene oxides are added, the additional method may be a block addition or a random addition form. The weight average molecular weight of the polymer of this embodiment may be 5,000 or more, preferably 10,000 or more, and may be 100,000 or less or 80,000 or less. When the weight average molecular weight is too small, the haze can not be sufficiently improved. When the weight average molecular weight is excessively large, the dependency of the addition amount of each characteristic is increased and the process margin is narrowed.

In the present specification, the main chain structure means a structure containing two or more repeating structural units including a tertiary amine for graft-polymerizing a polyalkylene oxide group. In addition, the tertiary amine constituting the main chain structure of the present embodiment preferably contains an N-alkylene group. The number of C atoms constituting the N-alkylene group is not particularly limited, and a linear or branched alkylene group having 2 to 10 C atoms may be selected.

As a specific example of the polymer of the present embodiment, there may be a polymer represented by the following general formula (4), which is produced by addition polymerization of an alkylene oxide and a polyethylene polyamine and containing at least a tertiary amine structure in the main chain structure.

[Chemical Formula 4]

In the general formula (4), x and y are positive integers, and R ₄ represents an alkylene group. R ₃ And R < ₄ > represent a linear or branched alkylene group having 2 or more carbon atoms, and most preferably an ethylene group from the viewpoint of improving productivity, cost to performance ratio and haze. In the present embodiment, x may be in the range of 2 to 1,000, preferably in the range of 2 to 20, and y may be in the range of 2 to 10,000, preferably in the range of 2 to 500. If the chain length of the R ₄ O chain is too long, the effect of improving the surface properties is reduced. If y is more than 10,000, the dependency of each property on the amount of addition becomes large, which adversely affects the process margin. R ₄ O may be formed using two or more alkylene oxides, and in the case of this embodiment, the different alkylene oxide groups may be in a block form or a random form.

It is preferable to make the solubility parameter of the compound given in the above general formulas (1) to (4) of the present invention be in the range of 9 to 16. In the present specification, the solubility parameter (SP) is a value determined by the method described in Ueda et al., "Study of Coatings" 152, Oct. 2010, pp. 41-46). The SP value of the water-soluble polymer is based on the SP value of the monomer determined according to the method of Fedors,

Further, other water-soluble polymers may be used in the present invention. Examples of such water-soluble polymers include homopolymers or copolymers produced by polymerizing vinyl monomers. Examples of such vinyl monomers include styrene, chlorostyrene,? -Methylstyrene, divinylbenzene; Vinyl carboxylate such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl octylate, vinyl caprate, vinyl laurate, vinyl myristate, vinyl stearate, vinyl adipate, vinyl (meth) acrylate , Vinyl crotonate, vinyl sorbate, vinyl benzoate, or vinyl cinnamate, acrylonitrile, limonene, cyclohexene; N-vinyl compounds such as 2-vinylpyridine, 3-vinylpyridine, 4-vinylpyridine, N-vinylpyrrolidone, N-vinyl acetamide or N-vinylmethylacetoamide, cyclic ether vinyl compounds, examples Such as vinyl furane or 2-vinyloxytetrahydropyran, monovinyl ethers such as methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, amyl vinyl ether, 2-ethylhexyl vinyl ether, But are not limited to, ether, nonyl vinyl ether, dodecyl vinyl ether, hexadecyl vinyl ether, octadecyl vinyl ether, butoxyethyl vinyl ether, cetyl vinyl ether, phenoxyethyl vinyl ether, allyl vinyl ether, Ether, 2-chloroethyl vinyl ether or cyclohexyl vinyl ether, ethylene glycol monovinyl ether, polyethylene glycol monovinyl ether, propylene glycol monovinyl ether, Butylene glycol monovinyl ether, 1,3-butylene glycol monovinyl ether, tetramethylene glycol monovinyl ether, hexamethylene glycol monovinyl ether, neopentyl glycol monovinyl ether, trimethylolpropane monovinyl ether, glycerin monovinyl ether, A water-soluble polymer or copolymer, which is a homopolymer such as erythritol monovinyl ether or 1,4-cyclohexanedimethanol monovinyl ether, and any combination thereof, Can be adjusted.

In addition to the above-mentioned acrylic resin, cellulose derivatives such as methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methylcellulose and the like can be used in the present invention. A cellulose derivative having an average molecular weight of 50,000 to 2,000,000 can be used.

Specific examples of the water-soluble polymer that can be used in combination include poly-N-vinylpyrrolidone, poly-N-vinyl acetamide, polyglycerin, PEG / PEO having a molecular weight of 1,000 to 1,000,000, PEG- (Average molecular weight: 200,000), polyacrylic acid (average molecular weight: 200,000), and a polyoxyalkylene polyoxyalkylene adduct of ethylene oxide (EO weight ratio: 35%, PPG molecular weight: 4400, reverse type) (Average molecular weight: 25,000), and polyacrylate (average molecular weight: 5,000).

When an alkylene-polyalkylene oxide amine polymer is present in the slurry composition of the present invention, the amount added may be in the range of 1 ppm (0.001 wt%) to 5000 ppm (0.5 wt%). From the viewpoint of maintaining the polishing rate of the silicon wafer to allow realistic production throughput, the addition amount is preferably in the range of 5 ppm to 1000 ppm, and in the range of 5 ppm to 500 ppm Is more preferable.

In addition to the water-soluble polymers described above, the slurry compositions of the present invention may contain abrasive particles, acids or bases, buffers, catalysts or various abrasive ingredients such as salts. The abrasive grains generally used for polishing may be used as abrasive grains to be used in the present invention. Examples of abrasive grains include carbides, nitrides, oxides, borides and diamonds of metals, metals or semimetals.

The abrasive grains usable in the present invention are preferably metal oxides capable of polishing the surface of the substrate without introducing harmful scratches or other defects on the surface of the substrate. Preferred examples of metal oxide abrasive particles include alumina, silica, titania, ceria, zirconia, magnesia and their co-formed products, mixtures thereof and their chemical admixtures. The abrasive particles are typically selected from the group consisting of alumina, ceria, silica, zirconia, and combinations thereof. Silica, especially colloidal silica and ceria, are preferred abrasive particles, with colloidal silica being more preferred.

The abrasive grains of the slurry composition of the present invention can be formed in the form of a dispersion or a suspension by dispersing abrasive grains in a preferable liquid carrier and adding various additives such as water-soluble polymers. In many cases, the slurry composition is produced at a concentration higher than that used when used in polishing to reduce transportation costs. In the following description, when the concentration of the slurry composition is described, it indicates the concentration after being diluted with the polishing liquid used for polishing. Examples of a preferable liquid carrier include a polar solvent, preferably water or an aqueous solvent. When the abrasive grains are contained in the slurry, the slurry preferably contains the abrasive grains in a concentration of 0.1 wt% or more , More preferably from 0.1 wt% to 50 wt%, and more preferably from 0.1 wt% to 10 wt% of abrasive particles in the form of colloidal silica may be added to the slurry composition.

The pH of the slurry composition of the present invention can be appropriately adjusted in consideration of the polishing rate. In the present invention, the pH of the slurry composition is preferably in the range of 5 to 12, more preferably in the range of 7 to 12 when the polishing treatment of the silicon wafer is carried out.

The average particle diameter of the primary particles of the abrasive particles is preferably 0.01 탆 to 3 탆, more preferably 0.01 탆 to 0.8 탆, and particularly preferably 0.02 탆 to 0.5 탆, from the viewpoint of improving the polishing rate. When secondary particles are formed by aggregation of the primary particles, the average particle diameter of the secondary particles is preferably in the range of 0.02 mu m to 3 mu m from the viewpoint of improving the polishing rate and reducing the surface roughness of the object to be polished, Mu] m, more preferably 0.05 mu m to 1 mu m, and particularly preferably 0.03 mu m to 0.15 mu m. The average particle diameter of the primary particles of the abrasive grains can be determined by observing with a scanning electron microscope or a transmission electron microscope, analyzing the resulting image, and measuring the particle diameter. The average particle diameter of the secondary particles can be measured as the volume average particle diameter using the laser light scattering method.

In the present invention, various other additives may be used depending on the polishing substrate. Examples of preferred additives that may be present in the polishing system include amines, ammonium salts, alkali metal ions, film formers, complexing agents, surfactants, rheology control agents, polymeric stabilizers or dispersants and / or halide ions have. The additive may be present in the polishing system at any suitable concentration.

Also, the amine compound may be added to the slurry composition, and the amine compound may be selected from aliphatic amines, cyclic amines, heterocyclic amines, aromatic amines, polyamines, and combinations thereof. In a preferred embodiment, the amine compound may contain one or more oxygen atoms and one or more polar moieties, such as amino acids or amino alcohols, and specific examples thereof include dimethylpropanolamine (2-dimethylamino-2-methyl- 2-methyl-1-propanol (AMP), 2- (2-aminoethylamino) ethanol, 2- (isopropylamino) ethanol, 2- Ethanol, 2- (diethylamino) ethanol, 2- (2- (dimethylamino) ethoxy) ethanol, 1,1 '- [[3- (dimethylamino) propyl] imino] 2- (butylamino) ethanol, 2- (tert-butylamino) ethanol, 2- (diisopropylamino) ethanol, N- (3-aminopropyl) morpholine and mixtures thereof.

In the present invention, in addition to the amine compound, an ammonium salt can be added, and for example, a hydroxylated amine (e.g., tetramethylammonium hydroxide (TMAH)) and a quaternary ammonium compound can be used.

In the slurry composition, alkali metal ions may also be present in the counter ion form of various salts. Preferable examples of the alkali metal ion include a monovalent base metal belonging to Group 1 of the periodic table. Specific examples of the alkali metal ion include sodium ion, potassium ion, rubidium ion, and cesium ion. Potassium ion and cesium ion are preferable, and potassium ion is more preferable.

In the present invention, an antiseptic agent may be used together with a polishing system. Examples of anticorrosion agents include alkylamines, alkanolamines, hydroxylamines, phosphoric acid esters, sodium laurylsulfate, fatty acids, polyacrylates, polymethacrylates Polyvinyl phosphonate, polymaleate, polystyrenesulfonate, polyvinylsulfonate, benzotriazole, triazole, benzimidazole, and mixtures thereof.

Further, in the present invention, a chelating reagent or the like may optionally be added to the slurry composition. Examples of chelating reagents include carbonyl compounds such as acetylacetonate, carboxylates such as acetate, aryl carboxylates, carboxylates comprising at least one hydroxy group, such as glycolate, But are not limited to, lactates, glycinates, glycans and their salts, dicarboxylates, tricarboxylates and polycarboxylates such as oxalates, phthalates, citrates, succinates, tartrates, EDTA and the like, and mixtures thereof. Examples of preferred chelating reagents include dialcohols, trialcohols, or polyhydric alcohols, such as ethylene glycol, pyrocatechol, pyrogallol, tannic acid, and phosphate-containing compounds.

In the present invention, a surfactant, a viscosity modifier or a coagulant may optionally be used together with the polishing system. Preferred examples of viscosity modifiers include urethane polymers and acrylates comprising at least one acrylic unit. Specific examples of the viscosity adjuster include a low molecular weight carboxylate and a high molecular weight polyacrylamide compound. Preferable examples of the surfactant include a cationic surfactant, an anionic surfactant, an anionic polymer electrolyte, An amphoteric surfactant, an amphoteric surfactant, a fluorinated surfactant, and mixtures thereof.

The substrate can be polished into a polishing system equipped with a suitable polishing pad. For example, a woven or non-woven polishing pad may preferably be used as a polishing pad. Specific examples of preferable polishing pads which can be used include synthetic resin polishing pads, and preferable examples of the used polymers include, for example, polyvinyl chloride, polyvinyl fluoride, nylon, hydrogen fluoride, polycarbonate, poly Esters, polyacrylates, polyethers, polyethylenes, polyamides, polyurethanes, polystyrenes, polypropylenes and their co-formed products and mixtures.

In addition, the slurry composition and a substrate polishing method of the present invention as well as a silicon substrate, a polishing process, such as a silicon substrate, a sapphire substrate, SiC substrate, GaAs substrate, a GaN substrate or a polysilicon film, SiO TSV substrate ₂ film or a metal wiring film is formed The present invention can also be applied to a substrate to which the present invention can be applied. The present invention also relates to a method of polishing a slurry composition prepared by previously preparing a slurry composition with a polishing pad while supplying the slurry composition to a polishing substrate, as well as a method of supplying a diluted solution and an undiluted slurry onto a polishing pad, So-called on-platen blending, and a polishing method in which the production is carried out, including a step of producing a slurry composition for use in the present invention.

In the present invention, water and an aqueous solution containing a water-soluble polymer represented by the general formula (1) can be used as the rinsing liquid used for rinsing the polishing substrate after the polishing treatment. The rinse composition of the present embodiment can be prepared by mixing water and a water-soluble polymer represented by the general formula (1) in addition to a water-soluble polymer such as a cellulose polymer, a polyalkylene oxide polymer or a water-soluble polymer or a pH adjuster such as an acid or a base It can be used after addition of additives.

Although the present invention has been described in detail with reference to the specific embodiments thereof, it will be understood by those skilled in the art that the present invention is not limited thereto. Further, the embodiments described below are for the purpose of understanding the present invention and are not intended to limit the present invention in any sense.

Example

The slurry composition of the present invention was prepared by adding an additive having the following structural formula to a slurry solution and measuring LPD and surface haze (DWO haze). The preparation of the slurry composition and the polishing conditions of the silicon wafer are as follows.

1. Preparation of slurry composition (polishing liquid concentrate)

Exemplary compounds of the structural formula (2) were obtained in the form of a polyvinyl alcohol-polyethylene oxide graft copolymer (80:20 mol%, molecular weight = 93,600, gelation rate: 98.5%, main chain: polyvinyl alcohol, side chain: polyethylene oxide) , An exemplary compound of the structural formula (3) is a polyethylene oxide-polyvinyl alcohol graft copolymer (25:75 mol%, molecular weight = 45,000, gelation rate: 92% to 99%, main chain: polyethylene oxide, side chain: (EO: PO = 8: 2, average number of nitrogen atoms: 5, molecular weight = 46,000) in the form of an alkylene-polyalkylene oxide polyamine polymer To prepare slurry compositions each having the composition shown in Table 1 below. Examples 1 to 3 are examples of the present invention, while Example 4 is a comparative example.

2. Polishing condition

After rinsing with a hydrogen fluoride (0.5%) at 23 캜 for 2 minutes on a 12-inch p-type silicon wafer having resistivity of 0.1 Ω · cm to 100 Ω · cm and crystal orientation of <100>, the natural oxide film was removed, Using the slurry composition thus prepared, a concentrated solution of the slurry composition was diluted 20 times with water and used as a polishing solution, and a polishing treatment was applied under the following conditions.

(One) Grinding machine: Okamoto machine Tool Works Ltd.'s 12-inch single side grinding machine model SPP800S

(2) Wafer head: template type

(3) Polishing pad: SPM3100 from Dow Corp.

(4) Platen rotational speed: 31 rpm

(5) Number of revolutions of polishing pad: 33 rpm

(6) Polishing pressure: 3 psi = 210 g / cm ² = 20.7 kPa

(7) Slurry feed rate: 500 mL / min (free flow)

After polishing, the silicon wafer was subjected to batch cleaning at 23 DEG C for 20 minutes with SC-1 (a solution containing ammonia (29 wt% aqueous solution), hydrogen peroxide (31 wt% aqueous solution) and pure water in a ratio of 1: 1: 4 (Solution containing ammonia (29 wt% aqueous solution), hydrogen peroxide (31 wt% aqueous solution), and pure water in a ratio of 1: 4: 20 (volume ratio)) and SC-1 (Shibaura Mechatronics Corp.) After further scrubbing with PVA brush at 23 ° C using a model SC-200S Brush Scrubber, rinse with pure water.

3. Measurement method

The DWO haze value measured in the dark background incident light channel (DWO) mode using the Surfscan SP2 manufactured by KLA-Tencor Ltd. was calculated as the surface roughness of the surface of the silicon wafer after polishing (Haze). &Lt; / RTI &gt; The LPD values used were similarly determined in the dark night incident channel (DCO) mode using the Surfscan SP2 from KLA-Tencor Corporation. Nanoscale polishing defects are defined as the number of signals having an intensity lower than the intensity of the LPD signal and the scattering intensity from the surface is locally greater than the intensity of the reference value. More specifically, in the present embodiment, evaluation was made by counting the number of signals observed in the set area. Each of the measured values was measured at least twice under the same conditions for the same additive and the average value was used to perform relative evaluation of Excellent (A), Good (B), Average (C), or Bad (E).

4. Results

The measurement results are shown in Table 2 below.

Further, a rinse composition containing no abrasive grains was prepared, and the abrasive substrates of Examples 1 and 2 were rubbed by brush scrubbing with the rinse composition following the above polishing, and LPD, haze (DWO), and nanoscale polishing defects were evaluated , Favorable results were obtained.

As described above, according to the present invention, it is possible to provide a slurry composition and a substrate polishing method capable of simultaneously improving haze, LPD and nanoscale polishing defects.

While the present invention has been described with reference to the embodiment thereof, it is to be understood that the invention is not limited to the disclosed embodiments, but may be modified within the scope of the other embodiments, additions, Are included in the scope of the present invention as long as they exert the action and effect of the present invention in any form.

Claims (15)

water,
Abrasive particles, and
At least one water-soluble polymer containing a polyvinyl alcohol structural unit
&Lt; / RTI &gt; The slurry composition of claim 1, wherein the water soluble polymer is at least one water soluble polymer containing a polyoxyalkylene oxide structural unit or a polyvinyl alcohol structural unit, respectively. 3. The water-soluble polymer according to claim 1 or 2, wherein when one of said water-soluble polymers is present in the slurry composition, the polyoxyalkylene oxide structural unit or the polyvinyl alcohol structural unit thereof forms a main skeleton or a side chain of the water- &Lt; / RTI &gt; The slurry composition according to any one of claims 1 to 3, further comprising a pH adjusting agent. The slurry composition according to any one of claims 1 to 4, comprising a water-soluble polymer selected from a cellulosic polymer and a polyalkylene oxide polymer. 6. The slurry composition according to any one of claims 1 to 5, further comprising a haze improving agent. 7. The slurry composition according to any one of claims 1 to 6, comprising from 1 ppm to 5000 ppm of said water soluble polymer. Water, and
One or more polyvinyl alcohol structural units
Wherein the rinse composition for polishing substrate comprises: 9. The rinse composition of claim 8, wherein the water soluble polymer is at least one water soluble polymer each comprising a polyoxyalkylene oxide structural unit or a polyvinyl alcohol structural unit. 10. The water-soluble polymer according to claim 8 or 9, wherein, when one of the water-soluble polymers is present in the rinse composition, the polyoxyalkylene oxide structural unit or the polyvinyl alcohol structural unit forms a main skeleton or a side chain of the water- Lt; / RTI &gt; 11. The rinse composition according to any one of claims 8 to 10, comprising a water-soluble polymer selected from a cellulose-based polymer and a polyalkylene oxide-based polymer. 12. The rinse composition according to any one of claims 8 to 11, further comprising a haze improving agent. 13. The rinse composition according to any one of claims 8 to 12, comprising 1 ppm to 5000 ppm of the water-soluble polymer. A method for manufacturing a polishing slurry, comprising the steps of: adhering the slurry composition according to any one of claims 1 to 7 to a polishing substrate;
And polishing the polishing substrate with a polishing pad using the slurry composition. A rinsing method of a polishing substrate comprising rinsing a polishing substrate with the rinsing composition according to any one of claims 8 to 13.