KR20170076058A - Abrasive particle-dispersion layer complex and polishing slurry composition comprising the same - Google Patents

Abrasive particle-dispersion layer complex and polishing slurry composition comprising the same Download PDF

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KR20170076058A
KR20170076058A KR1020150185821A KR20150185821A KR20170076058A KR 20170076058 A KR20170076058 A KR 20170076058A KR 1020150185821 A KR1020150185821 A KR 1020150185821A KR 20150185821 A KR20150185821 A KR 20150185821A KR 20170076058 A KR20170076058 A KR 20170076058A
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dispersant
polishing
slurry composition
film
group
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KR1020150185821A
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Korean (ko)
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권장국
이성표
권창길
황준하
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주식회사 케이씨텍
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Publication of KR20170076058A publication Critical patent/KR20170076058A/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/14—Anti-slip materials; Abrasives
    • C09K3/1454—Abrasive powders, suspensions and pastes for polishing
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09G—POLISHING COMPOSITIONS; SKI WAXES
    • C09G1/00—Polishing compositions
    • C09G1/02—Polishing compositions containing abrasives or grinding agents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/14—Anti-slip materials; Abrasives
    • C09K3/1454—Abrasive powders, suspensions and pastes for polishing
    • C09K3/1481—Pastes, optionally in the form of blocks or sticks
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/304—Mechanical treatment, e.g. grinding, polishing, cutting
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
    • H01L21/30625—With simultaneous mechanical treatment, e.g. mechanico-chemical polishing

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Physics & Mathematics (AREA)
  • Power Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Mechanical Treatment Of Semiconductor (AREA)
  • Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)

Abstract

Disclosed is an abrasive particle-dispersion layer composite and a polishing slurry composition comprising the same. The abrasive particle-dispersion layer composite according to an embodiment of the present invention comprises abrasive particles; A first dispersant which is at least one cationic compound selected from the group consisting of amino acid, organic acid, polyalkylene glycol and a polysaccharide in which a glucosamine compound is bonded, and a second dispersant which is a cationic polymer containing two or more ionized cations in the molecular formula Dispersing agent; And a third dispersant which is at least one anionic compound selected from the group consisting of a copolymer having a resonance structural group, a carboxyl group-containing polymer and a carboxyl group-containing organic acid.

Description

TECHNICAL FIELD [0001] The present invention relates to abrasive particle-dispersion layer composites, and abrasive slurry compositions containing the same. BACKGROUND ART [0002]

The present invention relates to abrasive particle-dispersion layer composites and polishing slurry compositions comprising the same.

As the semiconductor devices are diversified and highly integrated, a finer pattern forming technique is used, thereby complicating the surface structure of the semiconductor device and increasing the step difference of the surface films. A chemical mechanical polishing (CMP) process is used as a planarization technique for removing a step in a specific film formed on a substrate in manufacturing a semiconductor device. For example, an interlayer dielectric (ILD) and a shallow trench isolation (STI) insulating film for insulation between chips are formed in a process for removing an insulating film formed in an excessive amount for interlayer insulation. And a process for forming a metal conductive film such as wiring, contact plugs, via contacts, and the like. In the CMP process, the slurry is supplied to these contact portions while the polishing pad is in contact with the surface of the wafer to be processed, while the wafer and the polishing pad are relatively moved while chemically reacting the surface of the wafer to chemically react and planarize It is a wide-area planarization technology. In the CMP process, the polishing rate, the degree of planarization of the polishing surface and the degree of occurrence of scratches are important, and they are determined by the CMP process conditions, the kind of slurry, the type of polishing pad, and the like. As the degree of integration increases and the specification of the process becomes more rigid, it is necessary to rapidly planarize the insulating film having a very large step difference. Therefore, it is necessary to develop an abrasive having an automatic stop function because the step removal speed is early in the initial stage of polishing and the polishing speed becomes very slow after the step difference is removed. On the other hand, the mixed single layer type slurry using the anionic polymer and the anionic copolymer can realize the selectivity and the high polishing rate in the high-stage region, but it is difficult to control the flatness and the dishing in the low-stage region do. In addition, there is a problem that the scratch occurrence probability is high due to the inherent hardness of abrasive grains.

SUMMARY OF THE INVENTION It is an object of the present invention to solve the above-described problems, and an object of the present invention is to provide a polishing apparatus and a method of polishing a polishing target which have a high polishing rate and a high selectivity in a high- Disclosed is an abrasive particle-dispersion layer composite which is very slow and can realize an automatic stop function and is excellent in dishing and scratch improvement, and a polishing slurry composition containing the same.

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

According to a first aspect of the present invention, there is provided a polishing composition comprising abrasive grains; A first dispersant which is at least one cationic compound selected from the group consisting of amino acid, organic acid, polyalkylene glycol and a polysaccharide in which a glucosamine compound is bonded, and a second dispersant which is a cationic polymer containing two or more ionized cations in the molecular formula Dispersing agent; And a third dispersant which is at least one anionic compound selected from the group consisting of a copolymer having a resonance structural group, a carboxyl group-containing polymer and a carboxyl group-containing organic acid.

The bond between the abrasive grains and at least one of the first dispersant and the second dispersant is a chemical bond, and the bond between the at least one dispersant and the third dispersant is an electrostatic bond.

The abrasive particle surface, the first dispersant and the second dispersant may exhibit a positive charge, and the third dispersant may exhibit a negative charge.

The cationic polymer may comprise two or more of the cations activated by nitrogen.

At least one of the first dispersant and the second dispersant is contained in the abrasive particle-dispersion layer composite in an amount of 0.1 to 5 wt%, and the third dispersant is contained in the abrasive particle- % To 10% by weight.

The abrasive particle-dispersion layer composite may be formed of a material selected from the group consisting of polyethylene glycol (PEG), polypropylene glycol (PPG), polyethylene-propylene copolymer, polyalkyl oxide, polyoxyethylene oxide (PEO) And at least one nonionic compound selected from the group consisting of polyethylene oxide and polypropylene oxide.

The nonionic compound may be contained in the abrasive particle-dispersion layer composite in an amount of 0.01 wt% to 10 wt%.

Wherein the abrasive particles comprise at least one selected from the group consisting of a metal oxide coated with a metal oxide, an organic or inorganic material, and a metal oxide in a colloidal state, and the metal oxide is at least one selected from the group consisting of silica, ceria, zirconia, alumina , At least one selected from the group consisting of titania, barium titania, germania, manganese, and magnesia.

The abrasive particles may be 0.1 wt% to 10 wt% of the abrasive particle-dispersion layer composite.

The diameter of the abrasive grains may be 10 nm to 300 nm.

The abrasive grains may be prepared by a liquid phase method, and the particle surfaces may be dispersed so as to have a positive charge.

According to a second aspect of the present invention, there is provided a polishing slurry composition comprising an abrasive particle-dispersion layer composite according to the first aspect.

The polishing slurry composition may have a pH of 6 to 10.

The polishing slurry composition may have a zeta potential of -20 mV to -60 mV.

When polishing the substrate including the oxide film and the nitride film or the oxide film and the poly film in the blanket wafer using the polishing slurry composition, the polishing selectivity ratio of the oxide film: nitride film or oxide film: poly film may be 10: 1 to 40: have.

The polishing selectivity ratio of the oxide film: nitride film or oxide film: poly film may be 1: 1 to 5: 1 at the time of polishing the oxide film and the nitride film in the pattern wafer using the polishing slurry composition or the substrate including the oxide film and the poly film have.

After polishing the substrate including the oxide film and the nitride film or the oxide film and the poly film using the polishing slurry composition, the amount of dishing may be less than 100 angstroms.

The abrasive particle-dispersion layer composite according to an embodiment of the present invention is characterized in that the dispersing agents surrounding the abrasive particles form an abrasive particle-dispersed layer composite by chemical bonding and electrostatic bonding to increase the amount of dispersant adsorbed on the abrasive particles Thereby reducing the hardness of the abrasive grains and improving the lubricity, aggregated particles and dispersibility.

The polishing slurry composition according to an embodiment of the present invention includes the abrasive particle-dispersed layer composite, whereby the polishing rate in the high-stage region can be quickly removed to polish the oxide film and the nitride film or the oxide film and the poly film, And the polishing rate is very slow after the step is removed, thereby realizing an automatic polishing stop function in the poly-film, and has an excellent effect on dishing and scratch improvement.

1 is a view showing a sectional structure of a wafer after pattern evaluation of a wafer using a slurry composition according to an embodiment of the present invention.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. In the following description of the present invention, detailed description of known functions and configurations incorporated herein will be omitted when it may make the subject matter of the present invention rather unclear. In addition, terms used in this specification are terms used to appropriately express the preferred embodiments of the present invention, which may vary depending on the user, the intention of the operator, or the practice of the field to which the present invention belongs. Therefore, the definitions of these terms should be based on the contents throughout this specification. Like reference symbols in the drawings denote like elements.

Throughout the specification, when an element is referred to as "comprising ", it means that it can include other elements as well, without excluding other elements unless specifically stated otherwise.

Hereinafter, the abrasive particle-dispersion layer composite of the present invention and the polishing slurry composition containing the same will be described in detail with reference to examples and drawings. However, the present invention is not limited to these embodiments and drawings.

According to a first aspect of the present invention, there is provided a polishing composition comprising abrasive grains; A first dispersant which is at least one cationic compound selected from the group consisting of amino acid, organic acid, polyalkylene glycol and a polysaccharide in which a glucosamine compound is bonded, and a second dispersant which is a cationic polymer containing two or more ionized cations in the molecular formula At least one selected from the group consisting of dispersants; And a third dispersant which is at least one anionic compound selected from the group consisting of a copolymer having a resonance structural group, a carboxyl group-containing polymer and a carboxyl group-containing organic acid.

The abrasive particle-dispersion layer composite of the present invention is characterized in that the dispersing agents surrounding the abrasive particles form a dispersed layer by chemical bonding and electrostatic bonding to increase the amount of the dispersing agent adsorbed to the abrasive particles, reduce the hardness of the abrasive particles, , Aggregated particles, and dispersibility.

The abrasive particle-dispersion layer composite according to one embodiment of the present invention is characterized in that the bond between the abrasive particles and at least one of the first dispersant and the second dispersant is a chemical bond and the at least one dispersant and the third dispersant May be an electrostatic coupling.

At least one of the first dispersant and the second dispersant exhibits the same charge as the surface of the abrasive grain and at least one of the first dispersant and the second dispersant and the third dispersant exhibit opposite charges . Therefore, the first dispersant is chemically bonded to the surface of the abrasive grains, the third dispersant is electrostatically bonded to the first dispersant, or the second dispersant is chemically bonded to the abrasive particle surface, and the second The third dispersant is electrostatically bonded to the dispersant or the first dispersant and the second dispersant are chemically bonded to the surface of the abrasive grains and the third dispersant is electrostatically bonded to the first dispersant and the second dispersant have. More specifically, the first dispersant chemically bonds to the surface of the abrasive grains, and the third dispersant can electrostatically bind to the surface of at least one of the second dispersants.

The abrasive particle surface, the first dispersant and the second dispersant may exhibit a positive charge, and the third dispersant may exhibit a negative charge.

The first dispersant may include at least one selected from the group consisting of a polymeric polysaccharide having an amino acid, an organic acid, a polyalkylene glycol, and a glucosamine compound bonded as a cationic compound.

The amino acid has an effect of improving the dispersibility of the abrasive grains and further improving the polishing rate of the insulating film. Wherein the amino acid is selected from the group consisting of arginine, lysine, aspartic acid, glutamic acid, asparagine, glutamine, histidine, proline, tyrosine, tryptophan, serine, threonine, glycine, alanine,? -Alanine, methionine, cysteine, phenylalanine, leucine, valine and isoleucine , And the like.

The organic acid may be at least one selected from the group consisting of picolinic acid, nicotinic acid, isonicotinic acid, fusaric acid, dinicotinic acid, dipiconic acid, lutidonic acid, quinolic acid, glutamic acid, alanine, glycine, cystine, histidine, asparagine, guanidine, hydrazine, , Acetic acid, benzoic acid, oxalic acid, succinic acid, malic acid, malonic acid, citric acid, lactic acid, tricarboxylic acid, tartaric acid, aspartic acid, glutaric acid, adipic acid, suberic acid, fumaric acid, phthalic acid, And at least one selected from the group consisting of acids and salts thereof.

The polyalkylene glycol can improve polishing characteristics such as polishing selectivity and flatness. The polyalkylene glycols may include, for example, polyethylene glycol, polypropylene glycol, and polybutylene glycol.

Wherein the polysaccharide conjugated with the glucosamine compound is selected from the group consisting of chitin, chitosan, chitooligosaccharide, mucopolysaccharide, proteoglycan, heparin, alginic acid, cellulose, hyaruronic acid, carrageenan,? -Glucan and chondroitin sulfate Or at least one of them.

The second dispersant may be a cationic polymer containing two or more ionized cations in the molecular formula. The cationic polymer may comprise two or more of the cations activated by nitrogen. The cationic polymer may be in quaternary ammonium form.

The cationic polymer may be selected from the group consisting of poly (diallyldimethyl ammonium chloride), poly [bis (2-chloroethyl) ether-alt-1,3-bis [3- (dimethylamino) N, N ', N', N'-bis (2-chloroethyl) ether-alt-1,3-bis [3- (dimethylamino) propyl] urea] 2,2 ', 2''-nitrilotris-, polymer with 1,4-diamine having tetramethyl-2-butene-1,4-diamine, dichloro-2-butene and N, N ', N'-tetramethyl-2-butene-1,4-diamine; hydroxyethylcellulose dimethyl diallylammonium chloride copolymer; Acrylamide / diallyldimethylammonium chloride; acrylamide / diallyldimethylammonium chloride; copolymers of acrylamide and quaternized dimethylammonium (meth) acrylate; acrylic acid / diallyldimethylammonium chloride; acrylamide / dimethylaminoethyl methacrylate methyl chloride copolymer; acrylic acid / diallyldimethylammonium chloride copolymer; acrylamide / dimethylaminoethyl methacrylate methyl chloride copolymer; Quaternized hydroxyethyl cellulose, vinylpyrrolidone / quaternized dimethylaminoethyl methacrylate copolymer (Copolymer of vinylpyrrolidone and quaternized dimethylaminoethyl methacrylate); Copolymers of vinylpyrrolidone / quaternized vinylimidazole; copolymers of vinylpyrrolidone and quaternized vinylimidazole; Vinylpyrrolidone / methacrylamidopropylmethylammonium copolymer (Copolymer of vinylpyrrolidone and methacrylamidopropyl trimethylammonium); Poly (2-methacryloxyethyltrimethylammonium chloride); poly (2-methacryloxyethyl) trimethylammonium chloride; Poly (acrylamide 2-methacryloxyethyltrimethyl ammonium chloride), poly [2- (dimethylamino) ethyl methacrylate) methyl chloride] (poly [2- (dimethylaminoethyl methacrylate poly [3-methacrylamidopropyl trimethylammonium chloride], poly [3-methacrylamidopropyl trimethylammonium chloride], poly [3-methacrylamidopropyl trimethylammonium chloride] ); Poly (oxyethylene (dimethylimino) ethylene (dimethylimino) ethylene dichloride] (poly (oxyethylene (ethyleneimine) Terpolymer of acrylic acid, acrylamide and diallyldimethylammonium Chloride); acrylic acid / methacrylamidopropyltrimethylammonium chloride / methyl Vinylpyrrolidone, and quaternized vinylimidazole), vinylpyrrolidone / vinylpyrrolidone / vinylpyrrolidone / quaternized vinylimidazole, polyvinylpyrrolidone / quaternized vinylimidazole, terpolymer of acrylic acid, 2-methacryloxyethyl phosphorylcholine-co-n-butyl methacrylate); poly [(dimethylamino) ethyl acrylate benzyl chloride quaternary salt] (PDMAEA BCQ) and poly [(dimethylamino) ethyl acrylate methyl chloride quaternary salt] (PDMAEA MCQ).

The third dispersant may be at least one selected from the group consisting of a copolymer having a resonance structural functional group, a carboxyl group-containing polymer and a carboxyl group-containing organic acid as the anionic compound. The third dispersant may be at least one selected from the group consisting of polyacrylic acid, polysulfonic acid, ammonium polyacrylate, polymethacrylic acid, polymethacrylic acid ammonium salt, polyacrylic maleic acid, acrylic styrene copolymer, polystyrene / acrylic acid copolymer, polyacrylamide / acrylic acid copolymer , Polyacrylic acid / sulfonic acid copolymer, polysulfonic acid / acrylamide copolymer, and polyacrylic acid / malonic acid copolymer.

At least one of the first dispersant and the second dispersant is contained in the abrasive particle-dispersion layer composite in an amount of 0.1 wt% to 5 wt%, and the third dispersant is contained in the abrasive particle- By weight to 10% by weight. If the first dispersant is less than 0.1% by weight, the second dispersant is less than 0.1% by weight, and the third dispersant is less than 1% by weight, abrasive grains may flocculate, When the second dispersant is more than 5 wt% and the third dispersant is more than 10 wt%, it is difficult to form an abrasive particle-dispersed layer composite. At least one of the first dispersant and the second dispersant can not be added in excess of the content of the third dispersant, and if it exceeds the above range, aggregation and polishing performance may be deteriorated.

The abrasive particle-dispersion layer composite may further include a nonionic compound to realize the polishing function of polishing the polished film. The nonionic compound may be at least one selected from the group consisting of polyethylene glycol (PEG), polypropylene glycol (PPG), polyethylene-propylene copolymer, polyalkyl oxide, polyoxyethylene oxide (PEO), polyethylene oxide polyethylene oxide, and polypropylene oxide. The non-ionic compound may be at least one selected from the group consisting of polyethylene oxide and polypropylene oxide.

The nonionic compound may be contained in the abrasive particle-dispersion layer composite in an amount of 0.01 wt% to 10 wt%. If the amount of the nonionic compound is less than 0.01% by weight, the polymembrane stopping function may not be realized, and the polymalee may be excessively polished. If the nonionic compound is more than 10% by weight, dispersion stability may be lowered and micro scratches may occur .

Wherein the abrasive particles comprise at least one selected from the group consisting of a metal oxide coated with a metal oxide, an organic or inorganic material, and a metal oxide in a colloidal state, and the metal oxide is at least one selected from the group consisting of silica, ceria, zirconia, alumina , At least one selected from the group consisting of titania, barium titania, germania, manganese, and magnesia.

The abrasive particles may be 0.1 wt% to 10 wt% of the abrasive particle-dispersion layer composite. If the abrasive grains are less than 0.1% by weight, the polishing rate is lowered. If the abrasive grains are more than 10% by weight, there is a concern that the abrasive grains may cause defects.

The diameter of the abrasive grains may be 10 nm to 300 nm. When the diameter of the abrasive grains is less than 10 nm, the size of the abrasive grains-dispersed layer composite is small, resulting in a decrease in the polishing rate. When the diameter exceeds 300 nm, the size of the abrasive grains- It is difficult to control dishing, surface defects, polishing rate, and selection ratio.

The abrasive grains may include those prepared by the liquid phase method. The liquid phase method includes a sol-gel method in which an abrasive particle precursor is caused to undergo a chemical reaction in an aqueous solution and crystals are grown to obtain fine particles, a coprecipitation method in which abrasive particle ions are precipitated in an aqueous solution, A hydrothermal synthesis method such as a hydrothermal synthesis method. The abrasive grains produced by the liquid phase method are dispersed so that the surfaces of the abrasive grains have a positive charge.

The abrasive grains may be monocrystalline. When monocrystalline abrasive grains are used, the scratch reduction effect can be achieved compared to the polycrystalline abrasive grains, the dishing can be improved, and the cleaning ability after polishing can be improved.

The shape of the abrasive grains may be at least one selected from the group consisting of spherical, angular, needle-like, and plate-like shapes, and may be spherical.

The abrasive particle-dispersion layer composite according to an embodiment of the present invention has a negative charge, increases the amount of the dispersant adsorbed on the abrasive particles, decreases the hardness of the abrasive particles, and increases lubricity, aggregated particles, .

According to a second aspect of the present invention, there is provided a polishing slurry composition comprising an abrasive particle-dispersion layer composite according to the first aspect.

The polishing slurry composition according to the present invention has a high selectivity in the polishing of the oxide film at a high stage difference region by removing the polishing rate in a high stage region and has a high polishing rate after the polishing step is removed, To implement the automatic polishing stop function. Further, it has an excellent effect on dishing and scratch improvement of the film to be polished after polishing.

The polishing slurry composition according to the present invention is characterized by comprising an inorganic acid or an inorganic acid salt containing at least one selected from the group consisting of nitric acid, hydrochloric acid, phosphoric acid, sulfuric acid, hydrofluoric acid, bromic acid, iodic acid and salts thereof; And organic acids such as formic acid, malonic acid, maleic acid, oxalic acid, acetic acid, citric acid, adipic acid, acetic acid, propionic acid, fumaric acid, lactic acid, salicylic acid, pimelic acid, benzoic acid, succinic acid, phthalic acid, butyric acid, glutaric acid, An organic acid or an organic acid salt containing at least one selected from the group consisting of glycolic acid, lactic acid, aspartic acid, tartaric acid and salts thereof.

The pH adjusting agent may be added in an amount to adjust the pH of the polishing slurry composition, and the pH of the polishing slurry composition according to the present invention may have a pH range of 6 to 10. [

The polishing slurry composition may have a negative zeta potential with a zeta potential of -20 mV to -60 mV.

When the substrate including the oxide film and the nitride film or the oxide film and the poly film using the polishing slurry composition is polished, the oxide film can be polished at a high speed, and the oxide film is polished to 1,000 angstroms / min or more, Lt; / RTI >

When the patterned wafer is polished using the polishing slurry composition, a high polishing rate can be ensured not only in a wafer having a small pattern density but also in a wafer having a large pattern density.

The polishing selectivity ratio of the oxide film: nitride film or oxide film: poly film in the blanket wafer may be 10: 1 to 40: 1 when polishing the substrate including the oxide film and the nitride film or the oxide film and the poly film using the polishing slurry composition, And may have a nitride film or a poly-film automatic polishing stop function. Further, when evaluating the dishing by overpolishing when the polishing stopper film is exposed on the pattern wafer, it is preferable that the polishing selectivity ratio of the oxide film: nitride film or oxide film: poly film is 1: 1 to 5: 1, preferably 1: 3: 1 < / RTI >

The polishing slurry composition may have a dishing generation amount of 100 angstroms or less and a scratch generation amount of 50 ea or less after polishing a substrate including an oxide film and a nitride film or an oxide film and a poly film.

The abrasive particle-dispersion layer composite according to an embodiment of the present invention may have high stability in the polishing slurry composition.

Hereinafter, the present invention will be described in detail with reference to the following examples and comparative examples. However, the technical idea of the present invention is not limited or limited thereto.

[Example 1]

5 wt% of colloidal cerium oxide abrasive grains having an average particle size of 100 nm were added to the solvent, and 2 wt% of picolinic acid and 2 wt% of poly [bis (2-chloroethyl) Dispersed layer composite was prepared by mixing 1% by weight of an acrylic-styrene-ethylene-ether-aldehyde-1,3-bis [3- (dimethylamino) propyl] urea as a dispersing agent and 5% by weight of an acrylic styrene copolymer as a third dispersing agent . Nitric acid was added to the slurry composition containing the prepared abrasive particle-dispersion layer composite to prepare a polishing slurry composition having a pH of 8.

[Example 2]

A polishing slurry composition was prepared in the same manner as in Example 1 except that only the second dispersant and the third dispersant were added.

[Example 3]

A polishing slurry composition was prepared in the same manner as in Example 1 except that only the first dispersant and the third dispersant were added.

[Comparative Example]

A polishing slurry composition was prepared in the same manner as in Example 1 except that only the third dispersant was added.

Using the polishing slurry compositions of Examples 1 to 3 and Comparative Examples thus prepared, the silicon pattern wafers were polished under the following polishing conditions.

[Polishing condition]

1. Grinder: AP-300 (CTS)

2. Pad: K7 (Rohm & Hass)

3. Polishing time: 60 s

Table RPM (Table RPM): 87

5. Spindle RPM: 93

6. Flow rate: 300 ml / min

7. Wafers used: line / space 100 占 퐉 / 100 占 퐉 pattern wafer (NIT (nitride film) 1,000 Å, HDP (oxide film) 2,000 Å on Si) 12-inch wafer

8. Pressure: 4.0 psi

1 is a view showing a sectional structure of a wafer after pattern evaluation of a wafer using a slurry composition according to an embodiment of the present invention. Based on the information of the patterned wafer shown in Fig. 1, the initial step was removed to 1,200 Å to 1,400 Å in steps and 1,000 Å in steps of the silicon oxide film in the primary polishing, and then the over polishing was further performed for 40 seconds in the secondary polishing, Respectively.

Table 1 below shows the polishing rate and the dishing results after pattern wafer polishing using the polishing slurry composition including the abrasive particle-dispersion layer composite of Examples 1 to 3 of the present invention and the polishing slurry composition of the comparative example.

Item 1st
Dispersant Second
Dispersant Third
Dispersant Overpolishing
(Oxide
1,000 Å
Removal criteria) Abrasion rate
(Å / min) Dishing (Å) Pattern density
(100 탆 / 100 탆) Example 1 ○ ○ ○ 50% 1601 41 Example 2 × ○ ○ 50% 1622 71 Example 3 ○ × ○ 50% 1810 75 Comparative Example × × ○ 50% 1720 105

Referring to Table 1, it can be confirmed that the polishing slurry composition of Example 2 using the second dispersant and the third dispersant, as compared with the slurry composition of the comparative example using only the third dispersant, has excellent dishing less than 100 Å. It can be seen that the polishing rate of the slurry composition of Example 3 using the first dispersant and the third dispersant together is higher than that of the polishing slurry composition of Example 2. [ The slurry composition of Example 1 using both the first dispersant, the second dispersant, and the third dispersant was able to significantly reduce the dishing to 41 Å while maintaining an excellent polishing rate, as compared with the polishing slurry composition of the comparative example. Therefore, it can be seen that the polishing slurry compositions of Examples 1 to 3 including the abrasive particle-dispersion layer composite of the present invention have excellent dishing improving effect.

While the invention has been shown and described with reference to certain preferred embodiments thereof, it will be understood by those of ordinary skill in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims. This is possible. Therefore, the scope of the present invention should not be limited by the described embodiments, but should be determined by the equivalents of the appended claims, as well as the appended claims.

Claims (17)

Abrasive particles;
A first dispersant which is at least one cationic compound selected from the group consisting of amino acid, organic acid, polyalkylene glycol and a polysaccharide in which the glucosamine compound is bonded, and a second dispersant which is a cationic polymer containing two or more ionized cations in the molecular formula Dispersing agent; And
A third dispersant which is at least one anionic compound selected from the group consisting of a copolymer having a resonance structural group, a carboxyl group-containing polymer and a carboxyl group-containing organic acid;
≪ / RTI >
The method according to claim 1,
Wherein at least one of the abrasive particles and the first dispersant and the second dispersant is in a chemical bond and the bond between the at least one dispersant and the third dispersant is an electrostatic bond, Complex.
The method according to claim 1,
Wherein the abrasive particle surface, the first dispersant and the second dispersant exhibit a positive charge and the third dispersant exhibits a negative charge.
The method according to claim 1,
Wherein the cationic polymer comprises two or more cations activated by nitrogen.
The method according to claim 1,
At least one of the first dispersant and the second dispersant is contained in the abrasive particle-dispersion layer composite in an amount of 0.1 wt% to 5 wt%
Wherein the third dispersant is included in the abrasive particle-dispersion layer composite in an amount of 1 wt% to 10 wt%
Abrasive particle-dispersion layer composite.
The method according to claim 1,
The abrasive particle-dispersion layer composite may be formed of a material selected from the group consisting of polyethylene glycol (PEG), polypropylene glycol (PPG), polyethylene-propylene copolymer, polyalkyl oxide, polyoxyethylene oxide (PEO) Wherein the abrasive particles further comprise at least one nonionic compound selected from the group consisting of polyethylene oxide and polypropylene oxide.
The method according to claim 6,
Wherein the nonionic compound is contained in the abrasive particle-dispersion layer composite in an amount of 0.01 wt% to 10 wt%.
The method according to claim 1,
Wherein the abrasive particles comprise at least one selected from the group consisting of a metal oxide coated with a metal oxide, an organic or inorganic material, and a metal oxide in a colloidal state,
Wherein the metal oxide comprises at least one selected from the group consisting of silica, ceria, zirconia, alumina, titania, barium titania, germania, manganese and magnesia.
The method according to claim 1,
Wherein the abrasive grains are 0.1 wt% to 10 wt% of the abrasive grain-dispersion layer composite.
The method according to claim 1,
Wherein the diameter of the abrasive grains is 10 nm to 300 nm.
The method according to claim 1,
Wherein the abrasive particles are produced by a liquid phase method and are dispersed so that the particle surfaces have a positive charge.
A polishing slurry composition comprising an abrasive particle-dispersion layer composite according to any one of claims 1 to 11.
13. The method of claim 12,
Wherein the polishing slurry composition has a pH of from 6 to 10.
13. The method of claim 12,
Wherein the polishing slurry composition has a zeta potential of -20 mV to -60 mV.
13. The method of claim 12,
The polishing selectivity ratio of the oxide film: the nitride film or the oxide film: the polishing film of the oxide film and the nitride film in the blanket wafer using the polishing slurry composition or the substrate including the oxide film and the poly film is 10: 1 to 40: 1 , A polishing slurry composition.
13. The method of claim 12,
The polishing selectivity ratio of the oxide film: nitride film or oxide film: poly film is 1: 1 to 5: 1 at the time of polishing the oxide film and the nitride film in the pattern wafer using the polishing slurry composition or the substrate including the oxide film and the poly film , A polishing slurry composition.
13. The method of claim 12,
Wherein the amount of generated dishing is 100 A or less after polishing the substrate including the oxide film and the nitride film or the oxide film and the poly film using the polishing slurry composition.
KR1020150185821A 2015-12-24 2015-12-24 Abrasive particle-dispersion layer complex and polishing slurry composition comprising the same KR20170076058A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20200048551A1 (en) * 2018-08-09 2020-02-13 Versum Materials Us, Llc Chemical Mechanical Planarization Composition For Polishing Oxide Materials And Method Of Use Thereof
KR20200141420A (en) * 2018-09-18 2020-12-18 주식회사 케이씨텍 Polishing slurry composition
US20210380842A1 (en) * 2018-11-16 2021-12-09 Kctech Co., Ltd. Polishing slurry composition and method for producing same

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20200048551A1 (en) * 2018-08-09 2020-02-13 Versum Materials Us, Llc Chemical Mechanical Planarization Composition For Polishing Oxide Materials And Method Of Use Thereof
US11718767B2 (en) * 2018-08-09 2023-08-08 Versum Materials Us, Llc Chemical mechanical planarization composition for polishing oxide materials and method of use thereof
KR20200141420A (en) * 2018-09-18 2020-12-18 주식회사 케이씨텍 Polishing slurry composition
US20210380842A1 (en) * 2018-11-16 2021-12-09 Kctech Co., Ltd. Polishing slurry composition and method for producing same

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