WO2013089338A1 - Texture etching solution composition of a crystalline silicon wafer and texture etching method - Google Patents

Texture etching solution composition of a crystalline silicon wafer and texture etching method Download PDF

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WO2013089338A1
WO2013089338A1 PCT/KR2012/007131 KR2012007131W WO2013089338A1 WO 2013089338 A1 WO2013089338 A1 WO 2013089338A1 KR 2012007131 W KR2012007131 W KR 2012007131W WO 2013089338 A1 WO2013089338 A1 WO 2013089338A1
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texture
acid
silicon wafer
composition
compound
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PCT/KR2012/007131
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French (fr)
Korean (ko)
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박면규
이재연
홍형표
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동우화인켐 주식회사
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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
    • C09K13/00—Etching, surface-brightening or pickling compositions
    • 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
    • C09K13/00—Etching, surface-brightening or pickling compositions
    • C09K13/02—Etching, surface-brightening or pickling compositions containing an alkali metal hydroxide
    • 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
    • C09K13/00—Etching, surface-brightening or pickling compositions
    • C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
    • C09K13/06—Etching, surface-brightening or pickling compositions containing an inorganic acid with organic material
    • 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
    • C09K13/00—Etching, surface-brightening or pickling compositions
    • C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
    • C09K13/08—Etching, surface-brightening or pickling compositions containing an inorganic acid containing a fluorine compound
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/02—Details
    • H01L31/0236—Special surface textures
    • H01L31/02363—Special surface textures of the semiconductor body itself, e.g. textured active layers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy

Definitions

  • the present invention relates to a texture etching solution composition and a texture etching method of the crystalline silicon wafer that can improve the light efficiency by minimizing the texture quality variation of each position on the surface of the crystalline silicon wafer.
  • Solar cells which are rapidly spreading in recent years, are electronic devices that directly convert solar energy, which is clean energy, into electricity as a next-generation energy source, and diffuse phosphorus on its surface based on P-type silicon semiconductors containing boron in silicon. It consists of the PN junction semiconductor substrate in which the N type silicon semiconductor layer was formed.
  • the surface of the solar cell silicon wafer constituting the PN junction semiconductor substrate is formed into a fine pyramid structure and the antireflection film is treated.
  • the surface of the silicon wafer textured with the fine pyramid structure increases the intensity of the light absorbed by lowering the reflectance of incident light having a wide wavelength band, thereby improving the performance of the solar cell.
  • U.S. Patent No. 4,137,123 discloses 0.5-10 weight in an anisotropic etching solution containing 0-75% by volume of ethylene glycol, 0.05-50% by weight of potassium hydroxide and the remaining amount of water.
  • a silicon texture etching solution in which% silicon is dissolved is disclosed.
  • this etchant can cause pyramid formation defects to increase the light reflectance and cause a decrease in efficiency.
  • European Patent No. 0477424 discloses a texture etching method of supplying oxygen to a texture etching solution in which silicon is dissolved in ethylene glycol, potassium hydroxide and residual water, that is, performing an air rating process.
  • this etching method has a disadvantage in that it causes poor pyramid formation, which leads to an increase in light reflectivity and a decrease in efficiency, and requires the installation of a separate air rating equipment.
  • Korean Patent No. 0180621 discloses a texture etching solution mixed at a ratio of 0.5-5% potassium hydroxide solution, 3-20% by volume of isopropyl alcohol, and 75-96.5% by volume of deionized water
  • US Patent No. 6,451,218 No. discloses a texture etching solution comprising an alkali compound, isopropyl alcohol, a water soluble alkaline ethylene glycol and water.
  • these etching solutions contain isopropyl alcohol having a low boiling point and need to be added during the texturing process, it is not economical in terms of productivity and cost, and the addition of isopropyl alcohol causes a temperature gradient of the etching solution, resulting in the surface of the silicon wafer.
  • the texture quality variation of each position may increase, resulting in poor uniformity.
  • Patent Document 1 US Patent Publication 4,137,123
  • Patent Document 2 European Patent Publication 0477424
  • Patent Document 3 Korea Patent Publication 10-0180621
  • a texture of a crystalline silicon wafer capable of forming a texture capable of increasing light efficiency and reducing reflectance by minimizing the quality variation of the texture at each location is reduced. It is an object to provide an etching liquid composition.
  • an object of the present invention is to provide a texture etching liquid composition of a crystalline silicon wafer that does not require the addition of a separate etching liquid component and the application of an air rating process during the etching process.
  • Another object of the present invention is to provide a texture etching method using the texture etching liquid composition of the crystalline silicon wafer.
  • Texture etching liquid composition of crystalline silicon wafer containing polycarboxylic acid type polymer 1.
  • polycarboxylic acid-based polymer is a texture etching solution composition of the crystalline silicon wafer comprising a repeating unit represented by the following formula (1):
  • R 1 , R 2 and R 3 are independently of each other hydrogen, an alkyl group having 1 to 5 carbon atoms, or — (CH 2 ) m 2 COOM 2
  • M 1 and M 2 are independently of each other hydrogen, an alkali metal
  • the polycarboxylic acid-based polymer is acrylic acid, methyl (meth) acrylic acid, ethyl (meth) acrylic acid, trimethyl acrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, citraconic acid, vinyl acetate, 4-pen Texture etching liquid composition of a crystalline silicon wafer formed by polymerizing at least one monomer selected from the group consisting of tenic acid and salts thereof.
  • the monomer is an amide compound, an aromatic vinyl compound, an unsaturated carboxylic acid ester compound, an unsaturated anhydride carboxylic acid compound, an unsaturated alcohol compound, a nonionic group addition unsaturated carboxylic acid ester compound, containing a hydroxyl group (meta)
  • metal A polycarboxylic acid polymer is formed by copolymerizing with at least one comonomer selected from the group consisting of an acrylic acid ester compound, a vinyl cyan compound, an aliphatic diene compound, a vinyl halide compound, a sulfonic acid compound and a phosphonic acid compound. Texture etching liquid composition of crystalline silicon wafer.
  • the polycarboxylic acid-based polymer has a weight average molecular weight of 10,000 to 50,000 texture etching liquid composition of the crystalline silicon wafer.
  • the texture etching liquid composition of the crystalline silicon wafer further comprising an alkali compound.
  • composition according to the above 7, wherein the alkali compound is at least one selected from the group consisting of potassium hydroxide, sodium hydroxide, ammonium hydroxide, tetrahydroxymethylammonium and tetrahydroxyethylammonium etch silicon.
  • the texture etching liquid composition of the crystalline silicon wafer further comprising a cyclic compound.
  • the cyclic compound has a boiling point of 100 °C or more texture etching liquid composition of the crystalline silicon wafer.
  • the texture etching solution composition of crystalline silicon wafer further comprising the fluorine-based surfactant as in 1 above.
  • the texture etching liquid composition of the crystalline silicon wafer further comprising a silica compound.
  • the silica compound is fine powder silica; Colloidal silica dispersion stabilized with Na 2 O; Colloidal silica dispersion stabilized with K 2 O; Colloidal silica dispersion stabilized with acid solution; Colloidal silica dispersion stabilized with NH 3 ; Colloidal silica dispersion stabilized with at least one organic solvent selected from the group consisting of ethyl alcohol, propyl alcohol, ethylene glycol, methyl ethyl ketone and methyl isobutyl ketone; Liquid sodium silicate; Liquid potassium silicate; And a liquid etching silicate composition of at least one crystalline silicon wafer selected from the group consisting of liquid lithium silicate.
  • the etching method according to the above 15, comprising spraying the etching solution composition for 30 seconds to 60 minutes at a temperature of 50 to 100 °C.
  • the texture etching solution composition and the texture etching method of the crystalline silicon wafer of the present invention to minimize the quality variation of the texture of each position on the surface of the crystalline silicon wafer, that is to improve the uniformity of the texture to maximize the amount of absorption of sunlight and lower the light reflectance Can be.
  • the texture etching liquid composition and the texture etching method of the crystalline silicon wafer of the present invention it is possible to increase the number of silicon wafers to be processed compared to the amount of the etching liquid composition, and it is not necessary to add a separate etching liquid component during the texturing process and introduce an air rating equipment. There is no need to improve quality and productivity, and it is economical in terms of process cost.
  • FIG. 1 is a SEM photograph showing the texture of a single crystal silicon wafer etched using the etching liquid composition for the texture of the crystalline silicon wafer of Example 1.
  • FIG. 1 is a SEM photograph showing the texture of a single crystal silicon wafer etched using the etching liquid composition for the texture of the crystalline silicon wafer of Example 1.
  • FIG. 2 is an SEM photograph showing the texture pyramid structure of the single crystal silicon wafer etched using the etching liquid composition for the texture of the crystalline silicon wafer of Example 1.
  • FIG. 2 is an SEM photograph showing the texture pyramid structure of the single crystal silicon wafer etched using the etching liquid composition for the texture of the crystalline silicon wafer of Example 1.
  • the present invention relates to a texture etching solution composition and texture of a crystalline silicon wafer comprising a polycarboxylic acid-based polymer and salts thereof, thereby forming a uniform fine pyramid structure on the surface of the crystalline silicon wafer to produce a low light reflectance texture. It relates to an etching method.
  • the texture etching solution composition of the crystalline silicon wafer of the present invention is characterized in that it comprises a polycarboxylic acid-based polymer.
  • the polycarboxylic acid-based polymer not only serves to reduce the etching rate difference between the Si 100 direction and the Si 111 direction by controlling the activity of OH - ions in the texture solution, thereby improving the wettability of the crystalline silicon surface. Rapid dropping of the etched and dissolved hydrogen bubbles prevents the bubble stick phenomenon from occurring.
  • the polycarboxylic acid-based polymer according to the present invention may be suitably used as long as it is a polymer having a carboxylic acid functional group, and more specifically, may include a repeating unit represented by the following Chemical Formula 1.
  • R 1 , R 2 and R 3 are independently of each other hydrogen, an alkyl group having 1 to 5 carbon atoms, or — (CH 2 ) m 2 COOM 2
  • M 1 and M 2 are independently of each other hydrogen, an alkali metal
  • m 1 and m 2 are each independently an integer of 0 to 2.
  • sodium or potassium is preferable as alkali metal;
  • alkaline earth metal magnesium and calcium are preferable;
  • As the alkylammonium group having 1 to 10 carbon atoms dimethyl ammonium, methylethylammonium, diethylammonium, trimethylammonium, triethylammonium, tetramethylammonium and the like are preferred.
  • Monoethanol ammonium, diisopropanol ammonium, etc. are preferable.
  • the polycarboxylic acid-based polymer according to the present invention may be formed by polymerizing a monomer capable of forming the repeating unit, for example acrylic acid, methyl (meth) acrylic acid, ethyl (meth) acrylic acid, trimethyl acrylic acid, maleic acid, fumaric acid , Monomers such as itaconic acid, crotonic acid, citraconic acid, vinyl acetic acid, 4-pentenoic acid, and salts thereof may be formed by polymerization alone or by mixing two or more kinds thereof, and thus a homopolymer or It may be a copolymer.
  • the aforementioned monomers may be selected from amide compounds such as acrylamide, methacrylamide, alkyl (meth) acrylamides having 1 to 5 carbon atoms; Aromatic vinyl compounds such as styrene, alpha-methylstyrene, vinyltoluene and styrene chloride; Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-amyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, ethylhexyl (meth) Acrylate, octyl (meth) acrylate, diethyl maleate, dimethyl itacate, (poly) ethylene glycol mono (meth) acrylate, (poly) propylene glycol mono (meth) acrylate, (poly) butylene glycol mono ( Unsaturation of
  • the polycarboxylic acid-based polymer according to the present invention can be prepared by adopting an appropriate one from various polymerization methods known in the art, the production method is not particularly limited.
  • the polycarboxylic acid-based polymer according to the present invention preferably has a weight average molecular weight of 10,000 to 50,000.
  • a weight average molecular weight in the above range there is an advantage that can prevent over-etching.
  • the polycarboxylic acid-based polymer according to the present invention may be included in an appropriate amount of the texture etching solution composition of the crystalline silicon wafer, for example, may be included in 0.1 to 20% by weight, preferably 0.1 to 5% by weight relative to the total weight of the composition. It is not limited to this. The effect of forming a uniform texture is most preferred in the above content range.
  • the polycarboxylic acid-based polymer according to the present invention can be applied to the texture etching solution composition of the crystalline silicon wafer commonly used in the art.
  • Crystalline silicon wafers typically comprise an alkali compound.
  • any alkaline compound commonly used in the art may be used without limitation.
  • the alkali compound that can be used include potassium hydroxide, sodium hydroxide, ammonium hydroxide, tetrahydroxymethylammonium, tetrahydroxyethylammonium, and the like, with potassium hydroxide and sodium hydroxide being preferred. These can be used individually or in mixture of 2 or more types.
  • the alkali compound is preferably included in an amount of 0.1 to 20% by weight based on the total weight of the texture etching solution composition of the crystalline silicon wafer, more preferably 1 to 5% by weight. When the content falls within the above range, the silicon wafer surface can be etched.
  • the texture etchant composition of the crystalline silicon wafer of the present invention may further comprise a cyclic compound.
  • the cyclic compound is preferably a cyclic hydrocarbon having 4-10 carbon atoms; And a heterocyclic hydrocarbon having 4 to 10 carbon atoms including one or more heteroatoms of N, O, or S, and improves the wettability of the surface of the crystalline silicon wafer to prevent overetching by alkali compounds. This minimizes the quality variation of the texture and at the same time rapidly reduces the amount of hydrogen bubbles generated by etching, thereby preventing the occurrence of bubble stick phenomenon.
  • the boiling point can be used in a small amount compared to isopropyl alcohol is conventionally used as well as increase the number of treatment for the same amount of use.
  • a boiling point of a cyclic compound is high as 100 degreeC or more, More preferably, it is 100-400 degreeC, Most preferably, it is 150-400 degreeC.
  • the cyclic compound preferably has a Hansen solubility parameter (HSP) ⁇ p of 6 to 15. Having a boiling point and solubility parameter in the above range is preferable in view of compatibility with other components included in the etching liquid composition.
  • the cyclic compound is not particularly limited as long as it satisfies the boiling point and the solubility parameter of Hansen.
  • Examples thereof include piperazine, morpholine, pyridine, piperidine, piperidone, pyrrolidine, pyrrolidone, Imidazolidinone type, furan type, aniline type, toluidine type, amine type, lactone type, carbonate type, carbazole type compound, etc. are mentioned.
  • piperazine N-methylpiperazine, N-ethylpiperazine, N-vinylpiperazine, N-vinylmethylpiperazine, N-vinylethylpiperazine, N-vinyl-N'-methylpiperazine, N-acryloylpiperazine, N-acryloyl-N'-methylpiperazine, hydroxyethylpiperazine, N- (2-aminoethyl) piperazine, N, N'-dimethylpiperazine; Morpholine, N-methylmorpholine, N-ethylmorpholine, N-phenylmorpholine, N-vinylmorpholine, N-vinylmethylmorpholine, N-vinylethylmorpholine, N-acryloylmorpholine, N Cocomorpholine, N- (2-aminoethyl) morpholine, N- (2-cyanoethyl) morpholine, N- (2-hydroxyethyl) morpho
  • the cyclic compound is preferably included in 0.1 to 50% by weight, more preferably 1 to 10% by weight relative to the total weight of the composition. If the content falls within the above range, uniformity may be improved by effectively improving the wettability of the silicon wafer surface to minimize texture quality variation.
  • the cyclic compound may be mixed with a water soluble polar solvent.
  • the water-soluble polar solvent is not particularly limited as long as it is compatible with other components and water included in the texture etching solution composition of the crystalline silicon wafer, and both proton or aprotic polar solvents can be used.
  • ethylene glycol monomethyl ether As a proton polar solvent, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, polyethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, ethylene glycol monobutyl ether Ether compounds such as diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, propylene glycol monomethyl ether and dipropylene glycol monomethyl ether; Alcohol compounds such as propanol, butanol, isopropanol, tetrahydroperfuryl alcohol, ethylene glycol, propylene glycol and the like, and the like, and aprotic polar solvents such as N-methylformamide, N, N-dimethylformamide, etc.
  • aprotic polar solvents such as N-methylformamide, N, N-dimethylformamide, etc.
  • Sulfoxide compounds such as dimethyl sulfoxide and sulfolane
  • Phosphate type compounds such as a triethyl phosphate and a tributyl phosphate, etc. are mentioned. These can be used individually or in mixture of 2 or more types.
  • the water soluble polar solvent may be included in an amount of 0.1 to 30% by weight based on 100% by weight of the cyclic compound.
  • the texture etching solution composition of the crystalline silicon wafer of the present invention may further include a surfactant.
  • a surfactant used in the art may be used, and preferably a fluorine-based surfactant may be used.
  • the fluorine-based surfactant lowers the surface tension of the texture solution to improve the wettability of the crystalline silicon surface to prevent over-etching by the alkali compound.
  • fluorine-based surfactants examples include anionic surfactants, cationic surfactants, amphoteric surfactants, and nonionic surfactants, which may be used alone or in combination of two or more. .
  • anionics such as perfluoroalkyl carboxylate, perfluoroalkyl sulfonate, perfluoroalkyl sulfate, and fluoroalkyl phosphate
  • Cationic systems such as perfluoroalkyl amine salts and perfluoroalkyl quaternized ammonium salts
  • Amphoteric ionic systems such as perfluoroalkyl carboxy betaine and perfluoroalkyl sulfobetaine
  • nonionics such as fluorinated alkyl polyoxyethylene and perfluoroalcohol polyoxyethylene.
  • the alkyl group in the surfactant may be an alkyl group having 1 to 10 carbon atoms.
  • the surfactant may be included in an amount of 10 -6 to 10% by weight, preferably 10 -4 to 1% by weight based on the total weight of the composition. If the content falls within the above range, uniformity may be improved by effectively improving the wettability of the silicon wafer surface to minimize texture quality variation.
  • the texture etchant composition of the crystalline silicon wafer of the present invention may further comprise a silica compound.
  • the silica compound is a component that allows the crystalline silicon wafer surface to have a fine pyramid shape by physically adsorbing on the surface of the crystalline silicon wafer to serve as a kind of mask, and has an excellent effect on the uniform surface of the wafer. Indicates.
  • silica compound which can be used by this invention a powder type, a colloidal dispersion type, a liquid metal silicate compound, etc. are mentioned. Specifically, fine powder silica; Colloidal silica dispersion stabilized with Na 2 O; Colloidal silica dispersion stabilized with K 2 O; Colloidal silica dispersion stabilized with acid solution; Colloidal silica dispersion stabilized with NH 3 ; Colloidal silica dispersion stabilized with at least one organic solvent selected from the group consisting of ethyl alcohol, propyl alcohol, ethylene glycol, methyl ethyl ketone and methyl isobutyl ketone; Liquid sodium silicate; Liquid potassium silicate; And liquid lithium silicate etc. can be mentioned, These can be used individually or in mixture of 2 or more types, respectively.
  • the silica compound may be included in an amount of 10 ⁇ 5 to 10 wt% based on the total weight of the texture etching solution composition of the crystalline silicon wafer, and preferably 10 ⁇ 4 to 1 wt%. If the content falls within the above range, it is possible to easily form a fine pyramid on the surface of the crystalline silicon wafer.
  • the texture etching solution composition of the crystalline silicon wafer according to the present invention after appropriately adopting the above components according to specific needs, water is added to adjust the overall composition so that the remaining amount of the total composition is occupied by water.
  • the components are adjusted to have the aforementioned content ranges.
  • the kind of water is not specifically limited, It is preferable that it is deionized distilled water, More preferably, it is preferable that the specific resistance value is 18 kW / cm or more as deionized distilled water for a semiconductor process.
  • the texture etching solution composition of the crystalline silicon wafer of the present invention comprising the above components, in particular, by including a polymer having a polycarboxylic acid system to minimize the quality variation of the texture by position on the surface of the crystalline silicon wafer, that is, the uniformity of the texture
  • a polymer having a polycarboxylic acid system to minimize the quality variation of the texture by position on the surface of the crystalline silicon wafer, that is, the uniformity of the texture
  • the absorption of sunlight can be maximized and the light reflectance can be lowered to increase the light efficiency.
  • there is no need to add a separate etchant component during the texture etching process and there is no need to introduce an air rating equipment, which is advantageous in terms of productivity and cost.
  • the texture etching liquid composition of the crystalline silicon wafer of the present invention can be applied to all conventional etching processes, such as dip, spray and single wafer etching processes.
  • the present invention provides a texture etching method of a crystalline silicon wafer using the texture etching liquid composition of the crystalline silicon wafer.
  • Texture etching method of the crystalline silicon wafer is a step of depositing the crystalline silicon wafer in the texture etching liquid composition of the crystalline silicon wafer of the present invention, or spraying the texture etching liquid composition of the crystalline silicon wafer of the present invention on the crystalline silicon wafer Or both of the above steps.
  • the number of depositions and sprays is not particularly limited, and the order of both deposition and spraying is not limited.
  • Deposition, spraying or depositing and spraying may be performed for 30 seconds to 60 minutes at a temperature of 50 to 100 ° C.
  • the texture etching method of the crystalline silicon wafer of the present invention does not need to introduce a separate air-rating apparatus for supplying oxygen, so it is economical in terms of initial production and processing costs, and is uniform even in a simple process. It is possible to form the structure, and the shape of the pyramid can also reduce the reflectance by having a structure in which the inclined surface is indented into the pyramid.
  • the single crystal silicon wafers were immersed in the etching liquid composition for texture of the crystalline silicon wafers of Examples 1 to 15 and Comparative Examples 1 to 4, respectively, to etch.
  • the texture conditions at this time were the temperature of 80 degreeC, and time 20 minutes.
  • Texture uniformity was evaluated using visual evaluation (digital camera), optical microscope, SEM, and pyramid size using SEM.
  • Texture reflectance measured the average reflectance when irradiating light with a wavelength range of 400-800 nm using ultraviolet-ray.
  • FIG. 1 is a SEM photograph showing the texture of a single crystal silicon wafer etched using the etching liquid composition for the texture of the crystalline silicon wafer of Example 1, and the texture of the crystalline silicon wafer of Example 1 in FIG. SEM photographs showing the texture pyramid structure of the single crystal silicon wafer etched using the etchant composition were shown. 1 and 2, it can be seen that the texture is uniformly formed over the entire surface of the silicon wafer.
  • Comparative Example 4 shows an inferior effect than the embodiment in terms of texture uniformity, pyramid size, reflectance.

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Abstract

The present invention relates to a texture etching solution composition of a crystalline silicon wafer and to a texture etching method, and more particularly, to a texture etching solution composition containing a polycarboxylic acid-based polymer and a salt thereof to form a uniform fine pyramid structure on the surface of a crystalline silicon wafer to thereby manufacture a texture having low optical reflection, and to a texture etching method.

Description

결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물 및 텍스쳐 에칭방법Texture Etching Compositions and Texture Etching Methods of Crystalline Silicon Wafers
본 발명은 결정성 실리콘 웨이퍼 표면의 위치별 텍스쳐 품질 편차를 최소화하여 광효율을 높일 수 있는 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물 및 텍스쳐 에칭방법에 관한 것이다.The present invention relates to a texture etching solution composition and a texture etching method of the crystalline silicon wafer that can improve the light efficiency by minimizing the texture quality variation of each position on the surface of the crystalline silicon wafer.
최근 들어 급속하게 보급되고 있는 태양전지는 차세대 에너지원으로서 클린 에너지인 태양 에너지를 직접 전기로 변환하는 전자 소자로서, 실리콘에 붕소를 첨가한 P형 실리콘 반도체를 기본으로 하여 그 표면에 인을 확산시켜 N형 실리콘 반도체층을 형성시킨 PN 접합 반도체 기판으로 구성되어 있다.Solar cells, which are rapidly spreading in recent years, are electronic devices that directly convert solar energy, which is clean energy, into electricity as a next-generation energy source, and diffuse phosphorus on its surface based on P-type silicon semiconductors containing boron in silicon. It consists of the PN junction semiconductor substrate in which the N type silicon semiconductor layer was formed.
PN 접합에 의해 전계가 형성된 기판에 태양광과 같은 빛을 조사할 경우 반도체 내의 전자(-)와 정공(+)이 여기되어 반도체 내부를 자유로이 이동하는 상태가 되며, 이러한 PN 접합에 의해 생긴 전계에 들어오게 되면 전자(-)는 N형 반도체에, 정공(+)은 P형 반도체에 이르게 된다. P형 반도체와 N형 반도체 표면에 전극을 형성하여 전자를 외부회로로 흐르게 하면 전류가 발생하게 되는데, 이와 같은 원리로 태양 에너지가 전기 에너지로 변환된다. 따라서 태양 에너지의 변환 효율을 높이기 위해서 PN 접합 반도체 기판의 단위 면적당 전기적 출력을 극대화시켜야 하며, 이를 위해서 반사율은 낮게 하고 광 흡수량은 최대화시켜야 한다. 이러한 점을 고려하여 PN 접합 반도체 기판을 구성하는 태양전지용 실리콘 웨이퍼의 표면을 미세 피라미드 구조로 형성시키고 반사 방지막을 처리하고 있다. 미세 피라미드 구조로 텍스쳐링된 실리콘 웨이퍼의 표면은 넓은 파장대를 갖는 입사광의 반사율을 낮춰 기 흡수된 광의 강도를 증가시킴으로써 태양전지의 성능, 즉 효율을 높일 수 있게 된다.When light such as sunlight is irradiated onto a substrate on which an electric field is formed by a PN junction, electrons (-) and holes (+) in the semiconductor are excited to move freely inside the semiconductor, and the electric field generated by the PN junction Upon entering, electrons (-) reach the N-type semiconductor and holes (+) reach the P-type semiconductor. When electrodes are formed on the surfaces of the P-type semiconductor and the N-type semiconductor to flow electrons to an external circuit, current is generated. Solar energy is converted into electrical energy based on the same principle. Therefore, in order to increase the conversion efficiency of solar energy, the electrical output per unit area of the PN junction semiconductor substrate should be maximized. For this purpose, the reflectance should be low and the light absorption amount should be maximized. In view of this point, the surface of the solar cell silicon wafer constituting the PN junction semiconductor substrate is formed into a fine pyramid structure and the antireflection film is treated. The surface of the silicon wafer textured with the fine pyramid structure increases the intensity of the light absorbed by lowering the reflectance of incident light having a wide wavelength band, thereby improving the performance of the solar cell.
실리콘 웨이퍼 표면을 미세 피라미드 구조로 텍스쳐하는 방법으로, 미국특허 제4,137,123호에는 0-75부피%의 에틸렌글리콜, 0.05-50중량%의 수산화칼륨 및 잔량의 물을 포함하는 이방성 에칭액에 0.5-10중량%의 실리콘이 용해된 실리콘 텍스쳐 에칭액이 개시되어 있다. 그러나, 이 에칭액은 피라미드 형성 불량을 일으켜 광 반사율을 증가시키고 효율의 저하를 초래할 수 있다.As a method of texturing a silicon wafer surface with a fine pyramid structure, U.S. Patent No. 4,137,123 discloses 0.5-10 weight in an anisotropic etching solution containing 0-75% by volume of ethylene glycol, 0.05-50% by weight of potassium hydroxide and the remaining amount of water. A silicon texture etching solution in which% silicon is dissolved is disclosed. However, this etchant can cause pyramid formation defects to increase the light reflectance and cause a decrease in efficiency.
또한, 유럽특허 제0477424호에는 에틸렌글리콜, 수산화칼륨 및 잔량의 물에 실리콘을 용해시킨 텍스쳐 에칭액에 산소를 공급시키는, 즉 에어레이팅 공정을 수행하는 텍스쳐 에칭 방법이 개시되어 있다. 그러나, 이 에칭 방법은 피라미드 형성 불량을 일으켜 광 반사율 증가와 효율의 저하를 초래할 뿐만 아니라 별도의 에어레이팅 장비의 설치를 필요로 한다는 단점이 있다.In addition, European Patent No. 0477424 discloses a texture etching method of supplying oxygen to a texture etching solution in which silicon is dissolved in ethylene glycol, potassium hydroxide and residual water, that is, performing an air rating process. However, this etching method has a disadvantage in that it causes poor pyramid formation, which leads to an increase in light reflectivity and a decrease in efficiency, and requires the installation of a separate air rating equipment.
또한, 한국등록특허 제0180621호에는 수산화칼륨 용액 0.5-5%, 이소프로필알코올 3-20부피%, 탈이온수 75-96.5부피%의 비율로 혼합된 텍스쳐 에칭 용액이 개시되어 있고, 미국특허 제6,451,218호에는 알칼리 화합물, 이소프로필알코올, 수용성 알카리성 에틸렌글리콜 및 물을 포함하는 텍스쳐 에칭 용액이 개시되어 있다. 그러나, 이들 에칭 용액은 비점이 낮은 이소프로필알코올을 포함하고 있어 텍스쳐 공정 중 이를 추가 투입해야 하므로 생산성 및 비용 면에서 경제적이지 못하며, 추가 투입된 이소프로필알코올로 인해 에칭액의 온도 구배가 발생하여 실리콘 웨이퍼 표면의 위치별 텍스쳐 품질 편차가 커져 균일성이 떨어질 수 있다.In addition, Korean Patent No. 0180621 discloses a texture etching solution mixed at a ratio of 0.5-5% potassium hydroxide solution, 3-20% by volume of isopropyl alcohol, and 75-96.5% by volume of deionized water, US Patent No. 6,451,218 No. discloses a texture etching solution comprising an alkali compound, isopropyl alcohol, a water soluble alkaline ethylene glycol and water. However, since these etching solutions contain isopropyl alcohol having a low boiling point and need to be added during the texturing process, it is not economical in terms of productivity and cost, and the addition of isopropyl alcohol causes a temperature gradient of the etching solution, resulting in the surface of the silicon wafer. The texture quality variation of each position may increase, resulting in poor uniformity.
[선행기술문헌][Preceding technical literature]
[특허문헌][Patent Documents]
(특허문헌 1) 특허문헌 1: 미국 특허공보 4,137,123(Patent Document 1) Patent Document 1: US Patent Publication 4,137,123
(특허문헌 2) 특허문헌 2: 유럽 특허공보 0477424(Patent Document 2) Patent Document 2: European Patent Publication 0477424
(특허문헌 3) 특허문헌 3: 한국 등록특허공보 10-0180621(Patent Document 3) Patent Document 3: Korea Patent Publication 10-0180621
본 발명은 결정성 실리콘 웨이퍼의 표면에 미세 피라미드 구조를 형성함에 있어서 위치별 텍스쳐의 품질 편차를 최소화하여 광 효율을 증가시키고, 반사율을 저감시킬 수 있는 텍스쳐를 형성할 수 있는 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물을 제공하는 것을 목적으로 한다.In the present invention, in forming a fine pyramid structure on the surface of a crystalline silicon wafer, a texture of a crystalline silicon wafer capable of forming a texture capable of increasing light efficiency and reducing reflectance by minimizing the quality variation of the texture at each location is reduced. It is an object to provide an etching liquid composition.
또한, 본 발명은 에칭 공정 중 별도의 에칭액 성분의 투입과 에어레이팅 공정의 적용이 필요 없는 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물을 제공하는 것을 목적으로 한다.In addition, an object of the present invention is to provide a texture etching liquid composition of a crystalline silicon wafer that does not require the addition of a separate etching liquid component and the application of an air rating process during the etching process.
또한, 본 발명은 상기 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물을 이용한 텍스쳐 에칭방법을 제공하는 것을 다른 목적으로 한다.Another object of the present invention is to provide a texture etching method using the texture etching liquid composition of the crystalline silicon wafer.
1. 폴리카르복시산계 고분자를 포함하는 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물.1. Texture etching liquid composition of crystalline silicon wafer containing polycarboxylic acid type polymer.
2. 위 1에 있어서, 폴리카르복시산계 고분자는 하기 화학식 1로 표시되는 반복단위를 포함하는 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물:2. In the above 1, wherein the polycarboxylic acid-based polymer is a texture etching solution composition of the crystalline silicon wafer comprising a repeating unit represented by the following formula (1):
화학식 1
Figure PCTKR2012007131-appb-C000001
 Formula 1
Figure PCTKR2012007131-appb-C000001
(식 중, R1, R2 및 R3는 서로 독립적으로 수소, 탄소수 1 내지 5인 알킬기, 또는 -(CH2)m2COOM2이며, M1 및 M2는 서로 독립적으로 수소, 알칼리 금속, 알칼리 토금속, 암모늄기, 또는 히드록시기로 치환가능한 탄소수 1 내지 10의 알킬암모늄기이며, m1 및 m2는 서로 독립적으로 0 내지 2인 정수임).Wherein R 1 , R 2 and R 3 are independently of each other hydrogen, an alkyl group having 1 to 5 carbon atoms, or — (CH 2 ) m 2 COOM 2 , and M 1 and M 2 are independently of each other hydrogen, an alkali metal , An alkylammonium group having 1 to 10 carbon atoms, which may be substituted with an alkaline earth metal, an ammonium group, or a hydroxy group, and m 1 and m 2 are each independently an integer of 0 to 2).
3. 위 1에 있어서, 폴리카르복시산계 고분자는 아크릴산, 메틸(메타)아크릴산, 에틸(메타)아크릴산, 트리메틸아크릴산, 말레산, 푸마르산, 이타콘산, 크로톤산, 시트라콘산, 비닐초산, 4-펜텐산 및 이들의 염으로 이루어진 군에서 선택되는 적어도 1종의 단량체를 중합하여 형성되는 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물.3. In the above 1, the polycarboxylic acid-based polymer is acrylic acid, methyl (meth) acrylic acid, ethyl (meth) acrylic acid, trimethyl acrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, citraconic acid, vinyl acetate, 4-pen Texture etching liquid composition of a crystalline silicon wafer formed by polymerizing at least one monomer selected from the group consisting of tenic acid and salts thereof.
4. 위 3에 있어서, 상기 단량체는 아미드계 화합물, 방향족비닐계 화합물, 불포화카르복시산에스테르계 화합물, 불포화무수카르복시산계 화합물, 불포화알콜계 화합물, 비이온성기 부가 불포화카르복시산에스테르계 화합물, 히드록시기함유 (메타)아크릴산에스테르계 화합물, 비닐시안계 화합물, 지방족 디엔계 화합물, 할로겐화 비닐계 화합물, 술폰산계 화합물 및 포스폰산계 화합물 이루어진 군에서 선택되는 적어도 1종의 공단량체와 공중합하여 폴리카르복시산계 고분자를 형성하는 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물.4. In the above 3, the monomer is an amide compound, an aromatic vinyl compound, an unsaturated carboxylic acid ester compound, an unsaturated anhydride carboxylic acid compound, an unsaturated alcohol compound, a nonionic group addition unsaturated carboxylic acid ester compound, containing a hydroxyl group (meta A polycarboxylic acid polymer is formed by copolymerizing with at least one comonomer selected from the group consisting of an acrylic acid ester compound, a vinyl cyan compound, an aliphatic diene compound, a vinyl halide compound, a sulfonic acid compound and a phosphonic acid compound. Texture etching liquid composition of crystalline silicon wafer.
5. 위 1에 있어서, 폴리카르복시산계 고분자는 중량평균 분자량이 10,000 내지 50,000인 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물.5. In the above 1, the polycarboxylic acid-based polymer has a weight average molecular weight of 10,000 to 50,000 texture etching liquid composition of the crystalline silicon wafer.
6. 위 1에 있어서, 폴리카르복시산계 고분자는 조성물 총 중량 대비 0.1 내지 20중량%인 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물.6. In the above 1, wherein the polycarboxylic acid-based polymer is 0.1 to 20% by weight of the texture etching solution composition of the crystalline silicon wafer relative to the total weight of the composition.
7. 위 1에 있어서, 알칼리 화합물을 더 포함하는 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물.7. according to the above 1, the texture etching liquid composition of the crystalline silicon wafer further comprising an alkali compound.
8. 위 7에 있어서, 알칼리 화합물은 수산화칼륨, 수산화나트륨, 수산화암모늄, 테트라히드록시메틸암모늄 및 테트라히드록시에틸암모늄으로 이루어진 군으로부터 선택되는 1종 이상인 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물.8. The composition according to the above 7, wherein the alkali compound is at least one selected from the group consisting of potassium hydroxide, sodium hydroxide, ammonium hydroxide, tetrahydroxymethylammonium and tetrahydroxyethylammonium etch silicon.
9. 위 1에 있어서, 고리형 화합물을 더 포함하는 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물.9. according to the above 1, the texture etching liquid composition of the crystalline silicon wafer further comprising a cyclic compound.
10. 위 9에 있어서, 고리형 화합물은 비점이 100℃ 이상인 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물.10. In the above 9, the cyclic compound has a boiling point of 100 ℃ or more texture etching liquid composition of the crystalline silicon wafer.
11. 위 9에 있어서, 고리형 화합물은 한센의 용해도 파라미터가 6 내지 15인 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물.11. The etch compound according to the above 9, wherein the cyclic compound has a solubility parameter of Hansen of 6 to 15.
12. 위 1에 있어서, 불소계 계면활성제를 더 포함하는 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물.12. The texture etching solution composition of crystalline silicon wafer further comprising the fluorine-based surfactant as in 1 above.
13. 위 1에 있어서, 실리카 화합물을 더 포함하는 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물.13. In the above 1, the texture etching liquid composition of the crystalline silicon wafer further comprising a silica compound.
14. 위 13에 있어서, 상기 실리카 화합물은 미분말 실리카; Na2O로 안정화시킨 콜로이드 실리카 분산액; K2O로 안정화시킨 콜로이드 실리카 분산액; 산성액으로 안정화시킨 콜로이드 실리카 분산액; NH3로 안정화시킨 콜로이드 실리카 분산액; 에틸알코올, 프로필알코올, 에틸렌글리콜, 메틸에틸케톤 및 메틸이소부틸케톤으로 이루어진 군으로부터 선택된 1종 이상의 유기용매로 안정화시킨 콜로이드 실리카 분산액; 액상 규산나트륨; 액상 규산칼륨; 및 액상 규산리튬으로 이루어진 군으로부터 선택된 1종 이상인 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물.14. In the above 13, wherein the silica compound is fine powder silica; Colloidal silica dispersion stabilized with Na 2 O; Colloidal silica dispersion stabilized with K 2 O; Colloidal silica dispersion stabilized with acid solution; Colloidal silica dispersion stabilized with NH 3 ; Colloidal silica dispersion stabilized with at least one organic solvent selected from the group consisting of ethyl alcohol, propyl alcohol, ethylene glycol, methyl ethyl ketone and methyl isobutyl ketone; Liquid sodium silicate; Liquid potassium silicate; And a liquid etching silicate composition of at least one crystalline silicon wafer selected from the group consisting of liquid lithium silicate.
15. 위 1 내지 14 중 어느 한 항의 에칭액 조성물에 의한 결정성 실리콘 웨이퍼의 텍스쳐 에칭 방법.15. Texture etching method of the crystalline silicon wafer by the etching solution composition of any one of 1 to 14.
16. 위 15에 있어서, 상기 에칭액 조성물을 50 내지 100℃의 온도에서 30초 내지 60분 동안 분무시키는 것을 포함하는 에칭 방법.16. The etching method according to the above 15, comprising spraying the etching solution composition for 30 seconds to 60 minutes at a temperature of 50 to 100 ℃.
17. 위 15에 있어서, 상기 에칭액 조성물에 상기 웨이퍼를 50 내지 100℃의 온도에서 30초 내지 60분 동안 침적시키는 에칭 방법.17. The etching method of 15, wherein the etching solution composition is deposited for 30 seconds to 60 minutes at a temperature of 50 to 100 ℃.
본 발명의 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물 및 텍스쳐 에칭방법에 따르면 결정성 실리콘 웨이퍼 표면의 위치별 텍스쳐의 품질 편차를 최소화, 즉 텍스쳐의 균일성을 향상시켜 태양광의 흡수량을 극대화시키고 광 반사율을 낮출 수 있다.According to the texture etching solution composition and the texture etching method of the crystalline silicon wafer of the present invention to minimize the quality variation of the texture of each position on the surface of the crystalline silicon wafer, that is to improve the uniformity of the texture to maximize the amount of absorption of sunlight and lower the light reflectance Can be.
본 발명의 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물 및 텍스쳐 에칭방법에 따르면 에칭액 조성물 사용량 대비 처리되는 실리콘 웨이퍼의 매수를 증가시킬 수 있으며 텍스쳐 공정 중 별도의 에칭액 성분을 투입할 필요가 없고 에어레이팅 장비도 도입할 필요가 없어 품질과 생산성을 향상시킬 수 있고 공정 비용 면에서도 경제적이다.According to the texture etching liquid composition and the texture etching method of the crystalline silicon wafer of the present invention, it is possible to increase the number of silicon wafers to be processed compared to the amount of the etching liquid composition, and it is not necessary to add a separate etching liquid component during the texturing process and introduce an air rating equipment. There is no need to improve quality and productivity, and it is economical in terms of process cost.
도 1은 실시예 1의 결정성 실리콘 웨이퍼의 텍스쳐용 에칭액 조성물을 이용하여 에칭된 단결정 실리콘 웨이퍼의 텍스쳐를 나타낸 SEM 사진이다.1 is a SEM photograph showing the texture of a single crystal silicon wafer etched using the etching liquid composition for the texture of the crystalline silicon wafer of Example 1. FIG.
도 2는 실시예 1의 결정성 실리콘 웨이퍼의 텍스쳐용 에칭액 조성물을 이용하여 에칭된 단결정 실리콘 웨이퍼의 텍스쳐 피라미드 구조를 나타낸 SEM 사진이다.FIG. 2 is an SEM photograph showing the texture pyramid structure of the single crystal silicon wafer etched using the etching liquid composition for the texture of the crystalline silicon wafer of Example 1. FIG.
본 발명은, 폴리카르복시산계 고분자 및 이의 염을 포함함으로써, 결정성 실리콘 웨이퍼의 표면에 균일한 미세 피라미드 구조를 형성함으로써 광 반사율이 낮은 텍스쳐를 제조할 수 있는 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물 및 텍스쳐 에칭방법에 관한 것이다.The present invention relates to a texture etching solution composition and texture of a crystalline silicon wafer comprising a polycarboxylic acid-based polymer and salts thereof, thereby forming a uniform fine pyramid structure on the surface of the crystalline silicon wafer to produce a low light reflectance texture. It relates to an etching method.
이하, 본 발명을 구체적으로 설명하도록 한다.Hereinafter, the present invention will be described in detail.
본 발명의 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물은 폴리카르복시산계 고분자를 포함하는 것을 특징으로 한다. The texture etching solution composition of the crystalline silicon wafer of the present invention is characterized in that it comprises a polycarboxylic acid-based polymer.
본 발명에 있어서, 폴리카르복시산계 고분자는 텍스쳐 용액 중 OH- 이온의 활동도를 조절하여 Si100 방향과 Si111 방향의 에칭 속도 차이를 감소시키는 역할을 할 뿐만 아니라 결정성 실리콘 표면의 젖음성을 개선시켜 에칭되어 용해된 수소 버블을 빠르게 떨어뜨림으로써 버블 스틱 현상이 발생하는 것을 방지한다. In the present invention, the polycarboxylic acid-based polymer not only serves to reduce the etching rate difference between the Si 100 direction and the Si 111 direction by controlling the activity of OH - ions in the texture solution, thereby improving the wettability of the crystalline silicon surface. Rapid dropping of the etched and dissolved hydrogen bubbles prevents the bubble stick phenomenon from occurring.
본 발명에 따른 폴리카르복시산계 고분자는, 카르복시산 작용기를 갖는 고분자라면 적절하게 사용될 수 있으며, 보다 구체적으로는 하기 화학식 1로 표시되는 반복단위를 포함할 수 있다:The polycarboxylic acid-based polymer according to the present invention may be suitably used as long as it is a polymer having a carboxylic acid functional group, and more specifically, may include a repeating unit represented by the following Chemical Formula 1.
[화학식 1][Formula 1]
Figure PCTKR2012007131-appb-I000001
Figure PCTKR2012007131-appb-I000001
식 중, R1, R2 및 R3는 서로 독립적으로 수소, 탄소수 1 내지 5인 알킬기, 또는 -(CH2)m2COOM2이며, M1 및 M2는 서로 독립적으로 수소, 알칼리 금속, 알칼리 토금속, 암모늄기, 또는 히드록시기로 치환가능한 탄소수 1 내지 10의 알킬암모늄기이며, m1 및 m2는 서로 독립적으로 0 내지 2인 정수이다.Wherein R 1 , R 2 and R 3 are independently of each other hydrogen, an alkyl group having 1 to 5 carbon atoms, or — (CH 2 ) m 2 COOM 2 , and M 1 and M 2 are independently of each other hydrogen, an alkali metal, An alkylammonium group having 1 to 10 carbon atoms which may be substituted with an alkaline earth metal, an ammonium group, or a hydroxy group, and m 1 and m 2 are each independently an integer of 0 to 2.
상기 식 중에서, 알칼리 금속으로는 나트륨 또는 칼륨이 바람직하고; 알칼리 토금속으로는 마그네슘, 칼슘이 바람직하고; 탄소수 1 내지 10의 알킬암모늄기로는 디메틸암모늄, 메틸에틸암모늄, 디에틸암모늄, 트리메틸암모늄, 트리에틸암모늄, 테트라메틸암모늄 등이 바람직하고, 히드록시기로 치환된 탄소수 1 내지 10의 알킬암모늄기로는 트리에탄올암모늄, 모노에탄올암모늄, 디이소프로판올암모늄 등이 바람직하다.In said formula, sodium or potassium is preferable as alkali metal; As alkaline earth metal, magnesium and calcium are preferable; As the alkylammonium group having 1 to 10 carbon atoms, dimethyl ammonium, methylethylammonium, diethylammonium, trimethylammonium, triethylammonium, tetramethylammonium and the like are preferred. , Monoethanol ammonium, diisopropanol ammonium, etc. are preferable.
본 발명에 따른 폴리카르복시산계 고분자는 상기 반복단위를 형성할 수 있는 단량체를 중합하여 형성될 수 있으며, 예를 들면 아크릴산, 메틸(메타)아크릴산, 에틸(메타)아크릴산, 트리메틸아크릴산, 말레산, 푸마르산, 이타콘산, 크로톤산, 시트라콘산, 비닐초산, 4-펜텐산 및 이들의 염 등의 단량체를 각각 단독으로 또는 2종 이상 혼합하여 중합하여 형성될 수 있으며, 그에 따라 단일 중합체(homopolymer) 또는 공중합체(copolymer)일 수 있다. The polycarboxylic acid-based polymer according to the present invention may be formed by polymerizing a monomer capable of forming the repeating unit, for example acrylic acid, methyl (meth) acrylic acid, ethyl (meth) acrylic acid, trimethyl acrylic acid, maleic acid, fumaric acid , Monomers such as itaconic acid, crotonic acid, citraconic acid, vinyl acetic acid, 4-pentenoic acid, and salts thereof may be formed by polymerization alone or by mixing two or more kinds thereof, and thus a homopolymer or It may be a copolymer.
선택적으로, 전술한 단량체는 아크릴아미드, 메타크릴아미드, 탄소수 1 내지 5인 알킬(메타)아크릴아미드 등의 아미드계 화합물; 스티렌, 알파-메틸스티렌, 비닐톨루엔, 염화스티렌 등의 방향족비닐계 화합물; 메틸(메타)아크릴레이트, 에틸(메타)아크릴레이트, 프로필(메타)아크릴레이트, n-아밀(메타)아크릴레이트, 이소아밀(메타)아크릴레이트, 헥실(메타)아크릴레이트, 에틸헥실(메타)아크릴레이트, 옥틸(메타)아크릴레이트, 말레산디에틸, 이타콘산디메틸, (폴리)에틸렌글리콜모노(메타)아크릴레이트, (폴리)프로필렌글리콜모노(메타)아크릴레이트, (폴리)부틸렌글리콜모노(메타)아크릴레이트, (폴리)스티렌글리콜모노(메타)아크릴레이트 등의 불포화카르복시산에스테르계 화합물; 무수말레인, 무수이타콘산등의 불포화무수카르복시산계 화합물; 비닐알콜, 알릴알콜, 메틸비닐알콜, 에틸비닐알콜, 비닐글리콜산등의 불포화알콜계 화합물: 폴리에틸렌옥사이드부가(메타)아크릴레이트 등의 비이온성기 부가 불포화카르복시산에스테르계 화합물; 하이드록시메틸(메타)아크릴레이트, 하이드록시에틸(메타)아크릴레이트, 하이드록시프로필(메타)아크릴레이트, 폴리에틸렌글리콜모노(메타)아크릴레이트, 폴리프로필렌글리콜모노(메타)아크릴레이트, 글리세롤모노(메타)아크릴레이트, 글리세롤디(메타)아크릴레이트, 폴리테트라메틸렌글리콜모노(메타)아크릴레이트, 폴리테트라메틸렌글리콜디(메타)아크릴레이트, 부탄디올(메타)아크릴레이트, 헥산디올(메타)아크릴레이트 등의 수산기함유(메타)아크릴산에스테르류; (메타)아크릴로니트릴등의 비닐시안계 화합물; 1,3-부타디엔, 이소프렌, 2.3-디메틸-1,3-부타디엔, 1,3-펜타디엔, 2-클로르-1,3-부타디엔, 1-클로로-1,3-부타디엔등의 지방족 디엔계 화합물; 염화비닐등의 할로겐화 비닐계 화합물; 2-아크릴아미드-2-메틸프로판술폰산, 스티렌술폰산나트륨 등의 술폰산계 화합물; 비닐포스폰산등의 포스폰산계 화합물에서 선택되는 적어도 1종의 공단량체와 공중합되어 본 발명에 따른 폴리카르복시산계 고분자를 형성할 수 있다.Optionally, the aforementioned monomers may be selected from amide compounds such as acrylamide, methacrylamide, alkyl (meth) acrylamides having 1 to 5 carbon atoms; Aromatic vinyl compounds such as styrene, alpha-methylstyrene, vinyltoluene and styrene chloride; Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-amyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, ethylhexyl (meth) Acrylate, octyl (meth) acrylate, diethyl maleate, dimethyl itacate, (poly) ethylene glycol mono (meth) acrylate, (poly) propylene glycol mono (meth) acrylate, (poly) butylene glycol mono ( Unsaturated carboxylic acid ester compounds such as meta) acrylate and (poly) styrene glycol mono (meth) acrylate; Unsaturated anhydride carboxylic acid compounds such as maleic anhydride and itaconic anhydride; Unsaturated alcohol compounds such as vinyl alcohol, allyl alcohol, methyl vinyl alcohol, ethyl vinyl alcohol and vinyl glycol acid: nonionic group addition unsaturated carboxylic acid ester compounds such as polyethylene oxide addition (meth) acrylate; Hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, glycerol mono (meth) ) Acrylate, glycerol di (meth) acrylate, polytetramethylene glycol mono (meth) acrylate, polytetramethylene glycol di (meth) acrylate, butanediol (meth) acrylate, hexanediol (meth) acrylate Hydroxyl group-containing (meth) acrylic acid esters; Vinyl cyan compounds such as (meth) acrylonitrile; Aliphatic diene compounds such as 1,3-butadiene, isoprene, 2.3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-chlor-1,3-butadiene, 1-chloro-1,3-butadiene ; Vinyl halide compounds such as vinyl chloride; Sulfonic acid compounds such as 2-acrylamide-2-methylpropanesulfonic acid and sodium styrene sulfonate; It may be copolymerized with at least one comonomer selected from phosphonic acid compounds such as vinyl phosphonic acid to form the polycarboxylic acid polymer according to the present invention.
본 발명에 따른 폴리카르복시산계 고분자는 당업계에 알려진 다양한 중합 방법 중에서 적절한 것을 채택하여 제조될 수 있으며, 제조방법이 특별히 제한되지 않는다.The polycarboxylic acid-based polymer according to the present invention can be prepared by adopting an appropriate one from various polymerization methods known in the art, the production method is not particularly limited.
본 발명에 따른 폴리카르복시산계 고분자는 중량평균 분자량이 10,000 내지 50,000인 것이 바람직하다. 상기 범위의 중량평균 분자량을 갖는 경우에 과에칭을 방지할 수 있는 장점이 있다.The polycarboxylic acid-based polymer according to the present invention preferably has a weight average molecular weight of 10,000 to 50,000. When having a weight average molecular weight in the above range there is an advantage that can prevent over-etching.
본 발명에 따른 폴리카르복시산계 고분자는 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물에 적절한 함량으로 포함될 수 있으며, 예를 들면 조성물 총 중량 대비 0.1 내지 20중량%, 바람직하게는 0.1 내지 5 중량%로 포함될 수 있으나, 이에 한정되는 것은 아니다. 상기 함량 범위에서 균일한 텍스쳐의 형성 효과가 가장 바람직하게 나타난다.The polycarboxylic acid-based polymer according to the present invention may be included in an appropriate amount of the texture etching solution composition of the crystalline silicon wafer, for example, may be included in 0.1 to 20% by weight, preferably 0.1 to 5% by weight relative to the total weight of the composition. It is not limited to this. The effect of forming a uniform texture is most preferred in the above content range.
본 발명에 따른 폴리카르복시산계 고분자는 당분야에서 통상적으로 사용되는 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물에 적용될 수 있다. 결정성 실리콘 웨이퍼는 통상적으로 알칼리 화합물을 포함한다.The polycarboxylic acid-based polymer according to the present invention can be applied to the texture etching solution composition of the crystalline silicon wafer commonly used in the art. Crystalline silicon wafers typically comprise an alkali compound.
본 발명에서 사용되는 알칼리 화합물 결정성 실리콘 웨이퍼의 표면을 에칭하는 성분으로서 당분야에서 통상적으로 사용하는 알칼리 화합물이라면 제한없이 사용될 수 있다. 사용가능한 알칼리 화합물로는 수산화칼륨, 수산화나트륨, 수산화암모늄, 테트라히드록시메틸암모늄, 테트라히드록시에틸암모늄 등을 들 수 있으며, 이 중에서 수산화칼륨, 수산화나트륨이 바람직하다. 이들은 단독 또는 2종 이상 혼합하여 사용할 수 있다.As the component for etching the surface of the alkaline compound crystalline silicon wafer used in the present invention, any alkaline compound commonly used in the art may be used without limitation. Examples of the alkali compound that can be used include potassium hydroxide, sodium hydroxide, ammonium hydroxide, tetrahydroxymethylammonium, tetrahydroxyethylammonium, and the like, with potassium hydroxide and sodium hydroxide being preferred. These can be used individually or in mixture of 2 or more types.
알칼리 화합물은 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물 총 중량 대비 0.1 내지 20중량%로 포함되는 것이 바람직하고, 보다 바람직하게는 1 내지 5중량%인 것이 좋다. 함량이 상기 범위에 해당되는 경우 실리콘 웨이퍼 표면을 에칭할 수 있게 된다.The alkali compound is preferably included in an amount of 0.1 to 20% by weight based on the total weight of the texture etching solution composition of the crystalline silicon wafer, more preferably 1 to 5% by weight. When the content falls within the above range, the silicon wafer surface can be etched.
선택적으로, 본 발명의 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물은 고리형 화합물을 더 포함할 수 있다.Optionally, the texture etchant composition of the crystalline silicon wafer of the present invention may further comprise a cyclic compound.
본 발명에 있어서, 고리형 화합물은 바람직하게는 탄소수 4-10의 고리형 탄화수소; 및 N, O 또는 S의 헤테로원자를 1개 이상 포함하는 탄소수 4-10의 헤테로고리형 탄화수소를 포함하는 화합물을 의미하며, 결정성 실리콘 웨이퍼 표면의 젖음성을 개선시켜 알칼리 화합물에 의한 과에칭을 방지함으로써 텍스쳐의 품질 편차를 최소화시키는 동시에 에칭에 의해 생성된 수소 버블의 양을 빠르게 감소시킴으로써 버블 스틱 현상이 발생하는 것도 방지할 수 있는 성분이다. 또한, 비점이 높아 종래 사용되고 있는 이소프로필알코올에 비해 적은 함량으로 사용이 가능할 뿐만 아니라 동일 사용량에 대한 처리 매수도 증가시킬 수 있다.In the present invention, the cyclic compound is preferably a cyclic hydrocarbon having 4-10 carbon atoms; And a heterocyclic hydrocarbon having 4 to 10 carbon atoms including one or more heteroatoms of N, O, or S, and improves the wettability of the surface of the crystalline silicon wafer to prevent overetching by alkali compounds. This minimizes the quality variation of the texture and at the same time rapidly reduces the amount of hydrogen bubbles generated by etching, thereby preventing the occurrence of bubble stick phenomenon. In addition, the boiling point can be used in a small amount compared to isopropyl alcohol is conventionally used as well as increase the number of treatment for the same amount of use.
고리형 화합물은 비점이 100℃ 이상으로 높은 것이 바람직하고, 보다 바람직하게는 100 내지 400℃, 가장 바람직하게는 150 내지 400℃인 것이 좋다. 또한, 고리형 화합물은 한센의 용해도 파라미터(Hansen solubility parameter(HSP), δp)가 6 내지 15인 것이 바람직하다. 상기 범위의 비점과 용해도 파라미터를 갖는 것이 에칭액 조성물에 포함되는 다른 성분들과의 상용성 면에서 바람직하다.It is preferable that a boiling point of a cyclic compound is high as 100 degreeC or more, More preferably, it is 100-400 degreeC, Most preferably, it is 150-400 degreeC. In addition, the cyclic compound preferably has a Hansen solubility parameter (HSP) δp of 6 to 15. Having a boiling point and solubility parameter in the above range is preferable in view of compatibility with other components included in the etching liquid composition.
고리형 화합물은 비점과 한센의 용해도 파라미터를 만족시키는 것이라면 그 종류가 특별히 한정되지 않으며, 예컨대 피페라진계, 모르폴린계, 피리딘계, 피페리딘계, 피페리돈계, 피롤리딘계, 피롤리돈계, 이미다졸리디논계, 퓨란계, 아닐린계, 톨루이딘계, 아민계, 락톤계, 카보네이트계, 카바졸계 화합물 등을 들 수 있다. 구체적인 예로는, 피페라진, N-메틸피페라진, N-에틸피페라진, N-비닐피페라진, N-비닐메틸피페라진, N-비닐에틸피페라진, N-비닐-N'-메틸피페라진, N-아크릴로일피페라진, N-아크릴로일-N'-메틸피페라진, 히드록시에틸피페라진, N-(2-아미노에틸)피페라진, N,N'-디메틸피페라진; 모르폴린, N-메틸모르폴린, N-에틸모르폴린, N-페닐모르폴린, N-비닐모르폴린, N-비닐메틸모르폴린, N-비닐에틸모르폴린, N-아크릴로일모르폴린, N-코코모르폴린, N-(2-아미노에틸)모르폴린, N-(2-시아노에틸)모르폴린, N-(2-히드록시에틸)모르폴린, N-(2-히드록시프로필)모르폴린, N-아세틸모르폴린, N-포밀모르폴린, N-메틸모르폴린-N-옥사이드; 메틸피리딘; N-메틸피페리딘, 3,5-디메틸피페리딘, N-에틸피페리딘, N-(2-히드록시에틸)피페리딘; N-비닐피페리돈, N-비닐메틸피페리돈, N-비닐에틸피페리돈, N-아크릴로일피페리돈, N-메틸-4-피페리돈, N-비닐-2-피페리돈; N-메틸피롤리딘; N-비닐피롤리돈, N-비닐메틸피롤리돈, N-비닐에틸-2-피롤리돈, N-아크릴로일피롤리돈, N-메틸피롤리돈, N-에틸-2-피롤리돈, N-이소프로필-2-피롤리돈, N-부틸-2-피롤리돈, N-t-부틸-2-피롤리돈, N-헥실-2-피롤리돈, N-옥틸-2-피롤리돈, N-벤질-2-피롤리돈, N-시클로헥실-2-피롤리돈, N-비닐-2-피롤리돈, N-(2-히드록시에틸)-2-피롤리돈, N-(2-메톡시에틸)-2-피롤리돈, N-(2-메톡시프로필)-2-피롤리돈, N-(2-에톡시에틸)-2-피롤리돈; N-메틸 이미다졸리디논, 디메틸이미다졸리디논, N-(2-히드록시에틸)-2-이미다졸리디논; 테트라히드로퓨란, 테트라히드로-2-퓨란메탄올; N-메틸아닐린, N-에틸아닐린, N,N-디메틸아닐린, N-(2-히드록시에틸)아닐린, N,N-비스-(2-히드록시에틸)아닐린, N-에틸-N-(2-히드록시에틸)아닐린; N,N-디에틸-o-톨루이딘, N-에틸-N-(2-히드록시에틸)-m-톨루이딘; 디메틸벤질아민; γ-부티로락톤; 에틸렌카보네이트, 프로필렌카보네이트; N-비닐카바졸, N-아크릴로일카바졸 등을 들 수 있으며, 이들은 단독 또는 2종 이상 혼합하여 사용할 수 있다.The cyclic compound is not particularly limited as long as it satisfies the boiling point and the solubility parameter of Hansen. Examples thereof include piperazine, morpholine, pyridine, piperidine, piperidone, pyrrolidine, pyrrolidone, Imidazolidinone type, furan type, aniline type, toluidine type, amine type, lactone type, carbonate type, carbazole type compound, etc. are mentioned. Specific examples include piperazine, N-methylpiperazine, N-ethylpiperazine, N-vinylpiperazine, N-vinylmethylpiperazine, N-vinylethylpiperazine, N-vinyl-N'-methylpiperazine, N-acryloylpiperazine, N-acryloyl-N'-methylpiperazine, hydroxyethylpiperazine, N- (2-aminoethyl) piperazine, N, N'-dimethylpiperazine; Morpholine, N-methylmorpholine, N-ethylmorpholine, N-phenylmorpholine, N-vinylmorpholine, N-vinylmethylmorpholine, N-vinylethylmorpholine, N-acryloylmorpholine, N Cocomorpholine, N- (2-aminoethyl) morpholine, N- (2-cyanoethyl) morpholine, N- (2-hydroxyethyl) morpholine, N- (2-hydroxypropyl) morpho Pauline, N-acetylmorpholine, N-formylmorpholine, N-methylmorpholine-N-oxide; Methylpyridine; N-methylpiperidine, 3,5-dimethylpiperidine, N-ethylpiperidine, N- (2-hydroxyethyl) piperidine; N-vinylpiperidone, N-vinylmethylpiperidone, N-vinylethylpiperidone, N-acryloylpiperidone, N-methyl-4-piperidone, N-vinyl-2-piperidone; N-methylpyrrolidine; N-vinylpyrrolidone, N-vinylmethylpyrrolidone, N-vinylethyl-2-pyrrolidone, N-acryloylpyrrolidone, N-methylpyrrolidone, N-ethyl-2-pyrrolidone , N-isopropyl-2-pyrrolidone, N-butyl-2-pyrrolidone, Nt-butyl-2-pyrrolidone, N-hexyl-2-pyrrolidone, N-octyl-2-pyrroli Don, N-benzyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, N- (2-hydroxyethyl) -2-pyrrolidone, N -(2-methoxyethyl) -2-pyrrolidone, N- (2-methoxypropyl) -2-pyrrolidone, N- (2-ethoxyethyl) -2-pyrrolidone; N-methyl imidazolidinone, dimethylimidazolidinone, N- (2-hydroxyethyl) -2-imidazolidinone; Tetrahydrofuran, tetrahydro-2-furanmethanol; N-methylaniline, N-ethylaniline, N, N-dimethylaniline, N- (2-hydroxyethyl) aniline, N, N-bis- (2-hydroxyethyl) aniline, N-ethyl-N- ( 2-hydroxyethyl) aniline; N, N-diethyl-o-toluidine, N-ethyl-N- (2-hydroxyethyl) -m-toluidine; Dimethylbenzylamine; γ-butyrolactone; Ethylene carbonate, propylene carbonate; N-vinyl carbazole, N-acryloyl carbazole, etc. are mentioned, These can be used individually or in mixture of 2 or more types.
고리형 화합물은 조성물 총 중량 대비 0.1 내지 50중량%로 포함되는 것이 바람직하고, 보다 바람직하게는 1 내지 10중량%인 것이 좋다. 함량이 상기 범위에 해당되는 경우 실리콘 웨이퍼 표면의 젖음성을 효과적으로 개선시켜 텍스쳐 품질 편차를 최소화킴으로써 균일성을 향상시킬 수 있다.The cyclic compound is preferably included in 0.1 to 50% by weight, more preferably 1 to 10% by weight relative to the total weight of the composition. If the content falls within the above range, uniformity may be improved by effectively improving the wettability of the silicon wafer surface to minimize texture quality variation.
고리형 화합물은 수용성 극성 용매와 혼합된 것일 수도 있다.The cyclic compound may be mixed with a water soluble polar solvent.
수용성 극성 용매는 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물에 포함되는 다른 성분들 및 물과 상용성이 있는 것이라면 그 종류가 특별히 한정되지 않으며, 양자성 또는 비양자성 극성 용매를 모두 사용할 수 있다.The water-soluble polar solvent is not particularly limited as long as it is compatible with other components and water included in the texture etching solution composition of the crystalline silicon wafer, and both proton or aprotic polar solvents can be used.
양자성 극성 용매로는 에틸렌글리콜모노메틸에테르, 디에틸렌글리콜모노메틸에테르, 트리에틸렌글리콜모노메틸에테르, 폴리에틸렌글리콜모노메틸에테르, 에틸렌글리콜모노에틸에테르, 디에틸렌글리콜모노에틸에테르, 에틸렌글리콜모노부틸에테르, 디에틸렌글리콜모노부틸에테르, 트리에틸렌글리콜모노부틸에테르, 프로필렌글리콜모노메틸에테르, 디프로필렌글리콜모노메틸에테르 등의 에테르계 화합물; 프로판올, 부탄올, 이소프로판올, 테트라하이드로퍼푸릴알코올, 에틸렌글리콜, 프로필렌글리콜 등의 알코올계 화합물 등을 들 수 있으며, 비양자성 극성 용매로는 N-메틸포름아미드, N,N-디메틸포름아미드 등의 아미드계 화합물; 디메틸술폭사이드, 술폴란 등의 술폭사이드계 화합물; 트리에틸포스페이트, 트리부틸포스페이트 등의 포스페이트계 화합물 등을 들 수 있다. 이들은 단독 또는 2종 이상 혼합하여 사용할 수 있다.As a proton polar solvent, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, polyethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, ethylene glycol monobutyl ether Ether compounds such as diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, propylene glycol monomethyl ether and dipropylene glycol monomethyl ether; Alcohol compounds such as propanol, butanol, isopropanol, tetrahydroperfuryl alcohol, ethylene glycol, propylene glycol and the like, and the like, and aprotic polar solvents such as N-methylformamide, N, N-dimethylformamide, etc. System compounds; Sulfoxide compounds such as dimethyl sulfoxide and sulfolane; Phosphate type compounds, such as a triethyl phosphate and a tributyl phosphate, etc. are mentioned. These can be used individually or in mixture of 2 or more types.
수용성 극성 용매는 고리형 화합물 총 100중량%에 대하여 0.1 내지 30중량%로 포함될 수 있다.The water soluble polar solvent may be included in an amount of 0.1 to 30% by weight based on 100% by weight of the cyclic compound.
본 발명의 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물은 계면 활성제를 더 포함할 수 있다. 계면 활성제로는 당분야에서 사용되는 계면 활성제가 사용될 수 있으며, 바람직하게는 불소계 계면활성제를 사용할 수 있다. 본 발명에 있어서, 불소계 계면활성제는 텍스쳐 용액의 표면 장력을 낮추어 결정성 실리콘 표면의 젖음성을 개선시켜 주어 알칼리 화합물에 의한 과에칭을 방지하여 주는 역할을 한다.The texture etching solution composition of the crystalline silicon wafer of the present invention may further include a surfactant. As the surfactant, a surfactant used in the art may be used, and preferably a fluorine-based surfactant may be used. In the present invention, the fluorine-based surfactant lowers the surface tension of the texture solution to improve the wettability of the crystalline silicon surface to prevent over-etching by the alkali compound.
불소계 계면 활성제로는 음이온계 계면 활성제류, 양이온계 계면 활성제류, 양쪽성 이온계 계면 활성제류, 비이온계 계면 활성제 등을 들 수 있으며, 이들은 1종 단독으로 또는 2종 이상이 함께 사용될 수 있다. Examples of the fluorine-based surfactants include anionic surfactants, cationic surfactants, amphoteric surfactants, and nonionic surfactants, which may be used alone or in combination of two or more. .
구체적인 예로는 과불소알킬 카르복시산염, 과불소알킬 설폰산염, 과불소알킬 황산염, 불소알킬 인산염과 같은 음이온계; 과불소알킬 아민염, 과불소알킬 4급화 암모늄염과 같은 양이온계; 과불소알킬 카르복시 베타인, 과불소알킬 설포베타인과 같은 양쪽성 이온계; 및 불소화알킬 폴리옥시에틸렌, 과불소알콜 폴리옥시에틸렌과 같은 비이온계 등이 있으며 이들은 1종 단독으로 또는 2종 이상이 함께 사용될 수 있다. 상기 계면활성제에서 알킬기는 탄소수 1 내지 10인 알킬기일 수 있다.Specific examples include anionics such as perfluoroalkyl carboxylate, perfluoroalkyl sulfonate, perfluoroalkyl sulfate, and fluoroalkyl phosphate; Cationic systems such as perfluoroalkyl amine salts and perfluoroalkyl quaternized ammonium salts; Amphoteric ionic systems such as perfluoroalkyl carboxy betaine and perfluoroalkyl sulfobetaine; And nonionics such as fluorinated alkyl polyoxyethylene and perfluoroalcohol polyoxyethylene. These may be used alone or in combination of two or more. The alkyl group in the surfactant may be an alkyl group having 1 to 10 carbon atoms.
계면활성제는 조성물 총 중량 대비 10-6 내지 10 중량%, 바람직하게는 10-4 내지 1중량%로 포함될 수 있다. 함량이 상기 범위에 해당되는 경우 실리콘 웨이퍼 표면의 젖음성을 효과적으로 개선시켜 텍스쳐 품질 편차를 최소화킴으로써 균일성을 향상시킬 수 있다.The surfactant may be included in an amount of 10 -6 to 10% by weight, preferably 10 -4 to 1% by weight based on the total weight of the composition. If the content falls within the above range, uniformity may be improved by effectively improving the wettability of the silicon wafer surface to minimize texture quality variation.
선택적으로, 본 발명의 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물은 실리카 화합물을 더 포함할 수 있다.Optionally, the texture etchant composition of the crystalline silicon wafer of the present invention may further comprise a silica compound.
본 발명에 있어서, 실리카 화합물은 결정성 실리콘 웨이퍼 표면에 물리적으로 흡착하여 일종의 마스크 역할을 함으로써 결정성 실리콘 웨이퍼 표면이 미세 피라미드 형상을 갖도록 하는 성분으로서, 웨이퍼 표면이 균일한 텍스쳐 형상을 갖는데 우수한 효과를 나타낸다.In the present invention, the silica compound is a component that allows the crystalline silicon wafer surface to have a fine pyramid shape by physically adsorbing on the surface of the crystalline silicon wafer to serve as a kind of mask, and has an excellent effect on the uniform surface of the wafer. Indicates.
본 발명에서 사용 가능한 실리카 화합물은, 분말형, 콜로이드 분산액형 또는 액상 규산금속 화합물 등을 들 수 있다. 구체적으로, 미분말 실리카; Na2O로 안정화시킨 콜로이드 실리카 분산액; K2O로 안정화시킨 콜로이드 실리카 분산액; 산성액으로 안정화시킨 콜로이드 실리카 분산액; NH3로 안정화시킨 콜로이드 실리카 분산액; 에틸알코올, 프로필알코올, 에틸렌글리콜, 메틸에틸케톤 및 메틸이소부틸케톤으로 이루어진 군으로부터 선택된 1종 이상의 유기용매로 안정화시킨 콜로이드 실리카 분산액; 액상 규산나트륨; 액상 규산칼륨; 및 액상 규산리튬 등을 예로 들 수 있으며, 이들을 각각 단독으로 또는 2종 이상 혼합하여 사용할 수 있다.As a silica compound which can be used by this invention, a powder type, a colloidal dispersion type, a liquid metal silicate compound, etc. are mentioned. Specifically, fine powder silica; Colloidal silica dispersion stabilized with Na 2 O; Colloidal silica dispersion stabilized with K 2 O; Colloidal silica dispersion stabilized with acid solution; Colloidal silica dispersion stabilized with NH 3 ; Colloidal silica dispersion stabilized with at least one organic solvent selected from the group consisting of ethyl alcohol, propyl alcohol, ethylene glycol, methyl ethyl ketone and methyl isobutyl ketone; Liquid sodium silicate; Liquid potassium silicate; And liquid lithium silicate etc. can be mentioned, These can be used individually or in mixture of 2 or more types, respectively.
실리카 화합물은 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물 총 중량 대비 10-5 내지 10 중량%로 포함될 수 있고, 바람직하게는 10-4 내지 1 중량%인 것이 좋다. 함량이 상기 범위에 해당되는 경우 결정성 실리콘 웨이퍼 표면에 미세 피라미드를 용이하게 형성할 수 있다.The silica compound may be included in an amount of 10 −5 to 10 wt% based on the total weight of the texture etching solution composition of the crystalline silicon wafer, and preferably 10 −4 to 1 wt%. If the content falls within the above range, it is possible to easily form a fine pyramid on the surface of the crystalline silicon wafer.
본 발명에 따른 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물은 상기 성분들을 구체적인 필요에 따라 적절하게 채택한 후, 물을 첨가하여 전체 조성을 조절하게 되어 전체 조성물의 잔량은 물이 차지한다. 바람직하게는 상기 성분들이 전술한 함량 범위를 갖도록 조절한다.In the texture etching solution composition of the crystalline silicon wafer according to the present invention, after appropriately adopting the above components according to specific needs, water is added to adjust the overall composition so that the remaining amount of the total composition is occupied by water. Preferably the components are adjusted to have the aforementioned content ranges.
물의 종류는 특별히 한정되지 않으나, 탈이온 증류수인 것이 바람직하고, 보다 바람직하게는 반도체 공정용 탈이온 증류수로서 비저항값이 18㏁/㎝ 이상인 것이 좋다.Although the kind of water is not specifically limited, It is preferable that it is deionized distilled water, More preferably, it is preferable that the specific resistance value is 18 kW / cm or more as deionized distilled water for a semiconductor process.
상기와 같은 성분을 포함하여 구성되는 본 발명의 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물은, 특히 폴리카르복시산계 갖는 고분자를 포함함으로써 결정성 실리콘 웨이퍼 표면의 위치별 텍스쳐의 품질 편차를 최소화, 즉 텍스쳐의 균일성을 향상시켜 태양광의 흡수량을 극대화시키고 광 반사율을 낮춰 광효율을 높일 수 있다. 또한, 텍스쳐 에칭 공정 중 별도의 에칭액 성분을 투입할 필요가 없고 에어레이팅 장비도 도입할 필요가 없어 생산성과 비용 면에서 이점이 있다.The texture etching solution composition of the crystalline silicon wafer of the present invention comprising the above components, in particular, by including a polymer having a polycarboxylic acid system to minimize the quality variation of the texture by position on the surface of the crystalline silicon wafer, that is, the uniformity of the texture By improving the properties, the absorption of sunlight can be maximized and the light reflectance can be lowered to increase the light efficiency. In addition, there is no need to add a separate etchant component during the texture etching process, and there is no need to introduce an air rating equipment, which is advantageous in terms of productivity and cost.
본 발명의 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물은 통상의 에칭 공정, 예컨대 딥방식, 분무방식 및 매엽방식의 에칭 공정에 모두 적용 가능하다.The texture etching liquid composition of the crystalline silicon wafer of the present invention can be applied to all conventional etching processes, such as dip, spray and single wafer etching processes.
본 발명은 상기 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물을 이용한 결정성 실리콘 웨이퍼의 텍스쳐 에칭방법을 제공한다.The present invention provides a texture etching method of a crystalline silicon wafer using the texture etching liquid composition of the crystalline silicon wafer.
*결정성 실리콘 웨이퍼의 텍스쳐 에칭방법은 본 발명의 결정성 실리콘웨이퍼의 텍스쳐 에칭액 조성물에 결정성 실리콘 웨이퍼를 침적시키는 단계, 또는 본 발명의 결정성 실리콘웨이퍼의 텍스쳐 에칭액 조성물을 결정성 실리콘 웨이퍼에 분무하는 단계, 또는 상기 두 단계를 모두 포함한다.Texture etching method of the crystalline silicon wafer is a step of depositing the crystalline silicon wafer in the texture etching liquid composition of the crystalline silicon wafer of the present invention, or spraying the texture etching liquid composition of the crystalline silicon wafer of the present invention on the crystalline silicon wafer Or both of the above steps.
침적과 분무의 횟수는 특별히 한정되지 않으며, 침적과 분무를 모두 수행하는 경우 그 순서도 한정되지 않는다.The number of depositions and sprays is not particularly limited, and the order of both deposition and spraying is not limited.
침적, 분무 또는 침적 및 분무하는 단계는 50 내지 100℃의 온도에서 30초 내지 60분 동안 수행될 수 있다.Deposition, spraying or depositing and spraying may be performed for 30 seconds to 60 minutes at a temperature of 50 to 100 ° C.
상기한 바와 같은 본 발명의 결정성 실리콘 웨이퍼의 텍스쳐 에칭방법은 산소를 공급시키는 별도의 에어레이팅 장비를 도입할 필요가 없어 초기 생산 및 공정 비용 면에서 경제적일 뿐만 아니라 간단한 공정으로도 균일한 미세 피라미드 구조의 형성을 가능하게 하게 하며, 피라미드의 형상도 경사면이 피라미드 내부로 만입된 구조를 가지게 하여 반사율을 저감시킬 수 있다.As described above, the texture etching method of the crystalline silicon wafer of the present invention does not need to introduce a separate air-rating apparatus for supplying oxygen, so it is economical in terms of initial production and processing costs, and is uniform even in a simple process. It is possible to form the structure, and the shape of the pyramid can also reduce the reflectance by having a structure in which the inclined surface is indented into the pyramid.
이하, 본 발명의 이해를 돕기 위하여 바람직한 실시예를 제시하나, 이들 실시예는 본 발명을 예시하는 것일 뿐 첨부된 특허청구범위를 제한하는 것이 아니며, 본 발명의 범주 및 기술사상 범위 내에서 실시예에 대한 다양한 변경 및 수정이 가능함은 당업자에게 있어서 명백한 것이며, 이러한 변형 및 수정이 첨부된 특허청구범위에 속하는 것도 당연한 것이다.Hereinafter, preferred examples are provided to aid the understanding of the present invention, but these examples are merely illustrative of the present invention and are not intended to limit the scope of the appended claims, which are within the scope and spirit of the present invention. It is apparent to those skilled in the art that various changes and modifications can be made to the present invention, and such modifications and changes belong to the appended claims.
실시예 1-15 및 비교예 1-4Example 1-15 and Comparative Example 1-4
하기 표 1에 기재된 성분 및 조성비(중량%)에 잔량의 물을 첨가하여 결정성 실리콘 웨이퍼의 텍스쳐용 에칭액 조성물을 제조하였다.The remaining amount of water was added to the components and composition ratios (wt%) shown in Table 1 below to prepare an etching liquid composition for texture of the crystalline silicon wafer.
표 1
구분 알칼리화합물 고리형 화합물 폴리카르복시산계고분자 계면활성제 실리카화합물
종류 함량 종류 함량 종류 함량 종류 함량 종류 함량
실시예 1 KOH 2 NMP 4 PAA 0.3 PFAS 0.008 - -
실시예 2 KOH 2 NMP 4 PMA 0.3 PFAS 0.008 - -
실시예 3 KOH 2 NMP 4 PAMA 0.3 PFAS 0.008 - -
실시예 4 KOH 2 NMM 4 PAA 0.3 PFAP 0.008 - -
실시예 5 KOH 2 NMPAEP 3.80.2 PAA 0.3 PFAP 0.008 - -
실시예 6 KOH 2 NMPGBL 3.80.2 PAA 0.3 PFAP 0.008 - -
실시예 7 KOH 2 NMMAEP 3.80.2 PAA 0.3 PFAP 0.008 - -
실시예 8 KOH 2 NMMGBL 3.80.2 PAA 0.3 PFAP 0.008 - -
실시예 9 NaOH 2 NMP 4 PAA 0.3 PFAS 0.008 - -
실시예 10 KOH 3 NMP 4 PAA 0.3 PFAS 0.008 - -
실시예 11 KOH 4 NMP 4 PAA 0.3 PFAS 0.008 - -
실시예 12 KOH 2 NMP 4 PAA 0.8 PFAS 0.008 - -
실시예 13 KOH 2 NMP 4 PAA 0.3 PFAS 0.016 - -
실시예 14 KOH 2 NMP 3.8 PAA 0.3 PFAS 0.008 SSS 0.5
실시예 15 KOH 2 NMP 3.8 PAA 0.3 PFAS 0.008 SCS 0.5
비교예 1 KOH 1.5 IPA 5 - - - - - -
비교예 2 KOH 1.5 EG 5 - - - - - -
비교예 3 KOH 1.5 MDG 5 - - - - - -
비교예 4 KOH 1.5 MEA 5 - - - - - -
KOH : 수산화칼륨, NaOH: 수산화나트륨, NMP : N-메틸피롤리돈, NMM : N-메틸모폴린, AEP : 아미노에틸피페라진, GBL : g-부티로락톤, PAA : 폴리아크릴산, PMA : 폴리말레산, PAMA : 폴리아크릴-말레산 공중합체, PFAS: 과불소알킬황산염, PFAP: 과불소알킬인산염(탄소수 1-10인 알킬의 혼합물), IPA : 이소프로필알코올, EG : 에틸렌글리콜, MDG : 메틸디글리콜, MEA : 모노에틸아민, SSS: 액상규산나트륨, SCS: 콜로이드 실리카(Na2O 이용 안정화)
Table 1
division Alkali compounds Cyclic compound Polycarboxylic Acid Polymer Surfactants Silica compounds
Kinds content Kinds content Kinds content Kinds content Kinds content
Example 1 KOH 2 NMP 4 PAA 0.3 PFAS 0.008 - -
Example 2 KOH 2 NMP 4 PMA 0.3 PFAS 0.008 - -
Example 3 KOH 2 NMP 4 PAMA 0.3 PFAS 0.008 - -
Example 4 KOH 2 NMM 4 PAA 0.3 PFAP 0.008 - -
Example 5 KOH 2 NMPAEP 3.80.2 PAA 0.3 PFAP 0.008 - -
Example 6 KOH 2 NMPGBL 3.80.2 PAA 0.3 PFAP 0.008 - -
Example 7 KOH 2 NMMAEP 3.80.2 PAA 0.3 PFAP 0.008 - -
Example 8 KOH 2 NMMGBL 3.80.2 PAA 0.3 PFAP 0.008 - -
Example 9 NaOH 2 NMP 4 PAA 0.3 PFAS 0.008 - -
Example 10 KOH 3 NMP 4 PAA 0.3 PFAS 0.008 - -
Example 11 KOH 4 NMP 4 PAA 0.3 PFAS 0.008 - -
Example 12 KOH 2 NMP 4 PAA 0.8 PFAS 0.008 - -
Example 13 KOH 2 NMP 4 PAA 0.3 PFAS 0.016 - -
Example 14 KOH 2 NMP 3.8 PAA 0.3 PFAS 0.008 SSS 0.5
Example 15 KOH 2 NMP 3.8 PAA 0.3 PFAS 0.008 SCS 0.5
Comparative Example 1 KOH 1.5 IPA 5 - - - - - -
Comparative Example 2 KOH 1.5 EG 5 - - - - - -
Comparative Example 3 KOH 1.5 MDG 5 - - - - - -
Comparative Example 4 KOH 1.5 MEA 5 - - - - - -
KOH: potassium hydroxide, NaOH: sodium hydroxide, NMP: N-methylpyrrolidone, NMM: N-methylmorpholine, AEP: aminoethylpiperazine, GBL: g-butyrolactone, PAA: polyacrylic acid, PMA: poly Maleic acid, PAMA: polyacryl-maleic acid copolymer, PFAS: perfluoroalkyl sulfate, PFAP: perfluoroalkyl phosphate (mixture of alkyl having 1 to 10 carbon atoms), IPA: isopropyl alcohol, EG: ethylene glycol, MDG: Methyldiglycol, MEA: monoethylamine, SSS: liquid sodium silicate, SCS: colloidal silica (stabilized using Na 2 O)
실험예Experimental Example
단결정 실리콘 웨이퍼를 실시예 1 내지 실시예 15 및 비교예 1 내지 비교예 4의 결정성 실리콘 웨이퍼의 텍스쳐용 에칭액 조성물에 각각 침지시켜 에칭하였다. 이 때 텍스쳐 조건은 온도 80℃, 시간 20분이었다. The single crystal silicon wafers were immersed in the etching liquid composition for texture of the crystalline silicon wafers of Examples 1 to 15 and Comparative Examples 1 to 4, respectively, to etch. The texture conditions at this time were the temperature of 80 degreeC, and time 20 minutes.
각 조성물로 형성된 텍스쳐의 균일성, 피라미드 평균크기 및 반사율을 측정하였으며, 그 결과를 표 2에 나타내었다.The uniformity, pyramid average size and reflectance of the textures formed from each composition were measured, and the results are shown in Table 2.
텍스쳐 균일성은 육안 평가(디지털 카메라), 광학 현미경, SEM을 이용하고 피라미드 크기는 SEM을 이용하여 평가하였다. Texture uniformity was evaluated using visual evaluation (digital camera), optical microscope, SEM, and pyramid size using SEM.
◎: 웨이퍼 전면 피라미드 형성◎: wafer front pyramid formation
○: 웨이퍼 일부 피라미드 미형성 (피라미드 구조 미형성 정도 5% 미만)○: No pyramid formation on some wafers (less than 5% of pyramid structure formation)
△: 웨이퍼 일부 피라미드 미형성 (피라미드 구조 미형성 정도 5 내지 50% 미만)(Triangle | delta): Unformed part of pyramid of a wafer (Pyramid structure unformed grade less than 5-50%)
Х: 웨이퍼 피라미드 미형성 (피라미드 미형성 정도 50% 이상)Х: no wafer pyramid (more than 50% of pyramid formation)
텍스쳐 반사율은 자외선을 이용하여 400 내지 800㎚의 파장대를 갖는 빛을 조사하였을 때의 평균 반사율을 측정하였다. Texture reflectance measured the average reflectance when irradiating light with a wavelength range of 400-800 nm using ultraviolet-ray.
표 2
구분 텍스쳐 균일성 피라미드 평균크기(㎛) 평균 반사율 (%)
실시예 1 ◎ 4 12.02
실시예 2 ◎ 5 12.13
실시예 3 ◎ 5 12.16
실시예 4 ◎ 5 12.27
실시예 5 ◎ 4 12.16
실시예 6 ◎ 5 12.04
실시예 7 ◎ 4 12.15
실시예 8 ◎ 4 12.21
실시예 9 ◎ 5 12.08
실시예 10 ◎ 5 12.02
실시예 11 ◎ 7 12.11
실시예 12 ◎ 6 12.34
실시예 13 ◎ 4 12.14
실시예 14 ◎ 5 11.78
실시예 15 ◎ 4 11.89
비교예 1 ○ 5 13.22
비교예 2 X 10 21.13
비교예 3 X 7 19.54
비교예 4 X 7 23.48
TABLE 2
division Texture Uniformity Pyramid Average Size (㎛) Average reflectance (%)
Example 1 ◎ 4 12.02
Example 2 ◎ 5 12.13
Example 3 ◎ 5 12.16
Example 4 ◎ 5 12.27
Example 5 ◎ 4 12.16
Example 6 ◎ 5 12.04
Example 7 ◎ 4 12.15
Example 8 ◎ 4 12.21
Example 9 ◎ 5 12.08
Example 10 ◎ 5 12.02
Example 11 ◎ 7 12.11
Example 12 ◎ 6 12.34
Example 13 ◎ 4 12.14
Example 14 ◎ 5 11.78
Example 15 ◎ 4 11.89
Comparative Example 1 ○ 5 13.22
Comparative Example 2 X 10 21.13
Comparative Example 3 X 7 19.54
Comparative Example 4 X 7 23.48
표 2를 참고하면, 실시예 1 내지 6의 실리콘 웨이퍼의 텍스쳐용 에칭액 조성물은 단결정 실리콘 웨이퍼의 전면에 피라미드를 형성 정도가 매우 우수함을 알 수 있다. 이와 관련하여 도 1에 실시예 1의 결정성 실리콘 웨이퍼의 텍스쳐용 에칭액 조성물을 이용하여 에칭된 단결정 실리콘 웨이퍼의 텍스쳐를 나타낸 SEM 사진을 나타내었으며, 도 2에 실시예 1의 결정성 실리콘 웨이퍼의 텍스쳐용 에칭액 조성물을 이용하여 에칭된 단결정 실리콘 웨이퍼의 텍스쳐 피라미드 구조를 나타낸 SEM 사진을 나타내었다. 도 1 및 도 2를 참고하면, 실리콘 웨이퍼 표면 전체에 걸쳐 텍스쳐가 균일하게 형성되었음을 확인할 수 있다.Referring to Table 2, it can be seen that the etching liquid composition for texture of the silicon wafers of Examples 1 to 6 has a very good degree of pyramid formation on the entire surface of the single crystal silicon wafer. In this regard, FIG. 1 is a SEM photograph showing the texture of a single crystal silicon wafer etched using the etching liquid composition for the texture of the crystalline silicon wafer of Example 1, and the texture of the crystalline silicon wafer of Example 1 in FIG. SEM photographs showing the texture pyramid structure of the single crystal silicon wafer etched using the etchant composition were shown. 1 and 2, it can be seen that the texture is uniformly formed over the entire surface of the silicon wafer.
하지만, 낮은 비점의 IPA를 사용한 비교예 1의 경우에는 텍스쳐 공정 중에 증발로 인한 IPA의 감소를 보충하기 위해 IPA를 지속적으로 투입할 필요가 있었다. 이와 같은 공정 중 투입은 온도 구배를 발생시켰으며, 그에 따라 텍스쳐의 균일성이 저하되었음을 알 수 있다. However, in the case of Comparative Example 1 using a low boiling point IPA, IPA was continuously added to compensate for the reduction of IPA due to evaporation during the texture process. The input during such a process generated a temperature gradient, and thus, the uniformity of the texture may be reduced.
또한, 높은 비점의 EG, MDG를 사용한 비교예 2-3의 경우에도 텍스쳐 균일성, 피라미드 크기, 반사율 측면에서 본 발명의 조성물인 실시예들의 조성물을 사용한 경우보다 전체적으로 열등한 것을 알 수 있다. 그 외에 비교예 4 역시 텍스쳐 균일성, 피라미드 크기, 반사율 측면에서 실시예보다 열등한 효과를 나타내는 것을 알 수 있다.In addition, even in Comparative Example 2-3 using high boiling point EG, MDG it can be seen that the overall inferior in the texture uniformity, pyramid size, reflectance in the case of using the composition of the embodiments of the present invention composition. In addition, Comparative Example 4 also shows an inferior effect than the embodiment in terms of texture uniformity, pyramid size, reflectance.

Claims (17)

  1. 폴리카르복시산계 고분자를 포함하는 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물.Texture etching liquid composition of a crystalline silicon wafer containing a polycarboxylic acid-based polymer.
  2. 청구항 1에 있어서, 폴리카르복시산계 고분자는 하기 화학식 1로 표시되는 반복단위를 포함하는 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물:The texture etching solution composition of claim 1, wherein the polycarboxylic acid-based polymer comprises a repeating unit represented by Formula 1 below:
    [화학식 1][Formula 1]
    Figure PCTKR2012007131-appb-I000002
    Figure PCTKR2012007131-appb-I000002
    (식 중, R1, R2 및 R3는 서로 독립적으로 수소, 탄소수 1 내지 5인 알킬기, 또는 -(CH2)m2COOM2이며, M1 및 M2는 서로 독립적으로 수소, 알칼리 금속, 알칼리 토금속, 암모늄기, 또는 히드록시기로 치환가능한 탄소수 1 내지 10의 알킬암모늄기이며, m1 및 m2는 서로 독립적으로 0 내지 2인 정수임).Wherein R 1 , R 2 and R 3 are independently of each other hydrogen, an alkyl group having 1 to 5 carbon atoms, or — (CH 2 ) m 2 COOM 2 , and M 1 and M 2 are independently of each other hydrogen, an alkali metal , An alkylammonium group having 1 to 10 carbon atoms, which may be substituted with an alkaline earth metal, an ammonium group, or a hydroxy group, and m 1 and m 2 are each independently an integer of 0 to 2).
  3. 청구항 1에 있어서, 폴리카르복시산계 고분자는 아크릴산, 메틸(메타)아크릴산, 에틸(메타)아크릴산, 트리메틸아크릴산, 말레산, 푸마르산, 이타콘산, 크로톤산, 시트라콘산, 비닐초산, 4-펜텐산 및 이들의 염으로 이루어진 군에서 선택되는 적어도 1종의 단량체를 중합하여 형성되는 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물.The method of claim 1, wherein the polycarboxylic acid polymer is acrylic acid, methyl (meth) acrylic acid, ethyl (meth) acrylic acid, trimethyl acrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, citraconic acid, vinyl acetic acid, 4-pentenoic acid and Texture etching liquid composition of the crystalline silicon wafer formed by superposing | polymerizing at least 1 sort (s) of monomer chosen from the group which consists of these salts.
  4. 청구항 3에 있어서, 상기 단량체는 아미드계 화합물, 방향족비닐계 화합물, 불포화카르복시산에스테르계 화합물, 불포화무수카르복시산계 화합물, 불포화알콜계 화합물, 비이온성기 부가 불포화카르복시산에스테르계 화합물, 히드록시기함유 (메타)아크릴산에스테르계 화합물, 비닐시안계 화합물, 지방족 디엔계 화합물, 할로겐화 비닐계 화합물, 술폰산계 화합물 및 포스폰산계 화합물 이루어진 군에서 선택되는 적어도 1종의 공단량체와 공중합하여 폴리카르복시산계 고분자를 형성하는 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물.The method of claim 3, wherein the monomer is an amide compound, an aromatic vinyl compound, an unsaturated carboxylic acid ester compound, an unsaturated anhydride carboxylic acid compound, an unsaturated alcohol compound, a nonionic group addition unsaturated carboxylic acid ester compound, a hydroxy group-containing (meth) acrylic acid Crystalline to form a polycarboxylic acid polymer by copolymerizing with at least one comonomer selected from the group consisting of ester compounds, vinyl cyan compounds, aliphatic diene compounds, vinyl halide compounds, sulfonic acid compounds and phosphonic acid compounds Texture etching liquid composition of a silicon wafer.
  5. 청구항 1에 있어서, 폴리카르복시산계 고분자는 중량평균 분자량이 10,000 내지 50,000인 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물.The texture etching solution composition of claim 1, wherein the polycarboxylic acid polymer has a weight average molecular weight of 10,000 to 50,000.
  6. 청구항 1에 있어서, 폴리카르복시산계 고분자는 조성물 총 중량 대비 0.1 내지 20중량%인 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물.The texture etching solution composition of claim 1, wherein the polycarboxylic acid-based polymer is 0.1 to 20 wt% based on the total weight of the composition.
  7. 청구항 1에 있어서, 알칼리 화합물을 더 포함하는 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물.The texture etchant composition of claim 1, further comprising an alkali compound.
  8. 청구항 7에 있어서, 알칼리 화합물은 수산화칼륨, 수산화나트륨, 수산화암모늄, 테트라히드록시메틸암모늄 및 테트라히드록시에틸암모늄으로 이루어진 군으로부터 선택되는 1종 이상인 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물.8. The texture etching solution composition of claim 7, wherein the alkali compound is at least one selected from the group consisting of potassium hydroxide, sodium hydroxide, ammonium hydroxide, tetrahydroxymethylammonium and tetrahydroxyethylammonium.
  9. 청구항 1에 있어서, 고리형 화합물을 더 포함하는 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물.The texture etchant composition of claim 1, further comprising a cyclic compound.
  10. 청구항 9에 있어서, 고리형 화합물은 비점이 100℃ 이상인 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물.The texture etching solution composition of claim 9, wherein the cyclic compound has a boiling point of 100 ° C. or more.
  11. 청구항 9에 있어서, 고리형 화합물은 한센의 용해도 파라미터가 6 내지 15인 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물.The texture etchant composition of claim 9, wherein the cyclic compound has a Hansen solubility parameter of 6 to 15. 11.
  12. 청구항 1에 있어서, 불소계 계면활성제를 더 포함하는 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물.The texture etching solution composition of claim 1, further comprising a fluorine-based surfactant.
  13. 청구항 1에 있어서, 실리카 화합물을 더 포함하는 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물.The texture etchant composition of claim 1, further comprising a silica compound.
  14. 청구항 13에 있어서, 상기 실리카 화합물은 미분말 실리카; Na2O로 안정화시킨 콜로이드 실리카 분산액; K2O로 안정화시킨 콜로이드 실리카 분산액; 산성액으로 안정화시킨 콜로이드 실리카 분산액; NH3로 안정화시킨 콜로이드 실리카 분산액; 에틸알코올, 프로필알코올, 에틸렌글리콜, 메틸에틸케톤 및 메틸이소부틸케톤으로 이루어진 군으로부터 선택된 1종 이상의 유기용매로 안정화시킨 콜로이드 실리카 분산액; 액상 규산나트륨; 액상 규산칼륨; 및 액상 규산리튬으로 이루어진 군으로부터 선택된 1종 이상인 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물.The method of claim 13, wherein the silica compound is fine powder silica; Colloidal silica dispersion stabilized with Na 2 O; Colloidal silica dispersion stabilized with K 2 O; Colloidal silica dispersion stabilized with acid solution; Colloidal silica dispersion stabilized with NH 3 ; Colloidal silica dispersion stabilized with at least one organic solvent selected from the group consisting of ethyl alcohol, propyl alcohol, ethylene glycol, methyl ethyl ketone and methyl isobutyl ketone; Liquid sodium silicate; Liquid potassium silicate; And a liquid etching silicate composition of at least one crystalline silicon wafer selected from the group consisting of liquid lithium silicate.
  15. 청구항 1 내지 14 중 어느 한 항의 에칭액 조성물에 의한 결정성 실리콘 웨이퍼의 텍스쳐 에칭 방법.The texture etching method of the crystalline silicon wafer by the etching liquid composition of any one of Claims 1-14.
  16. 청구항 15에 있어서, 상기 에칭액 조성물을 50 내지 100℃의 온도에서 30초 내지 60분 동안 분무시키는 것을 포함하는 에칭 방법.The etching method of claim 15, wherein the etching solution composition is sprayed at a temperature of 50 to 100 ° C. for 30 seconds to 60 minutes.
  17. 청구항 15에 있어서, 상기 에칭액 조성물에 상기 웨이퍼를 50 내지 100℃의 온도에서 30초 내지 60분 동안 침적시키는 에칭 방법.The etching method according to claim 15, wherein the wafer is immersed in the etching liquid composition at a temperature of 50 to 100 ° C. for 30 seconds to 60 minutes.
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