WO2013002502A9 - Texture etchant composition for crystalline silicon wafer and texture etching method thereof - Google Patents

Texture etchant composition for crystalline silicon wafer and texture etching method thereof Download PDF

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WO2013002502A9
WO2013002502A9 PCT/KR2012/004786 KR2012004786W WO2013002502A9 WO 2013002502 A9 WO2013002502 A9 WO 2013002502A9 KR 2012004786 W KR2012004786 W KR 2012004786W WO 2013002502 A9 WO2013002502 A9 WO 2013002502A9
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texture
cellulose
silicon wafer
crystalline silicon
compound
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PCT/KR2012/004786
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French (fr)
Korean (ko)
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WO2013002502A2 (en
WO2013002502A3 (en
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홍형표
박면규
이재연
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동우화인켐 주식회사
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Priority claimed from KR1020120058485A external-priority patent/KR20130002258A/en
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Publication of WO2013002502A2 publication Critical patent/WO2013002502A2/en
Publication of WO2013002502A9 publication Critical patent/WO2013002502A9/en
Publication of WO2013002502A3 publication Critical patent/WO2013002502A3/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
    • C09K13/00—Etching, surface-brightening or pickling compositions
    • C09K13/02—Etching, surface-brightening or pickling compositions containing an alkali metal hydroxide
    • 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

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 No. 4,137,123
  • Patent Document 2 European Patent No. 0477424
  • Patent Document 3 Korean Registered Patent No. 0180621
  • the texture etching solution composition of the crystalline silicon wafer capable of minimizing the quality variation of the texture for each location to increase the light efficiency and increase the number of treatments for the unit usage.
  • the purpose is to provide.
  • 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.
  • composition according to the above 1, wherein the alkali compound is at least one selected from the group consisting of potassium hydroxide, sodium hydroxide, ammonium hydroxide, tetrahydroxymethylammonium and tetrahydroxyethylammonium.
  • polysaccharide is at least one selected from the group consisting of glucan-based compounds, fructan-based compounds, mannan-based compounds, galactan-based compounds and metal salts of the etching solution of the crystalline silicon wafer.
  • the polysaccharide is cellulose, dimethylaminoethyl cellulose, diethylaminoethyl cellulose, ethyl hydroxyethyl cellulose, methyl hydroxyethyl cellulose, 4-aminobenzyl cellulose, triethylaminoethyl cellulose, cyanoethyl cellulose , Ethyl cellulose, methyl cellulose, carboxymethyl cellulose, carboxyethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, alginic acid, amylose, amylopectin, pectin, starch, dextrin, ⁇ -cyclodextrin, ⁇ -cyclodextrin, ⁇ - 1 type selected from the group consisting of cyclodextrin, hydroxypropyl- ⁇ -cyclodextrin, methyl- ⁇ -cyclodextrin, dextran, dextransulfate sodium, sapon
  • the polysaccharide has an average molecular weight of 5,000 to 1,000,000 texture etching liquid composition of a crystalline silicon wafer.
  • the texture etching liquid composition of the crystalline silicon wafer further comprising a water-soluble polar solvent.
  • the water-soluble polar solvent is 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, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propanol, butanol, isopropanol, tetrahydroperfuryl alcohol, ethylene glycol, propylene glycol And texture etching solution composition of at least one crystalline silicon wafer selected from the group consisting of N-methylformamide, N, N-dimethylformamide, dimethyl sulfoxide, sulfolane, triethyl phosphate and tributyl phosphate.
  • the water-soluble polar solvent is a texture etching solution composition of the crystalline silicon wafer containing 0.1 to 30% by weight relative to the total 100% by weight of the cyclic compound.
  • the texture etching solution composition of claim 1 further comprising at least one selected from the group consisting of fatty acids and metal salts thereof.
  • the texture etching solution of crystalline silicon wafer further comprising at least one surfactant selected from the group consisting of polyoxyethylene-based (POE) compounds, polyoxypropylene-based (POP) compounds and copolymers thereof Composition.
  • POE polyoxyethylene-based
  • POP polyoxypropylene-based
  • fine powder silica Colloidal silica solution stabilized with Na 2 O; Colloidal silica solution stabilized with K 2 O; Colloidal silica solution stabilized with acid solution; Colloidal silica solution stabilized with NH 3 ; Colloidal silica solution 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 at least one silica compound selected from the group consisting of liquid lithium silicate.
  • the texture etching method of the crystalline silicon wafer comprising the step of depositing, spraying or depositing and spraying the crystalline silicon wafer with the texture etching liquid composition of any one of the above 1 to 13.
  • the deposition, spraying or deposition and spraying is a texture etching method of a crystalline silicon wafer is carried out for 30 seconds to 60 minutes at a temperature of 50 to 100 °C.
  • the quality variation of the texture for each position of the surface of the crystalline silicon wafer is minimized, that is, the uniformity of the texture is improved to maximize the amount of sunlight absorption and lower the light reflectance.
  • the light efficiency can be improved.
  • the present invention can increase the number of processing for the unit usage compared to the conventional texture etching solution composition, there is no need to add a separate etching solution components during the texture process and do not need to introduce an air rating equipment to improve the quality and productivity It can be improved and economic in terms of process cost.
  • Example 11 is a 3D optical micrograph showing the surface of a single crystal silicon wafer texture-etched with the texture etching solution composition of the crystalline silicon wafer of Example 11 of the present invention
  • Example 11 is a SEM photograph showing the surface of a single crystal silicon wafer textured etched with the texture etching liquid composition of the crystalline silicon wafer of Example 11 of the present invention.
  • the present invention relates to a texture etching liquid composition of a crystalline silicon wafer and a method of etching the texture of a crystalline silicon wafer using the same.
  • the texture etching solution composition of the crystalline silicon wafer of the present invention is an alkali compound; Cyclic compounds; Polysaccharides; And water in an optimal content.
  • the alkali compound 0.1 to 20% by weight; 0.1-50% by weight of the cyclic compound; Polysaccharides 10 -9 to 0.5% by weight; And residual amount of water.
  • An alkali compound is a component which etches the surface of a crystalline silicon wafer,
  • the kind is not specifically limited.
  • potassium hydroxide, sodium hydroxide, ammonium hydroxide, tetrahydroxymethylammonium, tetrahydroxyethylammonium, etc. are mentioned, Among these, potassium hydroxide and sodium hydroxide are preferable. 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, and more preferably 1 to 5% by weight, based on 100% by weight of the total amount of the texture etching solution composition of the crystalline silicon wafer.
  • the silicon wafer surface can be etched.
  • the cyclic compound may be 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, wherein the wettability of the surface of the crystalline silicon wafer is improved to prevent over-etching by an alkali compound.
  • a component that can prevent the bubble stick phenomenon from occurring by rapidly reducing the amount of hydrogen bubbles generated by etching By minimizing the quality variation of the texture by preventing it, it is also a component that can prevent the bubble stick phenomenon from occurring by rapidly reducing the amount of hydrogen bubbles generated by etching.
  • 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 150-400 degreeC.
  • the cyclic compound has a Hansen solubility parameter (HSP) of 6 to 15 in terms 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 an amount of 0.1 to 50% by weight, more preferably 1 to 10% by weight based on 100% by weight of the total amount of the texture etching solution composition of the crystalline silicon wafer. 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 present invention is characterized by including the polysaccharide in an optimum content.
  • Polysaccharide is a sugar in which two or more monosaccharides are glycosidic bonds to make a large molecule, and prevents overetching and accelerated etching by alkaline compounds to form a uniform fine pyramid and at the same time the hydrogen bubbles generated by etching It is a component that prevents bubble stick phenomenon by quickly falling from the silicon wafer surface.
  • polysaccharides examples include glucan compounds, fructan compounds, mannan compounds, galactan compounds, or metal salts thereof.
  • glucan compounds and metal salts thereof e.g., Alkali metal salts
  • These can be used individually or in mixture of 2 or more types.
  • glucan compound examples include cellulose, dimethylaminoethyl cellulose, diethylaminoethyl cellulose, ethyl hydroxyethyl cellulose, methyl hydroxyethyl cellulose, 4-aminobenzyl cellulose, triethylaminoethyl cellulose, cyanoethyl cellulose, ethyl cellulose, Methyl cellulose, carboxymethyl cellulose, carboxyethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, alginic acid, amylose, amylopectin, pectin, starch, dextrin, ⁇ -cyclodextrin, ⁇ -cyclodextrin, ⁇ -cyclodextrin, hydrate Oxypropyl- ⁇ -cyclodextrin, methyl- ⁇ -cyclodextrin, dextran, dextransulfate sodium, saponin, glycogen, zymoic acid
  • the polysaccharide may have an average molecular weight of 5,000 to 1,000,000, preferably 50,000 to 200,000.
  • the polysaccharide may be included in an amount of 10 -9 to 0.5% by weight based on 100% by weight of the total amount of the texture etching solution composition of the crystalline silicon wafer, preferably 10 -6 to 0.1% by weight. If the content falls within the above range, it is possible to effectively prevent over-etching and etching acceleration. When the content is more than 0.5% by weight, it is difficult to form a desired fine pyramid by drastically lowering the etching rate by the alkali compound.
  • the texture etching solution composition of the crystalline silicon wafer of the present invention is a fatty acid or a metal salt thereof; Surfactants that are polyoxyethylene-based (POE) compounds, polyoxypropylene-based (POP) compounds, and copolymers thereof; And one or more additives selected from the group consisting of silica compounds.
  • POE polyoxyethylene-based
  • POP polyoxypropylene-based
  • additives selected from the group consisting of silica compounds.
  • Fatty acids and their metal salts are used in conjunction with polysaccharides to prevent overetching by alkali compounds, forming a uniform fine pyramid and at the same time quickly dropping the hydrogen bubbles generated by etching from the surface of the silicon wafer to prevent the occurrence of bubble sticking. It is an ingredient to say.
  • Fatty acids are carboxylic acids of hydrocarbon chains containing carboxyl groups, specifically acetic acid, propionic acid, butyric acid, valeric acid, enantiic acid, caprylic acid, pelagonic acid, capric acid, lauric acid, myristic acid, palmitic acid, Stearic acid, arachidic acid, behenic acid, lignoseric acid, serotic acid, eicosapentaenoic acid, docosahexaenoic acid, linoleic acid, ⁇ -linolenic acid, ⁇ -linolenic acid, dihomo- ⁇ -linolenic acid, arachidonic acid, Oleic acid, elideic acid, erucic acid, nerbonic acid, and the like.
  • the metal salt of a fatty acid may include an ester reactant of the above fatty acid with a metal salt such as NaOH or KOH. These can be used individually or in mixture of 2 or more types.
  • the fatty acid and the metal salt thereof may be included in an amount of 10 -9 to 10% by weight, preferably 10 -6 to 1% by weight, based on 100% by weight of the texture etching solution composition of the crystalline silicon wafer. When the content falls within the above range, over-etching can be effectively prevented.
  • Polyoxyethylene-based (POE) compounds, polyoxypropylene-based (POP) compounds and copolymers thereof are surfactants having a hydroxyl group.
  • Hydroxy ions [OH in the texture etchant composition - ]
  • Si 100 Direction and Si 111 By controlling the activity of Si 100 Direction and Si 111 Not only does it reduce the difference in the etching rate with respect to the direction, but also improves the wettability of the surface of the crystalline silicon wafer, thereby rapidly dropping the hydrogen bubbles generated by etching to prevent the occurrence of bubble stick phenomenon.
  • polyoxyethylene type (POE) surfactant polyoxyethylene glycol, polyoxyethylene glycol methyl ether, polyoxyethylene monoallyl ether, polyoxyethylene neopentyl ether, polyethylene glycol mono (tristyrylphenyl) ether, polyoxy Ethylene cetyl ether, polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxyethylene stearyl ether, polyoxyethylene tridecyl ether, polyoxyethylene decyl ether, polyoxyethylene octyl ether, polyoxyethylene bisphenol-A Polyoxyethylene having 6 to 30 carbon atoms in ether, polyoxyethylene glycerin ether, polyoxyethylene nonylphenyl ether, polyoxyethylene benzyl ether, polyoxyethylene phenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene phenol ether, alkyl group Ethylene alkylcyclohexyl ether, polyoxyethylene (
  • polypropylene glycol is mentioned as polyoxypropylene system (POP) surfactant.
  • POP polyoxypropylene system
  • polyoxyethylene-polyoxypropylene copolymer polyoxyethylene-polyoxypropylene copolymer
  • polyoxyethylene-polyoxypropylene decanyl ether copolymer polyoxyethylene Polyoxypropylene undecanyl ether copolymer
  • polyoxyethylene-polyoxypropylene dodecanyl ether copolymer polyoxyethylene-polyoxypropylene tetradecanyl ether copolymer
  • polyoxyethylene-polyoxypropylene 2-ethylhexyl ether air Copolymer polyoxyethylene-polyoxypropylene lauryl ether copolymer
  • polyoxyethylene-polyoxypropylene stearyl ether copolymer polyoxyethylene-polyoxypropylene stearyl ether copolymer
  • the polyoxyethylene-based (POE) compound, the polyoxypropylene-based (POP) compound, and a copolymer thereof and a surfactant thereof may be included in an amount of 10 -9 to 10% by weight based on 100% by weight of the texture etching solution composition of the crystalline silicon wafer. Preferably, it is 0.00001 to 0.1% by weight, more preferably 10 -6 to 1% by weight. When the content falls within the above range, it is possible to reduce the variation of the texture quality by location when the surface of the crystalline silicon wafer surface is textured.
  • the silica compound is a component that physically adsorbs on the surface of the crystalline silicon wafer and serves as a kind of mask to make the surface of the crystalline silicon wafer into a fine pyramid shape.
  • silica compound examples include powder, colloidal solution, or liquid metal silicate compounds. Specifically, fine powder silica; Colloidal silica solution stabilized with Na 2 O; Colloidal silica solution stabilized with K 2 O; Colloidal silica solution stabilized with acid solution; Colloidal silica solution stabilized with NH 3 ; Colloidal silica solution 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; Liquid lithium silicate etc. can be mentioned, These can be used individually or in mixture of 2 or more types.
  • the silica compound may be included in an amount of 10 -9 to 10% by weight, preferably 10 -6 to 1% by weight, based on 100% by weight of the total amount of the texture etching solution composition of the crystalline silicon wafer. 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.
  • Water may be included in the remaining amount in the total 100% by weight of the texture etching solution composition of the crystalline silicon wafer.
  • 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.
  • Texture etching liquid composition of the crystalline silicon wafer of the present invention comprising the above components, in particular, by containing the polysaccharides with the optimal content in conjunction with the cyclic compound to minimize the quality variation of the texture of each position on the surface of the crystalline silicon wafer
  • by improving the uniformity of the texture to maximize the absorption of sunlight and lower the light reflectance can increase the light efficiency.
  • it is possible to increase the number of processing for the unit usage there is no need to add a separate etching solution component during the texture etching process, there is no need to introduce the air rating equipment there is an advantage 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.
  • the texture etching method of the crystalline silicon wafer includes depositing, spraying or depositing and spraying the crystalline silicon wafer using the texture etching liquid composition of the crystalline silicon wafer of the present invention.
  • 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 allows the formation of a structure.
  • a texture etching solution composition of a crystalline silicon wafer was prepared by mixing 2% by weight of potassium hydroxide (KOH), 4% by weight of N-methylmorpholine (NMM), 0.001% by weight of alginic acid (AA) and the remaining amount of deionized distilled water.
  • KOH potassium hydroxide
  • NMM N-methylmorpholine
  • AA alginic acid
  • Example 2 The same procedure as in Example 1, except that the same ingredients and contents as in Table 1 were used. Here, the content represents weight percent.
  • a 1.5% by weight potassium hydroxide (KOH), 5% by weight isopropyl alcohol (IPA) and the remaining amount of deionized distilled water was mixed to prepare a texture etching solution composition of the crystalline silicon wafer.
  • the single crystal silicon wafer substrate was immersed in the texture etching liquid composition of the prepared silicon wafer at a temperature of 80 ° C. for 20 minutes.
  • Texture variation that is, uniformity, formed on the surface of the etched single crystal silicon wafer substrate was visually observed using a digital camera, a 3D optical microscope, and a scanning electron microscope (SEM), and evaluated based on the following criteria. .
  • the size of the fine pyramid formed on the surface of the textured etched single crystal silicon wafer substrate was measured using a scanning electron microscope (SEM). At this time, the size of the fine pyramid formed in the unit area was measured and expressed as their average value.
  • the average reflectance when the surface of the texture-etched single crystal silicon wafer substrate was irradiated with light having a wavelength band of 400-800 nm using a UV spectrophotometer was measured.
  • Example 1 ⁇ 3 11.91 Example 2 ⁇ 3 12.15 Example 3 ⁇ 3 12.07 Example 4 ⁇ 3 12.02 Example 5 ⁇ 3 11.78 Example 6 ⁇ 3 11.98 Example 7 ⁇ 3 11.23 Example 8 ⁇ 2 12.31 Example 9 ⁇ 3 12.21 Example 10 ⁇ 3 12.07 Example 11 ⁇ 3 11.35 Example 12 ⁇ 3 11.78 Example 13 ⁇ 3 11.98 Example 14 ⁇ 3 11.78 Example 15 ⁇ 3 12.06 Example 16 ⁇ 3 11.89 Example 17 ⁇ 3 11.73 Example 18 ⁇ 2 12.01 Example 19 ⁇ 3 11.78 Example 20 ⁇ 3 11.99 Example 21 ⁇ 2 10.32 Example 22 ⁇ 2 10.21 Example 23 ⁇ 2 10.35 Example 24 ⁇ 3 12.05 Example 25 ⁇ 2 10.57 Example 26 ⁇ 3 12.13 Example 27 ⁇ 3 11.98 Example 28 ⁇ 3 11.87 Example 29 ⁇ 3 11.89 Example 30 ⁇ 3 11.87 Example 31 ⁇ 3 11.82 Example 32 ⁇ 3 11.87 Example 33 ⁇ 3 11.77 Comparative Example 1 ⁇ 3 11.91 Example 2 ⁇ 3 12.15 Example 3 ⁇ 3 12.07
  • the alkali compound according to the present invention As shown in Table 2, the alkali compound according to the present invention; Cyclic compounds; Polysaccharides; And when the texture is etched using the texture etching solution compositions of Examples 1 to 33 containing the optimum amount of water, the uniformity of the fine pyramids formed on the surface of the single crystal silicon wafer is small and the uniformity is excellent. Low light efficiency was also improved.
  • FIG. 1 is a 3D optical micrograph showing the surface of the crystalline silicon wafer texture etched with the texture etching solution composition of Example 15,
  • Figure 2 is a SEM photograph showing the surface of the texture etched crystalline silicon wafer. Through this, it can be seen that a fine pyramid is formed over the entire surface of the wafer so that the quality variation is small and the texture uniformity is improved.
  • Comparative Example 1 which does not include a polysaccharide, had a poor appearance of the textured silicon wafer substrate, and a portion of the pyramid was not present.
  • Comparative Example 2 which contained an excessive amount of polysaccharide, the etching rate was too slow to increase the reflectance.
  • Comparative Example 3 which does not include the cyclic compound, part of the pyramid was not observed similarly to Comparative Example 1, and Comparative Example 4, which contained the excess of the cyclic compound, was difficult to control the etching rate, so that the reflectance was low. It's high.
  • the texture etching solution composition of Comparative Example 5 due to the low temperature of the isopropyl alcohol (IPA) due to the temperature gradient generated by the continuous input of the texture during the texture failure and cost more,
  • the texture etchant composition showed significantly inferior characteristics in comparison with Examples in terms of texture uniformity and light reflectance.
  • the texture etching solution compositions of Comparative Examples 7 and 8 exhibited a change with time in the etching solution composition itself when heated to the texture process temperature.

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Abstract

The present invention relates to a texture etchant composition for a crystalline silicon wafer and a texture etching method thereof, and more specifically to a texture etchant composition for a crystalline silicon wafer, which is capable of maximizing the absorbed amount of sunlight by including the optimal amount of alkali compounds, cyclic compounds, polysaccharides and residual water, improving texture uniformity according to a position on the surface of the crystalline silicon wafer, improving optical efficiency by reducing light reflectivity, and increasing the number of processed wafers according to the amount used per unit, and a texture etching method thereof.

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: 미국특허 제4,137,123호Patent Document 1: US Patent No. 4,137,123
특허문헌 2: 유럽특허 제0477424호Patent Document 2: European Patent No. 0477424
특허문헌 3: 한국등록특허 제0180621호Patent Document 3: Korean Registered Patent No. 0180621
본 발명은 결정성 실리콘 웨이퍼의 표면에 미세 피라미드 구조를 형성함에 있어서 위치별 텍스쳐의 품질 편차를 최소화하여 광 효율을 증가시키고 단위 사용량에 대한 처리 매수를 증가시킬 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, the texture etching solution composition of the crystalline silicon wafer capable of minimizing the quality variation of the texture for each location to increase the light efficiency and increase the number of treatments for the unit usage. The purpose is to provide.
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. 알칼리 화합물 0.1 내지 20중량%; 고리형 화합물 0.1 내지 50중량%; 다당류 10-9 내지 0.5중량%; 및 잔량의 물을 포함하는 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물.1. 0.1-20% by weight of alkali compound; 0.1-50% by weight of the cyclic compound; Polysaccharides 10 -9 to 0.5% by weight; And a residual amount of water.
2. 위 1에 있어서, 알칼리 화합물은 수산화칼륨, 수산화나트륨, 수산화암모늄, 테트라히드록시메틸암모늄 및 테트라히드록시에틸암모늄으로 이루어진 군으로부터 선택되는 1종 이상인 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물.2. The composition according to the above 1, wherein the alkali compound is at least one selected from the group consisting of potassium hydroxide, sodium hydroxide, ammonium hydroxide, tetrahydroxymethylammonium and tetrahydroxyethylammonium.
3. 위 1에 있어서, 고리형 화합물은 비점이 100℃ 이상인 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물.3. In the above 1, wherein the cyclic compound has a boiling point of 100 ℃ or more texture etching liquid composition of the crystalline silicon wafer.
4. 위 3에 있어서, 고리형 화합물은 한센의 용해도 파라미터가 6 내지 15인 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물.4. In the above 3, wherein the cyclic compound is Hansen solubility parameter of 6 to 15 texture etching liquid composition of the crystalline silicon wafer.
5. 위 1에 있어서, 다당류는 글루칸계 화합물, 프룩탄계 화합물, 만난계 화합물, 갈락탄계 화합물 및 이들의 금속염으로 이루어진 군으로부터 선택된 1종 이상인 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물.5. The method according to the above 1, wherein the polysaccharide is at least one selected from the group consisting of glucan-based compounds, fructan-based compounds, mannan-based compounds, galactan-based compounds and metal salts of the etching solution of the crystalline silicon wafer.
6. 위 5에 있어서, 다당류는 셀룰로오스, 디메틸아미노에틸셀룰로오스, 디에틸아미노에틸셀룰로오스, 에틸히드록시에틸셀룰로오스, 메틸히드록시에틸셀룰로오스, 4-아미노벤질셀룰로오스, 트리에틸아미노에틸셀룰로오스, 시아노에틸셀룰로오스, 에틸셀룰로오스, 메틸셀룰로오스, 카르복시메틸셀룰로오스, 카르복시에틸셀룰로오스, 히드록시에틸셀룰로오스, 히드록시프로필셀룰로오스, 알긴산, 아밀로오스, 아밀로펙틴, 펙틴, 스타치, 덱스트린, α-시클로덱스트린, β-시클로덱스트린, γ-시클로덱스트린, 히드록시프로필-β-시클로덱스트린, 메틸-β-시클로덱스트린, 덱스트란, 덱스트란설페이트나트륨, 사포닌, 글리코겐, 자이모산, 렌티난, 시조피난 및 이들의 금속염으로 이루어진 군으로부터 선택된 1종 이상의 글루칸계 화합물인 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물.6. In the above 5, the polysaccharide is cellulose, dimethylaminoethyl cellulose, diethylaminoethyl cellulose, ethyl hydroxyethyl cellulose, methyl hydroxyethyl cellulose, 4-aminobenzyl cellulose, triethylaminoethyl cellulose, cyanoethyl cellulose , Ethyl cellulose, methyl cellulose, carboxymethyl cellulose, carboxyethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, alginic acid, amylose, amylopectin, pectin, starch, dextrin, α-cyclodextrin, β-cyclodextrin, γ- 1 type selected from the group consisting of cyclodextrin, hydroxypropyl-β-cyclodextrin, methyl-β-cyclodextrin, dextran, dextransulfate sodium, saponin, glycogen, zymoic acid, lentinan, sizopinean and metal salts thereof Crystalline silicone web which is the above glucan type compound Texture etching liquid composition of the buffer.
7. 위 5에 있어서, 다당류는 평균 분자량이 5,000 내지 1,000,000인 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물.7. In the above 5, the polysaccharide has an average molecular weight of 5,000 to 1,000,000 texture etching liquid composition of a crystalline silicon wafer.
8. 위 1에 있어서, 수용성 극성 용매를 더 포함하는 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물.8. according to the above 1, the texture etching liquid composition of the crystalline silicon wafer further comprising a water-soluble polar solvent.
9. 위 8에 있어서, 수용성 극성 용매는 에틸렌글리콜모노메틸에테르, 디에틸렌글리콜모노메틸에테르, 트리에틸렌글리콜모노메틸에테르, 폴리에틸렌글리콜모노메틸에테르, 에틸렌글리콜모노에틸에테르, 디에틸렌글리콜모노에틸에테르, 에틸렌글리콜모노부틸에테르, 디에틸렌글리콜모노부틸에테르, 트리에틸렌글리콜모노부틸에테르, 프로필렌글리콜모노메틸에테르, 디프로필렌글리콜모노메틸에테르, 프로판올, 부탄올, 이소프로판올, 테트라하이드로퍼푸릴알코올, 에틸렌글리콜, 프로필렌글리콜, N-메틸포름아미드, N,N-디메틸포름아미드, 디메틸술폭사이드, 술폴란, 트리에틸포스페이트 및 트리부틸포스페이트으로 이루어진 군으로부터 선택된 1종 이상인 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물.9. In the above 8, the water-soluble polar solvent is 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, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propanol, butanol, isopropanol, tetrahydroperfuryl alcohol, ethylene glycol, propylene glycol And texture etching solution composition of at least one crystalline silicon wafer selected from the group consisting of N-methylformamide, N, N-dimethylformamide, dimethyl sulfoxide, sulfolane, triethyl phosphate and tributyl phosphate.
10. 위 8에 있어서, 수용성 극성 용매는 고리형 화합물 총 100중량%에 대하여 0.1 내지 30중량%로 포함되는 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물.10. In the above 8, the water-soluble polar solvent is a texture etching solution composition of the crystalline silicon wafer containing 0.1 to 30% by weight relative to the total 100% by weight of the cyclic compound.
11. 위 1에 있어서, 지방산 및 이의 금속염으로 이루어진 군으로부터 선택된 1종 이상을 더 포함하는 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물.11. The texture etching solution composition of claim 1, further comprising at least one selected from the group consisting of fatty acids and metal salts thereof.
12. 위 1에 있어서, 폴리옥시에틸렌계(POE) 화합물, 폴리옥시프로필렌계(POP) 화합물 및 이들의 공중합체로 이루어진 군으로부터 선택된 1종 이상의 계면활성제를 더 포함하는 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물.12. The texture etching solution of crystalline silicon wafer further comprising at least one surfactant selected from the group consisting of polyoxyethylene-based (POE) compounds, polyoxypropylene-based (POP) compounds and copolymers thereof Composition.
13. 위 1에 있어서, 미분말 실리카; Na2O로 안정화시킨 콜로이드 실리카 용액; K2O로 안정화시킨 콜로이드 실리카 용액; 산성액으로 안정화시킨 콜로이드 실리카 용액; NH3로 안정화시킨 콜로이드 실리카 용액; 에틸알코올, 프로필알코올, 에틸렌글리콜, 메틸에틸케톤 및 메틸이소부틸케톤으로 이루어진 군으로부터 선택된 1종 이상의 유기용매로 안정화시킨 콜로이드 실리카 용액; 액상 규산나트륨; 액상 규산칼륨; 및 액상 규산리튬으로 이루어진 군으로부터 선택된 1종 이상의 실리카 화합물을 더 포함하는 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물.13. according to the above 1, fine powder silica; Colloidal silica solution stabilized with Na 2 O; Colloidal silica solution stabilized with K 2 O; Colloidal silica solution stabilized with acid solution; Colloidal silica solution stabilized with NH 3 ; Colloidal silica solution 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 at least one silica compound selected from the group consisting of liquid lithium silicate.
14. 위 1 내지 13 중 어느 한 항의 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물로 결정성 실리콘 웨이퍼를 침적, 분무 또는 침적 및 분무하는 단계를 포함하는 결정성 실리콘 웨이퍼의 텍스쳐 에칭방법.14. The texture etching method of the crystalline silicon wafer comprising the step of depositing, spraying or depositing and spraying the crystalline silicon wafer with the texture etching liquid composition of any one of the above 1 to 13.
15. 위 14에 있어서, 침적, 분무 또는 침적 및 분무는 50 내지 100℃의 온도에서 30초 내지 60분 동안 수행되는 결정성 실리콘 웨이퍼의 텍스쳐 에칭방법.15. The method of claim 14, the deposition, spraying or deposition and spraying is a texture etching method of a crystalline silicon wafer is carried out 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 낮춰 광효율을 높일 수 있다.According to the texture etching liquid composition and the texture etching method of the crystalline silicon wafer of the present invention, the quality variation of the texture for each position of the surface of the crystalline silicon wafer is minimized, that is, the uniformity of the texture is improved to maximize the amount of sunlight absorption and lower the light reflectance. The light efficiency can be improved.
또한, 본 발명은 종래의 텍스쳐 에칭액 조성물에 비해 단위 사용량에 대한 처리 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.In addition, the present invention can increase the number of processing for the unit usage compared to the conventional texture etching solution composition, there is no need to add a separate etching solution components during the texture process and do not need to introduce an air rating equipment to improve the quality and productivity It can be improved and economic in terms of process cost.
도 1은 본 발명의 실시예 11의 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물로 텍스쳐 에칭된 단결정 실리콘 웨이퍼의 표면을 나타낸 3D 광학현미경 사진이며,1 is a 3D optical micrograph showing the surface of a single crystal silicon wafer texture-etched with the texture etching solution composition of the crystalline silicon wafer of Example 11 of the present invention,
도 2는 본 발명의 실시예 11의 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물로 텍스쳐 에칭된 단결정 실리콘 웨이퍼의 표면을 나타낸 SEM 사진이다.2 is a SEM photograph showing the surface of a single crystal silicon wafer textured etched with the texture etching liquid composition of the crystalline silicon wafer of Example 11 of the present invention.
본 발명은 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물 및 이를 이용한 결정성 실리콘 웨이퍼의 텍스쳐 에칭방법에 관한 것이다.The present invention relates to a texture etching liquid composition of a crystalline silicon wafer and a method of etching the texture of a crystalline silicon wafer using the same.
이하 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.
본 발명의 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물은 알칼리 화합물; 고리형 화합물; 다당류; 및 물을 최적의 함량으로 포함하는 것을 특징으로 한다.The texture etching solution composition of the crystalline silicon wafer of the present invention is an alkali compound; Cyclic compounds; Polysaccharides; And water in an optimal content.
보다 상세하게, 알칼리 화합물 0.1 내지 20중량%; 고리형 화합물 0.1 내지 50중량%; 다당류 10-9 내지 0.5중량%; 및 잔량의 물을 포함한다.More specifically, the alkali compound 0.1 to 20% by weight; 0.1-50% by weight of the cyclic compound; Polysaccharides 10 -9 to 0.5% by weight; And residual amount of water.
알칼리 화합물은 결정성 실리콘 웨이퍼의 표면을 에칭하는 성분으로서 그 종류는 특별히 한정되지 않는다. 예컨대, 수산화칼륨, 수산화나트륨, 수산화암모늄, 테트라히드록시메틸암모늄, 테트라히드록시에틸암모늄 등을 들 수 있으며, 이 중에서 수산화칼륨, 수산화나트륨이 바람직하다. 이들은 단독 또는 2종 이상 혼합하여 사용할 수 있다.An alkali compound is a component which etches the surface of a crystalline silicon wafer, The kind is not specifically limited. For example, potassium hydroxide, sodium hydroxide, ammonium hydroxide, tetrahydroxymethylammonium, tetrahydroxyethylammonium, etc. are mentioned, Among these, potassium hydroxide and sodium hydroxide are preferable. These can be used individually or in mixture of 2 or more types.
알칼리 화합물은 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물 총 100중량%에 대하여 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, and more preferably 1 to 5% by weight, based on 100% by weight of the total amount of the texture etching solution composition of the crystalline silicon wafer. When the content falls within the above range, the silicon wafer surface can be etched.
고리형 화합물은 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.The cyclic compound may be 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, wherein the wettability of the surface of the crystalline silicon wafer is improved to prevent over-etching by an alkali compound. By minimizing the quality variation of the texture by preventing it, it is also a component that can prevent the bubble stick phenomenon from occurring by rapidly reducing the amount of hydrogen bubbles generated by etching. 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 150 내지 400℃인 것이 좋다. 동시에, 고리형 화합물은 한센의 용해도 파라미터(Hansen solubility parameter(HSP), δp)가 6 내지 15인 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 150-400 degreeC. At the same time, it is preferable that the cyclic compound has a Hansen solubility parameter (HSP) of 6 to 15 in terms 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, 카프로락탐; 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, 카프로락톤; 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, caprolactam; 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, caprolactone; 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 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물 총 100중량%에 대하여 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 an amount of 0.1 to 50% by weight, more preferably 1 to 10% by weight based on 100% by weight of the total amount of the texture etching solution composition of the crystalline silicon wafer. 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 발명에서는 특히, 다당류를 최적의 함량으로 포함하는데 특징이 있다.In particular, the present invention is characterized by including the polysaccharide in an optimum content.
다당류(polysaccharide)는 단당류 2개 이상이 글리코시드 결합하여 큰 분자를 만들고 있는 당류로서, 알칼리 화합물에 의한 과에칭과 에칭 가속화를 방지함으로써 균일한 미세 피라미드를 형성하는 동시에 에칭에 의해 생성된 수소 버블을 실리콘 웨이퍼 표면으로부터 빨리 떨어뜨려 버블 스틱 현상을 방지하는 성분이다.Polysaccharide (polysaccharide) is a sugar in which two or more monosaccharides are glycosidic bonds to make a large molecule, and prevents overetching and accelerated etching by alkaline compounds to form a uniform fine pyramid and at the same time the hydrogen bubbles generated by etching It is a component that prevents bubble stick phenomenon by quickly falling from the silicon wafer surface.
다당류로는 글루칸계(glucan) 화합물, 프룩탄계(fructan) 화합물, 만난계(mannan) 화합물, 갈락탄계(galactan) 화합물 또는 이들의 금속염 등을 들 수 있으며, 이 중에서 글루칸계 화합물과 이의 금속염(예컨대, 알칼리 금속염)이 바람직하다. 이들은 단독 또는 2종 이상 혼합하여 사용할 수 있다.Examples of the polysaccharides include glucan compounds, fructan compounds, mannan compounds, galactan compounds, or metal salts thereof. Among them, glucan compounds and metal salts thereof (e.g., Alkali metal salts) are preferred. These can be used individually or in mixture of 2 or more types.
글루칸계 화합물로는 셀룰로오스, 디메틸아미노에틸셀룰로오스, 디에틸아미노에틸셀룰로오스, 에틸히드록시에틸셀룰로오스, 메틸히드록시에틸셀룰로오스, 4-아미노벤질셀룰로오스, 트리에틸아미노에틸셀룰로오스, 시아노에틸셀룰로오스, 에틸셀룰로오스, 메틸셀룰로오스, 카르복시메틸셀룰로오스, 카르복시에틸셀룰로오스, 히드록시에틸셀룰로오스, 히드록시프로필셀룰로오스, 알긴산, 아밀로오스, 아밀로펙틴, 펙틴, 스타치, 덱스트린, α-시클로덱스트린, β-시클로덱스트린, γ-시클로덱스트린, 히드록시프로필-β-시클로덱스트린, 메틸-β-시클로덱스트린, 덱스트란, 덱스트란설페이트나트륨, 사포닌, 글리코겐, 자이모산, 렌티난, 시조피난 또는 이들의 금속염 등을 들 수 있다.Examples of the glucan compound include cellulose, dimethylaminoethyl cellulose, diethylaminoethyl cellulose, ethyl hydroxyethyl cellulose, methyl hydroxyethyl cellulose, 4-aminobenzyl cellulose, triethylaminoethyl cellulose, cyanoethyl cellulose, ethyl cellulose, Methyl cellulose, carboxymethyl cellulose, carboxyethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, alginic acid, amylose, amylopectin, pectin, starch, dextrin, α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin, hydrate Oxypropyl-β-cyclodextrin, methyl-β-cyclodextrin, dextran, dextransulfate sodium, saponin, glycogen, zymoic acid, lentinan, sizopinean or metal salts thereof.
다당류는 평균 분자량이 5,000 내지 1,000,000인 것일 수 있으며, 바람직하게 50,000 내지 200,000인 것이 좋다.The polysaccharide may have an average molecular weight of 5,000 to 1,000,000, preferably 50,000 to 200,000.
다당류는 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물 총 100중량%에 대하여 10-9 내지 0.5중량%로 포함될 수 있으며, 바람직하게는 10-6 내지 0.1중량%인 것이 좋다. 함량이 상기 범위에 해당되는 경우 과에칭과 에칭 가속화를 효과적으로 방지할 수 있다. 함량이 0.5중량% 초과인 경우 알칼리 화합물에 의한 에칭 속도를 급격하게 저하시켜 원하는 미세 피라미드를 형성하기 어렵다.The polysaccharide may be included in an amount of 10 -9 to 0.5% by weight based on 100% by weight of the total amount of the texture etching solution composition of the crystalline silicon wafer, preferably 10 -6 to 0.1% by weight. If the content falls within the above range, it is possible to effectively prevent over-etching and etching acceleration. When the content is more than 0.5% by weight, it is difficult to form a desired fine pyramid by drastically lowering the etching rate by the alkali compound.
본 발명의 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물은 지방산 또는 이의 금속염; 폴리옥시에틸렌계(POE) 화합물, 폴리옥시프로필렌계(POP) 화합물 및 이들의 공중합체인 계면활성제; 및 실리카 화합물로 이루어진 군으로부터 선택된 1종 이상의 첨가제를 더 포함할 수 있다.The texture etching solution composition of the crystalline silicon wafer of the present invention is a fatty acid or a metal salt thereof; Surfactants that are polyoxyethylene-based (POE) compounds, polyoxypropylene-based (POP) compounds, and copolymers thereof; And one or more additives selected from the group consisting of silica compounds.
지방산 및 이의 금속염은 다당류와 함께 사용되어 알칼리 화합물에 의한 과에칭을 방지함으로써 균일한 미세 피라미드를 형성하고 동시에 에칭에 의해 생성된 수소 버블을 실리콘 웨이퍼 표면으로부터 빨리 떨어뜨려 버블 스틱 현상이 발생하는 것도 방지하는 성분이다.Fatty acids and their metal salts are used in conjunction with polysaccharides to prevent overetching by alkali compounds, forming a uniform fine pyramid and at the same time quickly dropping the hydrogen bubbles generated by etching from the surface of the silicon wafer to prevent the occurrence of bubble sticking. It is an ingredient to say.
지방산은 카르복시기를 함유하는 탄화수소 사슬의 카르복시산으로서, 구체적으로 아세트산, 프로피온산, 부틸산, 발레르산, 에난틱산, 카프릴산, 펠라곤산, 카프릭산, 라우르산, 미리스트산, 팔미트산, 스테아르산, 아라키드산, 베헨산, 리그노세린산, 세로트산, 에이코사펜타엔산, 도코사헥사엔산, 리놀레산, α-리놀렌산, γ-리놀렌산, 디호모-γ-리놀렌산, 아라키돈산, 올레산, 엘라이드산, 에루스산, 네르본산 등을 들 수 있다. 또한, 지방산의 금속염은 위 지방산과 NaOH 또는 KOH와 같은 금속염의 에스테르 반응물을 들 수 있다. 이들은 단독 또는 2종 이상 혼합하여 사용할 수 있다.Fatty acids are carboxylic acids of hydrocarbon chains containing carboxyl groups, specifically acetic acid, propionic acid, butyric acid, valeric acid, enantiic acid, caprylic acid, pelagonic acid, capric acid, lauric acid, myristic acid, palmitic acid, Stearic acid, arachidic acid, behenic acid, lignoseric acid, serotic acid, eicosapentaenoic acid, docosahexaenoic acid, linoleic acid, α-linolenic acid, γ-linolenic acid, dihomo-γ-linolenic acid, arachidonic acid, Oleic acid, elideic acid, erucic acid, nerbonic acid, and the like. In addition, the metal salt of a fatty acid may include an ester reactant of the above fatty acid with a metal salt such as NaOH or KOH. These can be used individually or in mixture of 2 or more types.
지방산 및 이의 금속염은 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물 총 100중량%에 대하여 10-9 내지 10중량%로 포함될 수 있으며, 바람직하게는 10-6 내지 1중량%인 것이 좋다. 함량이 상기 범위에 해당되는 경우 과에칭을 효과적으로 방지할 수 있다.The fatty acid and the metal salt thereof may be included in an amount of 10 -9 to 10% by weight, preferably 10 -6 to 1% by weight, based on 100% by weight of the texture etching solution composition of the crystalline silicon wafer. When the content falls within the above range, over-etching can be effectively prevented.
폴리옥시에틸렌계(POE) 화합물, 폴리옥시프로필렌계(POP) 화합물 및 이들의 공중합체는 히드록시기를 갖는 계면활성제로서 텍스쳐 에칭액 조성물 중 히드록시 이온[OH-]의 활동도를 조절하여 Si100 방향과 Si111 방향에 대한 에칭 속도의 차이를 감소시킬 뿐만 아니라 결정성 실리콘 웨이퍼 표면의 젖음성을 개선시켜 에칭에 의해 생성된 수소 버블을 빠르게 떨어뜨려 버블 스틱 현상이 발생하는 것도 방지하는 성분이다.Polyoxyethylene-based (POE) compounds, polyoxypropylene-based (POP) compounds and copolymers thereof are surfactants having a hydroxyl group. Hydroxy ions [OH in the texture etchant composition-] By controlling the activity of Si100 Direction and Si111 Not only does it reduce the difference in the etching rate with respect to the direction, but also improves the wettability of the surface of the crystalline silicon wafer, thereby rapidly dropping the hydrogen bubbles generated by etching to prevent the occurrence of bubble stick phenomenon.
폴리옥시에틸렌계(POE) 계면활성제로는 폴리옥시에틸렌글리콜, 폴리옥시에틸렌글리콜메틸에테르, 폴리옥시에틸렌모노알릴에테르, 폴리옥시에틸렌네오펜틸에테르, 폴리에틸렌글리콜모노(트리스티릴페닐)에테르, 폴리옥시에틸렌세틸에테르, 폴리옥시에틸렌라우릴에테르, 폴리옥시에틸렌올레일에테르, 폴리옥시에틸렌스테아릴에테르, 폴리옥시에틸렌트리데실에테르, 폴리옥시에틸렌데실에테르, 폴리옥시에틸렌옥틸에테르, 폴리옥시에틸렌비스페놀-A에테르, 폴리옥시에틸렌글리세린에테르, 폴리옥시에틸렌노닐페닐에테르, 폴리옥시에틸렌벤질에테르, 폴리옥시에틸렌페닐에테르, 폴리옥시에틸렌옥틸페닐에테르, 폴리옥시에틸렌페놀에테르, 알킬기의 탄소수가 6-30인 폴리옥시에틸렌알킬시클로헥실에테르, 폴리옥시에틸렌β-나프톨에테르, 폴리옥시에틸렌 캐스터 에테르(polyoxyethylene castor ether), 폴리옥시에틸렌 수소화 캐스터 에테르(polyoxyethylene hydrogenated castor ether); 폴리옥시에틸렌라우릴에스테르, 폴리옥시에틸렌스테아릴에스테르, 폴리옥시에틸렌올레일에스테르; 폴리옥시에틸렌라우릴아민, 폴리옥시에틸렌스테아릴아민, 폴리옥시에틸렌탈로우아민 등을 들 수 있다. 또한, 폴리옥시프로필렌계(POP) 계면활성제로는 폴리프로필렌글리콜을 들 수 있다. 또한, 폴리옥시에틸렌계(POE) 화합물과 폴리옥시프로필렌계(POP)계 화합물의 공중합체로는 폴리옥시에틸렌-폴리옥시프로필렌 공중합체, 폴리옥시에틸렌-폴리옥시프로필렌 데카닐에테르 공중합체, 폴리옥시에틸렌-폴리옥시프로필렌 운데카닐에테르 공중합체, 폴리옥시에틸렌-폴리옥시프로필렌 도데카닐에테르 공중합체, 폴리옥시에틸렌-폴리옥시프로필렌 테트라데카닐에테르 공중합체, 폴리옥시에틸렌-폴리옥시프로필렌 2-에틸헥실에테르 공중합체, 폴리옥시에틸렌-폴리옥시프로필렌 라우릴에테르 공중합체, 폴리옥시에틸렌-폴리옥시프로필렌 스테아릴에테르 공중합체, 글리세린 부가형 폴리옥시에틸렌-폴리옥시프로필렌 공중합체, 에틸렌디아민 부가형 폴리옥시에틸렌-폴리옥시프로필렌 공중합체 등을 들 수 있다. 이들은 단독 또는 2종 이상 혼합하여 사용할 수 있다.As polyoxyethylene type (POE) surfactant, polyoxyethylene glycol, polyoxyethylene glycol methyl ether, polyoxyethylene monoallyl ether, polyoxyethylene neopentyl ether, polyethylene glycol mono (tristyrylphenyl) ether, polyoxy Ethylene cetyl ether, polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxyethylene stearyl ether, polyoxyethylene tridecyl ether, polyoxyethylene decyl ether, polyoxyethylene octyl ether, polyoxyethylene bisphenol-A Polyoxyethylene having 6 to 30 carbon atoms in ether, polyoxyethylene glycerin ether, polyoxyethylene nonylphenyl ether, polyoxyethylene benzyl ether, polyoxyethylene phenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene phenol ether, alkyl group Ethylene alkylcyclohexyl ether, polyoxyethylene (beta) -naphthol ether, polyox Ethylene castor ether (polyoxyethylene castor ether), polyoxyethylene hydrogenated castor ether (polyoxyethylene hydrogenated castor ether); Polyoxyethylene lauryl ester, polyoxyethylene stearyl ester, polyoxyethylene oleyl ester; Polyoxyethylene laurylamine, polyoxyethylene stearylamine, polyoxyethylene tallowamine, etc. are mentioned. Moreover, polypropylene glycol is mentioned as polyoxypropylene system (POP) surfactant. In addition, as a copolymer of a polyoxyethylene-based (POE) compound and a polyoxypropylene-based (POP) -based compound, polyoxyethylene-polyoxypropylene copolymer, polyoxyethylene-polyoxypropylene decanyl ether copolymer, polyoxyethylene Polyoxypropylene undecanyl ether copolymer, polyoxyethylene-polyoxypropylene dodecanyl ether copolymer, polyoxyethylene-polyoxypropylene tetradecanyl ether copolymer, polyoxyethylene-polyoxypropylene 2-ethylhexyl ether air Copolymer, polyoxyethylene-polyoxypropylene lauryl ether copolymer, polyoxyethylene-polyoxypropylene stearyl ether copolymer, glycerin addition polyoxyethylene-polyoxypropylene copolymer, ethylenediamine addition polyoxyethylene-polyoxypropylene And copolymers. These can be used individually or in mixture of 2 or more types.
폴리옥시에틸렌계(POE) 화합물, 폴리옥시프로필렌계(POP) 화합물 및 이들의 공중합체인 계면활성제는 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물 총 100중량%에 대하여 10-9 내지 10중량%로 포함될 수 있고, 바람직하게는 0.00001 내지 0.1중량%, 보다 바람직하게는 10-6 내지 1중량%인 것이 좋다. 함량이 상기 범위에 해당되는 경우 결정성 실리콘 웨이퍼 표면의 텍스쳐 시 위치별 텍스쳐 품질의 편차를 감소시킬 수 있다.The polyoxyethylene-based (POE) compound, the polyoxypropylene-based (POP) compound, and a copolymer thereof and a surfactant thereof may be included in an amount of 10 -9 to 10% by weight based on 100% by weight of the texture etching solution composition of the crystalline silicon wafer. Preferably, it is 0.00001 to 0.1% by weight, more preferably 10 -6 to 1% by weight. When the content falls within the above range, it is possible to reduce the variation of the texture quality by location when the surface of the crystalline silicon wafer surface is textured.
또한, 실리카 화합물은 결정성 실리콘 웨이퍼 표면에 물리적으로 흡착하여 일종의 마스크 역할을 함으로써 결정성 실리콘 웨이퍼 표면을 미세 피라미드 형상으로 만들어 주는 성분이다.In addition, the silica compound is a component that physically adsorbs on the surface of the crystalline silicon wafer and serves as a kind of mask to make the surface of the crystalline silicon wafer into a fine pyramid shape.
실리카 화합물로는 분말형, 콜로이드 용액형 또는 액상 규산금속 화합물 등을 들 수 있다. 구체적으로, 미분말 실리카; Na2O로 안정화시킨 콜로이드 실리카 용액; K2O로 안정화시킨 콜로이드 실리카 용액; 산성액으로 안정화시킨 콜로이드 실리카 용액; NH3로 안정화시킨 콜로이드 실리카 용액; 에틸알코올, 프로필알코올, 에틸렌글리콜, 메틸에틸케톤 및 메틸이소부틸케톤으로 이루어진 군으로부터 선택된 1종 이상의 유기용매로 안정화시킨 콜로이드 실리카 용액; 액상 규산나트륨; 액상 규산칼륨; 액상 규산리튬 등을 들 수 있으며, 이들은 단독 또는 2종 이상 혼합하여 사용할 수 있다.Examples of the silica compound include powder, colloidal solution, or liquid metal silicate compounds. Specifically, fine powder silica; Colloidal silica solution stabilized with Na 2 O; Colloidal silica solution stabilized with K 2 O; Colloidal silica solution stabilized with acid solution; Colloidal silica solution stabilized with NH 3 ; Colloidal silica solution 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; Liquid lithium silicate etc. can be mentioned, These can be used individually or in mixture of 2 or more types.
실리카 화합물은 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물 총 100중량%에 대하여 10-9 내지 10중량%로 포함될 수 있고, 바람직하게는 10-6 내지 1중량%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 -9 to 10% by weight, preferably 10 -6 to 1% by weight, based on 100% by weight of the total amount of the texture etching solution composition of the crystalline silicon wafer. 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.
물은 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물 총 100중량%에 잔량으로 포함될 수 있다.Water may be included in the remaining amount in the total 100% by weight of the texture etching solution composition of the crystalline silicon wafer.
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 고리형 화합물과 함께 다당류를 최적의 함량으로 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, 단위 사용량에 대한 처리 매수를 증가시킬 수 있으며, 텍스쳐 에칭 공정 중 별도의 에칭액 성분을 투입할 필요가 없고 에어레이팅 장비도 도입할 필요가 없어 생산성과 비용 면에서 이점이 있다.Texture etching liquid composition of the crystalline silicon wafer of the present invention comprising the above components, in particular, by containing the polysaccharides with the optimal content in conjunction with the cyclic compound to minimize the quality variation of the texture of each position on the surface of the crystalline silicon wafer In other words, by improving the uniformity of the texture to maximize the absorption of sunlight and lower the light reflectance can increase the light efficiency. In addition, it is possible to increase the number of processing for the unit usage, there is no need to add a separate etching solution component during the texture etching process, there is no need to introduce the air rating equipment there is an advantage 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 조성물을 이용하여 결정성 실리콘 웨이퍼를 침적, 분무 또는 침적 및 분무하는 단계를 포함한다.The texture etching method of the crystalline silicon wafer includes depositing, spraying or depositing and spraying the crystalline silicon wafer using the texture etching liquid composition of the crystalline silicon wafer of the present invention.
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 한다.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 allows the formation of a structure.
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.
실시예Example
실시예 1Example 1
수산화칼륨(KOH) 2중량%, N-메틸모르폴린(NMM) 4중량%, 알긴산(AA) 0.001중량% 및 잔량의 탈이온 증류수를 혼합하여 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물을 제조하였다.A texture etching solution composition of a crystalline silicon wafer was prepared by mixing 2% by weight of potassium hydroxide (KOH), 4% by weight of N-methylmorpholine (NMM), 0.001% by weight of alginic acid (AA) and the remaining amount of deionized distilled water.
실시예 2-33, 비교예 1-4Example 2-33, Comparative Example 1-4
상기 실시예 1과 동일하게 실시하되, 하기 표 1에서와 같은 성분 및 함량을 사용하였다. 여기서, 함량은 중량%를 나타낸다.The same procedure as in Example 1, except that the same ingredients and contents as in Table 1 were used. Here, the content represents weight percent.
표 1
구분 알칼리 화합물 고리형 화합물/용매 다당류 지방산/염 계면활성제 실리카 화합물
종류 함량 종류 함량 종류 함량 종류 함량 종류 함량 종류 함량
실시예1 KOH 2 NMM 4 AA 0.001 - - - - - -
실시예2 KOH 2 NMM 4 AANa 0.002 - - - - - -
실시예3 KOH 2 NMM 4 CMC 0.001 - - - - - -
실시예4 KOH 2 NMM 4 CMCNa 0.002 - - - - - -
실시예5 KOH 2 NMM 4 DSNa 0.001 - - - - - -
실시예6 KOH 2 NMP 4 CMCNa 0.002 - - - - - -
실시예7 KOH 2 NMPTP 40.2 CMCNa 0.002 - - - - - -
실시예8 KOH 2 NMPCTam 40.2 CMCNa 0.002 - - - - - -
실시예9 KOH 2 NMPAEP 3.80.2 AA 0.002 - - - - - -
실시예10 KOH 2 NMPGBL 3.80.2 AA 0.003 - - - - - -
실시예11 KOH 2 NMPGBLTP 3.80.20.2 AA 0.003 - - - - - -
실시예12 KOH 2 NMPGBLCTon 3.80.20.2 AA 0.003 - - - - - -
실시예13 KOH 2 NMPEC 3.80.2 AA 0.002 - - - - - -
실시예14 KOH 2 NMPPC 3.80.2 AA 0.003 - - - - - -
실시예15 KOH 2 NMPECPC 1.60.450.15 AA 0.002 - - - - - -
실시예16 KOH 2 NMPECPC 1.30.30.1 CMCNa 0.001 - - - - - -
실시예17 KOH 2 NMPECPCTP 1.30.30.10.2 CMCNa 0.001 - - - - - -
실시예18 KOH 2 NMPECPCCTam 1.30.30.10.2 CMCNa 0.001 - - - - - -
실시예19 NaOH 1 NMPECPC 1.30.20.2 CMCNa 0.002 - - - - - -
실시예20 KOH 2 NMMECPC 1.30.30.1 AA 0.003 - - - - - -
실시예 21 KOH 2 NVP 0.2 CMCNa 0.002 - - - - - -
실시예 22 KOH 2 NVPTP 0.20.2 CMCNa 0.002 - - - - - -
실시예 23 KOH 2 NVPCTon 0.20.2 CMCNa 0.002 - - - - - -
실시예24 KOH 2 NMP EC PC 1.6 0.45 0.15 CMCNa 0.002 LANa 0.003 - - - -
실시예25 KOH 2 NVP 0.2 CMCNa 0.002 LANa 0.003
실시예26 KOH 2 NMMAEP 1.60.6 AA 0.003 - - PBE 0.001 - -
실시예27 KOH 2 NMPGBL 1.60.6 CMCNa 0.002 - - POE 0.001 - -
실시예28 KOH 2 NMPGBL 1.60.6 AA 0.003 - - - - SSS 0.2
실시예29 KOH 2 NMMAEP 1.60.4 CMCNa 0.002 - - - - SCS 0.2
실시예30 KOH 2 NMMECPC 1.60.450.15 AA 0.003 LA 0.003 POE 0.001 - -
실시예31 KOH 2 NMPECPC 1.60.450.15 CMCNa 0.001 LANa 0.003 PBE 0.001 - -
실시예32 KOH 2 NMMECPC 1.60.450.15 AA 0.003 LA 0.003 POE 0.001 SSS 0.2
실시예33 KOH 2 NMPECPC 1.30.30.1 CMCNa 0.001 LANa 0.003 PBE 0.001 SCS 0.2
비교예1 KOH 2 NMPECPC 1.60.450.15 - - - - - - - -
비교예2 KOH 2 NMPECPC 1.60.450.15 AA 0.6 - - - - - -
비교예3 KOH 2 - - AA 0.003 - - - - - -
비교예4 KOH 2 NMP 51 AA 0.001 - - - - - -
KOH: 수산화칼륨NMM: N-메틸모르폴린NMP: N-메틸피롤리돈AEP: N-(2-아미노에틸)피페라진GBL: γ-부티로락톤EC: 에틸렌카보네이트PC: 프로필렌카보네이트NVP: N-비닐피롤리돈TP: 트리에틸포스페이트CTam: 카프로락탐CTon: 카프로락톤AA: 알긴산AANa: 알긴산나트륨CMC: 카르복시메틸셀룰로오스CMCNa: 카르복시메틸셀룰로오스나트륨DSNa: 덱스트란설페이트나트륨LANa: 라우르산나트륨 LA: 라우르산PBE: 폴리옥시에틸렌벤질에테르POE: 폴리옥시에틸렌옥틸페닐에테르SSS: 액상 규산나트륨SCS: Na2O로 안정화시킨 콜로이드 실리카 용액
Table 1
division Alkali compounds Cyclic Compounds / Solvents Polysaccharides Fatty acid / salt Surfactants Silica compounds
Kinds content Kinds content Kinds content Kinds content Kinds content Kinds content
Example 1 KOH 2 NMM 4 AA 0.001 - - - - - -
Example 2 KOH 2 NMM 4 AANa 0.002 - - - - - -
Example 3 KOH 2 NMM 4 CMC 0.001 - - - - - -
Example 4 KOH 2 NMM 4 CMCNa 0.002 - - - - - -
Example 5 KOH 2 NMM 4 DSNa 0.001 - - - - - -
Example 6 KOH 2 NMP 4 CMCNa 0.002 - - - - - -
Example 7 KOH 2 NMPTP 40.2 CMCNa 0.002 - - - - - -
Example 8 KOH 2 NMPCTam 40.2 CMCNa 0.002 - - - - - -
Example 9 KOH 2 NMPAEP 3.80.2 AA 0.002 - - - - - -
Example 10 KOH 2 NMPGBL 3.80.2 AA 0.003 - - - - - -
Example 11 KOH 2 NMPGBLTP 3.80.20.2 AA 0.003 - - - - - -
Example 12 KOH 2 NMPGBLCTon 3.80.20.2 AA 0.003 - - - - - -
Example 13 KOH 2 NMPEC 3.80.2 AA 0.002 - - - - - -
Example 14 KOH 2 NMPPC 3.80.2 AA 0.003 - - - - - -
Example 15 KOH 2 NMPECPC 1.60.450.15 AA 0.002 - - - - - -
Example 16 KOH 2 NMPECPC 1.30.30.1 CMCNa 0.001 - - - - - -
Example 17 KOH 2 NMPECPCTP 1.30.30.10.2 CMCNa 0.001 - - - - - -
Example 18 KOH 2 NMPECPCCTam 1.30.30.10.2 CMCNa 0.001 - - - - - -
Example 19 NaOH One NMPECPC 1.30.20.2 CMCNa 0.002 - - - - - -
Example 20 KOH 2 NMMECPC 1.30.30.1 AA 0.003 - - - - - -
Example 21 KOH 2 NVP 0.2 CMCNa 0.002 - - - - - -
Example 22 KOH 2 NVPTP 0.20.2 CMCNa 0.002 - - - - - -
Example 23 KOH 2 NVPCTon 0.20.2 CMCNa 0.002 - - - - - -
Example 24 KOH 2 NMP EC PC 1.6 0.45 0.15 CMCNa 0.002 LANa 0.003 - - - -
Example 25 KOH 2 NVP 0.2 CMCNa 0.002 LANa 0.003
Example 26 KOH 2 NMMAEP 1.60.6 AA 0.003 - - PBE 0.001 - -
Example 27 KOH 2 NMPGBL 1.60.6 CMCNa 0.002 - - POE 0.001 - -
Example 28 KOH 2 NMPGBL 1.60.6 AA 0.003 - - - - SSS 0.2
Example 29 KOH 2 NMMAEP 1.60.4 CMCNa 0.002 - - - - SCS 0.2
Example 30 KOH 2 NMMECPC 1.60.450.15 AA 0.003 LA 0.003 POE 0.001 - -
Example 31 KOH 2 NMPECPC 1.60.450.15 CMCNa 0.001 LANa 0.003 PBE 0.001 - -
Example 32 KOH 2 NMMECPC 1.60.450.15 AA 0.003 LA 0.003 POE 0.001 SSS 0.2
Example 33 KOH 2 NMPECPC 1.30.30.1 CMCNa 0.001 LANa 0.003 PBE 0.001 SCS 0.2
Comparative Example 1 KOH 2 NMPECPC 1.60.450.15 - - - - - - - -
Comparative Example 2 KOH 2 NMPECPC 1.60.450.15 AA 0.6 - - - - - -
Comparative Example 3 KOH 2 - - AA 0.003 - - - - - -
Comparative Example 4 KOH 2 NMP 51 AA 0.001 - - - - - -
KOH: potassium hydroxide NMM: N-methylmorpholine NMP: N-methylpyrrolidone AEP: N- (2-aminoethyl) piperazine GBL: γ-butyrolactone EC: ethylene carbonate PC: propylene carbonate NVP: N- Vinylpyrrolidone TP: Triethyl phosphate CTam: Caprolactam CTon: Caprolactone AA: Alginate AANa: Sodium alginate CMC: Carboxymethyl cellulose CMCNa: Carboxymethyl cellulose sodium DSNa: Dextran sulfate sodium LANa: Sodium laurate LA: La Urethane PBE: Polyoxyethylene benzyl ether POE: Polyoxyethylene octylphenyl ether SSS: Liquid sodium silicate SCS: Colloidal silica solution stabilized with Na 2 O
비교예 5Comparative Example 5
수산화칼륨(KOH) 1.5중량%, 이소프로필알코올(IPA) 5중량% 및 잔량의 탈이온 증류수를 혼합하여 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물을 제조하였다.A 1.5% by weight potassium hydroxide (KOH), 5% by weight isopropyl alcohol (IPA) and the remaining amount of deionized distilled water was mixed to prepare a texture etching solution composition of the crystalline silicon wafer.
비교예 6Comparative Example 6
상기 비교예 5와 동일하게 실시하되, 이소프로필알코올(IPA) 대신에 에틸렌글리콜(EG)을 사용하였다.In the same manner as in Comparative Example 5, ethylene glycol (EG) was used instead of isopropyl alcohol (IPA).
비교예 7Comparative Example 7
상기 비교예 5와 동일하게 실시하되, 이소프로필알코올(IPA) 대신에 메틸디글리콜(MDG)을 사용하였다.In the same manner as in Comparative Example 5, but instead of isopropyl alcohol (IPA) was used methyl diglycol (MDG).
비교예 8Comparative Example 8
상기 비교예 5와 동일하게 실시하되, 이소프로필알코올(IPA) 대신에 모노에틸아민(MEA)을 사용하였다.The same procedure as in Comparative Example 5 except that monoethylamine (MEA) was used instead of isopropyl alcohol (IPA).
시험예Test Example
상기 실시예 및 비교예에서 제조된 실리콘 웨이퍼의 텍스쳐 에칭액 조성물의 텍스쳐 에칭 효과를 하기 방법으로 평가하고, 그 결과를 하기 표 2에 나타내었다.The texture etching effect of the texture etching solution composition of the silicon wafers prepared in Examples and Comparative Examples was evaluated by the following method, and the results are shown in Table 2 below.
단결정 실리콘 웨이퍼 기판을 제조된 실리콘 웨이퍼의 텍스쳐 에칭액 조성물에 80℃의 온도로 20분 동안 침적시켰다.The single crystal silicon wafer substrate was immersed in the texture etching liquid composition of the prepared silicon wafer at a temperature of 80 ° C. for 20 minutes.
(1) 텍스쳐 균일성(1) texture uniformity
텍스쳐 에칭된 단결정 실리콘 웨이퍼 기판 표면에 형성된 텍스쳐의 편차, 즉 균일성을 디지털 카메라, 3D 광학현미경 및 주사전자현미경(Scanning electron microscope, SEM)을 이용하여 육안으로 관찰하고, 하기 기준에 의거하여 평가하였다.Texture variation, that is, uniformity, formed on the surface of the etched single crystal silicon wafer substrate was visually observed using a digital camera, a 3D optical microscope, and a scanning electron microscope (SEM), and evaluated based on the following criteria. .
<평가기준><Evaluation Criteria>
◎: 웨이퍼 기판 전부에 피라미드 형성.(Double-circle): Pyramid formation in all the wafer substrates.
○: 웨이퍼 기판 일부에 피라미드 미형성(미형성 부분 5% 미만).(Circle): Pyramidal non-formation (less than 5% of unformed part) in a part of wafer substrate.
△: 웨이퍼 기판 일부에 피라미드 미형성(미형성 부분 5-50%).(Triangle | delta): Pyramid non-formation in 5 part of wafer substrates (5-50% of unformed part).
×: 웨이퍼 기판 대부분에 피라미드 미형성(미형성 부분 90% 이상).X: Pyramid unformed in most wafer substrates (90% or more of unformed parts).
(2) 피라미드 평균 크기(㎛)(2) Pyramid average size (㎛)
텍스쳐 에칭된 단결정 실리콘 웨이퍼 기판 표면에 형성된 미세 피라미드의 크기를 주사전자현미경(Scanning electron microscope, SEM)을 이용하여 측정하였다. 이때, 단위 면적에 형성된 미세 피라미드의 크기를 측정한 후 이들의 평균값으로 나타내었다.The size of the fine pyramid formed on the surface of the textured etched single crystal silicon wafer substrate was measured using a scanning electron microscope (SEM). At this time, the size of the fine pyramid formed in the unit area was measured and expressed as their average value.
(3) 평균 반사율(%)(3) Average reflectance (%)
텍스쳐 에칭된 단결정 실리콘 웨이퍼 기판 표면에 UV 분광광도계를 이용하여 400-800㎚의 파장대를 갖는 광을 조사하였을 때의 평균 반사율을 측정하였다.The average reflectance when the surface of the texture-etched single crystal silicon wafer substrate was irradiated with light having a wavelength band of 400-800 nm using a UV spectrophotometer was measured.
표 2
구분 텍스쳐 균일성 피라미드 평균 크기(㎛) 평균 반사율(%)
실시예1 ◎ 3 11.91
실시예2 ◎ 3 12.15
실시예3 ◎ 3 12.07
실시예4 ◎ 3 12.02
실시예5 ◎ 3 11.78
실시예6 ◎ 3 11.98
실시예7 ◎ 3 11.23
실시예8 ◎ 2 12.31
실시예9 ◎ 3 12.21
실시예10 ◎ 3 12.07
실시예11 ◎ 3 11.35
실시예12 ◎ 3 11.78
실시예13 ◎ 3 11.98
실시예14 ◎ 3 11.78
실시예15 ◎ 3 12.06
실시예16 ◎ 3 11.89
실시예17 ◎ 3 11.73
실시예18 ◎ 2 12.01
실시예19 ◎ 3 11.78
실시예20 ◎ 3 11.99
실시예21 ◎ 2 10.32
실시예22 ◎ 2 10.21
실시예23 ◎ 2 10.35
실시예24 ◎ 3 12.05
실시예25 ◎ 2 10.57
실시예26 ◎ 3 12.13
실시예27 ◎ 3 11.98
실시예28 ◎ 3 11.87
실시예29 ◎ 3 11.89
실시예30 ◎ 3 11.87
실시예31 ◎ 3 11.82
실시예32 ◎ 3 11.87
실시예33 ◎ 3 11.77
비교예1 ○ 6 12.56
비교예2 △ 5 20.12
비교예3 ○ 5 12.14
비교예4 △ 5 22.87
비교예5 ○ 5 13.22
비교예6 × 10 21.13
비교예7 에칭액 변색
비교예8 에칭액 변색
TABLE 2
division Texture Uniformity Pyramid Average Size (μm) Average reflectance (%)
Example 1 ◎ 3 11.91
Example 2 ◎ 3 12.15
Example 3 ◎ 3 12.07
Example 4 ◎ 3 12.02
Example 5 ◎ 3 11.78
Example 6 ◎ 3 11.98
Example 7 ◎ 3 11.23
Example 8 ◎ 2 12.31
Example 9 ◎ 3 12.21
Example 10 ◎ 3 12.07
Example 11 ◎ 3 11.35
Example 12 ◎ 3 11.78
Example 13 ◎ 3 11.98
Example 14 ◎ 3 11.78
Example 15 ◎ 3 12.06
Example 16 ◎ 3 11.89
Example 17 ◎ 3 11.73
Example 18 ◎ 2 12.01
Example 19 ◎ 3 11.78
Example 20 ◎ 3 11.99
Example 21 ◎ 2 10.32
Example 22 ◎ 2 10.21
Example 23 ◎ 2 10.35
Example 24 ◎ 3 12.05
Example 25 ◎ 2 10.57
Example 26 ◎ 3 12.13
Example 27 ◎ 3 11.98
Example 28 ◎ 3 11.87
Example 29 ◎ 3 11.89
Example 30 ◎ 3 11.87
Example 31 ◎ 3 11.82
Example 32 ◎ 3 11.87
Example 33 ◎ 3 11.77
Comparative Example 1 ○ 6 12.56
Comparative Example 2 △ 5 20.12
Comparative Example 3 ○ 5 12.14
Comparative Example 4 △ 5 22.87
Comparative Example 5 ○ 5 13.22
Comparative Example 6 × 10 21.13
Comparative Example 7 Etching Discoloration
Comparative Example 8 Etching Discoloration
위 표 2와 같이, 본 발명에 따라 알칼리 화합물; 고리형 화합물; 다당류; 및 물을 최적의 함량으로 포함하는 실시예 1 내지 33의 텍스쳐 에칭액 조성물을 이용하여 텍스쳐 에칭한 경우 단결정 실리콘 웨이퍼의 표면에 형성된 미세 피라미드의 위치별 품질의 편차가 적어 균일성이 우수하며 광 반사율이 낮아 광효율도 높일 수 있었다. As shown in Table 2, the alkali compound according to the present invention; Cyclic compounds; Polysaccharides; And when the texture is etched using the texture etching solution compositions of Examples 1 to 33 containing the optimum amount of water, the uniformity of the fine pyramids formed on the surface of the single crystal silicon wafer is small and the uniformity is excellent. Low light efficiency was also improved.
도 1은 실시예 15의 텍스쳐 에칭액 조성물로 텍스쳐 에칭된 결정성 실리콘 웨이퍼의 표면을 나타낸 3D 광학현미경 사진이고, 도 2는 상기 텍스쳐 에칭된 결정성 실리콘 웨이퍼의 표면을 나타낸 SEM 사진이다. 이를 통하여, 웨이퍼 표면의 전부에 걸쳐 미세 피라미드가 형성되어 품질 편차가 적고 텍스쳐 균일성이 향상된 것을 알 수 있다.1 is a 3D optical micrograph showing the surface of the crystalline silicon wafer texture etched with the texture etching solution composition of Example 15, Figure 2 is a SEM photograph showing the surface of the texture etched crystalline silicon wafer. Through this, it can be seen that a fine pyramid is formed over the entire surface of the wafer so that the quality variation is small and the texture uniformity is improved.
반면, 다당류를 포함하지 않는 비교예 1은 텍스쳐된 실리콘 웨이퍼 기판의 외관이 좋지 않고 피라미드가 형성되지 않은 부분이 일부 존재하였고, 다당류를 과량 포함하는 비교예 2는 에칭 속도가 너무 느려져 반사율이 높아졌다. 또한, 고리형 화합물을 포함하지 않는 비교예 3은 비교예 1에서와 유사하게 피라미드가 형성되지 않은 부분이 일부 관찰되었고, 고리형 화합물을 과량 포함하는 비교예 4는 에칭 속도의 조절이 어려워 반사율이 높아졌따. 또한, 비교예 5의 텍스쳐 에칭액 조성물은 이소프로필알코올(IPA)의 낮은 비점으로 인해 텍스쳐 공정 중 이를 지속적으로 투입함으로써 발생되는 온도 구배에 기인하여 텍스쳐 불량이 일어나고 비용도 더 발생하였고, 비교예 6의 텍스쳐 에칭액 조성물은 텍스쳐 균일성과 광 반사율 면에서 실시예에 비해 크게 뒤떨어진 특성을 나타내었다. 비교예 7 및 8의 텍스쳐 에칭액 조성물은 텍스쳐 공정 온도로의 승온 시 에칭액 조성물 자체에 경시 변화가 발생하였다.On the other hand, Comparative Example 1, which does not include a polysaccharide, had a poor appearance of the textured silicon wafer substrate, and a portion of the pyramid was not present. In Comparative Example 2, which contained an excessive amount of polysaccharide, the etching rate was too slow to increase the reflectance. In Comparative Example 3, which does not include the cyclic compound, part of the pyramid was not observed similarly to Comparative Example 1, and Comparative Example 4, which contained the excess of the cyclic compound, was difficult to control the etching rate, so that the reflectance was low. It's high. In addition, the texture etching solution composition of Comparative Example 5 due to the low temperature of the isopropyl alcohol (IPA) due to the temperature gradient generated by the continuous input of the texture during the texture failure and cost more, The texture etchant composition showed significantly inferior characteristics in comparison with Examples in terms of texture uniformity and light reflectance. The texture etching solution compositions of Comparative Examples 7 and 8 exhibited a change with time in the etching solution composition itself when heated to the texture process temperature.

Claims (15)

  1. 알칼리 화합물 0.1 내지 20중량%; 고리형 화합물 0.1 내지 50중량%; 다당류 10-9 내지 0.5중량%; 및 잔량의 물을 포함하는 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물.0.1-20% by weight of alkaline compound; 0.1-50% by weight of the cyclic compound; Polysaccharides 10 -9 to 0.5% by weight; And a residual amount of water.
  2. 청구항 1에 있어서, 알칼리 화합물은 수산화칼륨, 수산화나트륨, 수산화암모늄, 테트라히드록시메틸암모늄 및 테트라히드록시에틸암모늄으로 이루어진 군으로부터 선택되는 1종 이상인 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물.The texture etching solution composition of claim 1, wherein the alkali compound is at least one selected from the group consisting of potassium hydroxide, sodium hydroxide, ammonium hydroxide, tetrahydroxymethylammonium, and tetrahydroxyethylammonium.
  3. 청구항 1에 있어서, 고리형 화합물은 비점이 100℃ 이상인 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물.The texture etching liquid composition of Claim 1 in which a cyclic compound has a boiling point of 100 degreeC or more.
  4. 청구항 3에 있어서, 고리형 화합물은 한센의 용해도 파라미터가 6 내지 15인 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물.The texture etching solution composition of claim 3, wherein the cyclic compound has a Hansen solubility parameter of 6 to 15. 5.
  5. 청구항 1에 있어서, 다당류는 글루칸계 화합물, 프룩탄계 화합물, 만난계 화합물, 갈락탄계 화합물 및 이들의 금속염으로 이루어진 군으로부터 선택된 1종 이상인 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물.The texture etching solution composition of claim 1, wherein the polysaccharide is at least one selected from the group consisting of a glucan compound, a fructan compound, a mannan compound, a galactan compound, and a metal salt thereof.
  6. 청구항 5에 있어서, 다당류는 셀룰로오스, 디메틸아미노에틸셀룰로오스, 디에틸아미노에틸셀룰로오스, 에틸히드록시에틸셀룰로오스, 메틸히드록시에틸셀룰로오스, 4-아미노벤질셀룰로오스, 트리에틸아미노에틸셀룰로오스, 시아노에틸셀룰로오스, 에틸셀룰로오스, 메틸셀룰로오스, 카르복시메틸셀룰로오스, 카르복시에틸셀룰로오스, 히드록시에틸셀룰로오스, 히드록시프로필셀룰로오스, 알긴산, 아밀로오스, 아밀로펙틴, 펙틴, 스타치, 덱스트린, α-시클로덱스트린, β-시클로덱스트린, γ-시클로덱스트린, 히드록시프로필-β-시클로덱스트린, 메틸-β-시클로덱스트린, 덱스트란, 덱스트란설페이트나트륨, 사포닌, 글리코겐, 자이모산, 렌티난, 시조피난 및 이들의 금속염으로 이루어진 군으로부터 선택된 1종 이상의 글루칸계 화합물인 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물.The method of claim 5, wherein the polysaccharide is cellulose, dimethylaminoethyl cellulose, diethylaminoethyl cellulose, ethyl hydroxyethyl cellulose, methyl hydroxyethyl cellulose, 4-aminobenzyl cellulose, triethylaminoethyl cellulose, cyanoethyl cellulose, ethyl Cellulose, methyl cellulose, carboxymethyl cellulose, carboxyethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, alginic acid, amylose, amylopectin, pectin, starch, dextrin, α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin At least one glucan selected from the group consisting of hydroxypropyl-β-cyclodextrin, methyl-β-cyclodextrin, dextran, dextransulfate sodium, saponin, glycogen, zymoic acid, lentinan, sizopinean and metal salts thereof Crystalline Silicone As A Compound Texture etching liquid composition of the wipers.
  7. 청구항 5에 있어서, 다당류는 평균 분자량이 5,000 내지 1,000,000인 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물.The texture etchant composition of claim 5, wherein the polysaccharide has an average molecular weight of 5,000 to 1,000,000.
  8. 청구항 1에 있어서, 수용성 극성 용매를 더 포함하는 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물.The texture etchant composition of claim 1, further comprising a water soluble polar solvent.
  9. 청구항 8에 있어서, 수용성 극성 용매는 에틸렌글리콜모노메틸에테르, 디에틸렌글리콜모노메틸에테르, 트리에틸렌글리콜모노메틸에테르, 폴리에틸렌글리콜모노메틸에테르, 에틸렌글리콜모노에틸에테르, 디에틸렌글리콜모노에틸에테르, 에틸렌글리콜모노부틸에테르, 디에틸렌글리콜모노부틸에테르, 트리에틸렌글리콜모노부틸에테르, 프로필렌글리콜모노메틸에테르, 디프로필렌글리콜모노메틸에테르, 프로판올, 부탄올, 이소프로판올, 테트라하이드로퍼푸릴알코올, 에틸렌글리콜, 프로필렌글리콜, N-메틸포름아미드, N,N-디메틸포름아미드, 디메틸술폭사이드, 술폴란, 트리에틸포스페이트 및 트리부틸포스페이트로 이루어진 군으로부터 선택된 1종 이상인 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물.The method of claim 8, wherein the water-soluble polar solvent is 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, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propanol, butanol, isopropanol, tetrahydrofurfuryl alcohol, ethylene glycol, propylene glycol, N -Texture etching solution composition of crystalline silicon wafer of at least one selected from the group consisting of -methyl formamide, N, N-dimethylformamide, dimethyl sulfoxide, sulfolane, triethyl phosphate and tributyl phosphate.
  10. 청구항 8에 있어서, 수용성 극성 용매는 고리형 화합물 총 100중량%에 대하여 0.1 내지 30중량%로 포함되는 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물.The texture etching solution composition of claim 8, wherein the water-soluble polar solvent is included in an amount of 0.1 to 30 wt% based on 100 wt% of the total cyclic compound.
  11. 청구항 1에 있어서, 지방산 및 이의 금속염으로 이루어진 군으로부터 선택된 1종 이상을 더 포함하는 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물.The texture etching solution composition of claim 1, further comprising at least one selected from the group consisting of fatty acids and metal salts thereof.
  12. 청구항 1에 있어서, 폴리옥시에틸렌계(POE) 화합물, 폴리옥시프로필렌계(POP) 화합물 및 이들의 공중합체로 이루어진 군으로부터 선택된 1종 이상의 계면활성제를 더 포함하는 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물.The texture etching solution composition of claim 1, further comprising at least one surfactant selected from the group consisting of polyoxyethylene-based (POE) compounds, polyoxypropylene-based (POP) compounds, and copolymers thereof.
  13. 청구항 1에 있어서, 미분말 실리카; Na2O로 안정화시킨 콜로이드 실리카 용액; K2O로 안정화시킨 콜로이드 실리카 용액; 산성액으로 안정화시킨 콜로이드 실리카 용액; NH3로 안정화시킨 콜로이드 실리카 용액; 에틸알코올, 프로필알코올, 에틸렌글리콜, 메틸에틸케톤 및 메틸이소부틸케톤으로 이루어진 군으로부터 선택된 1종 이상의 유기용매로 안정화시킨 콜로이드 실리카 용액; 액상 규산나트륨; 액상 규산칼륨; 및 액상 규산리튬으로 이루어진 군으로부터 선택된 1종 이상의 실리카 화합물을 더 포함하는 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물.The method of claim 1, further comprising: fine powder silica; Colloidal silica solution stabilized with Na 2 O; Colloidal silica solution stabilized with K 2 O; Colloidal silica solution stabilized with acid solution; Colloidal silica solution stabilized with NH 3 ; Colloidal silica solution 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 at least one silica compound selected from the group consisting of liquid lithium silicate.
  14. 청구항 1 내지 13 중 어느 한 항의 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물로 결정성 실리콘 웨이퍼를 침적, 분무 또는 침적 및 분무하는 단계를 포함하는 결정성 실리콘 웨이퍼의 텍스쳐 에칭방법.A method of etching a crystalline silicon wafer comprising depositing, spraying or depositing and spraying the crystalline silicon wafer with the texture etching liquid composition of any one of claims 1 to 13.
  15. 청구항 14에 있어서, 침적, 분무 또는 침적 및 분무는 50 내지 100℃의 온도에서 30초 내지 60분 동안 수행되는 결정성 실리콘 웨이퍼의 텍스쳐 에칭방법.The method of claim 14, wherein the deposition, spraying or deposition and spraying are performed at a temperature of 50-100 ° C. for 30 seconds to 60 minutes.
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