WO2013002502A2 - Composition de gravure de texture pour une tranche de silicium cristallin et procédé de gravure de texture de celle-ci - Google Patents

Composition de gravure de texture pour une tranche de silicium cristallin et procédé de gravure de texture de celle-ci Download PDF

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WO2013002502A2
WO2013002502A2 PCT/KR2012/004786 KR2012004786W WO2013002502A2 WO 2013002502 A2 WO2013002502 A2 WO 2013002502A2 KR 2012004786 W KR2012004786 W KR 2012004786W WO 2013002502 A2 WO2013002502 A2 WO 2013002502A2
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texture
cellulose
silicon wafer
crystalline silicon
compound
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PCT/KR2012/004786
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Korean (ko)
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WO2013002502A3 (fr
WO2013002502A9 (fr
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홍형표
박면규
이재연
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동우화인켐 주식회사
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Publication of WO2013002502A2 publication Critical patent/WO2013002502A2/fr
Publication of WO2013002502A9 publication Critical patent/WO2013002502A9/fr
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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

La présente invention concerne une composition de gravure de texture pour une tranche de silicium cristallin et un procédé de gravure de texture de celle-ci, et, plus spécifiquement, une composition de gravure de texture pour une tranche de silicium cristallin, qui est apte à rendre maximimale la quantité absorbée de lumière du soleil par le fait qu'elle comprend la quantité optimale de composés alcalins, de composés cycliques, de polysaccharides et d'eau résiduelle, permettant ainsi d'améliorer l'uniformité de texture selon une position sur la surface de la tranche de silicium cristallin, d'améliorer le rendement optique par réduction de la réflectivité de la lumière, et d'augmenter le nombre de tranches traitées selon la quantité utilisée par unité. L'invention concerne également un procédé de gravure de texture d'une tranche de silicium.
PCT/KR2012/004786 2011-06-28 2012-06-18 Composition de gravure de texture pour une tranche de silicium cristallin et procédé de gravure de texture de celle-ci WO2013002502A2 (fr)

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KR20110062735 2011-06-28
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KR10-2012-0058485 2012-05-31
KR1020120058485A KR20130002258A (ko) 2011-06-28 2012-05-31 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물 및 텍스쳐 에칭방법

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