WO2013100318A1 - Texture etchant composition for crystalline silicon wafer, and texture etching method - Google Patents

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

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Publication number
WO2013100318A1
WO2013100318A1 PCT/KR2012/007132 KR2012007132W WO2013100318A1 WO 2013100318 A1 WO2013100318 A1 WO 2013100318A1 KR 2012007132 W KR2012007132 W KR 2012007132W WO 2013100318 A1 WO2013100318 A1 WO 2013100318A1
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polyoxyethylene
ether
texture
silicon wafer
polyoxypropylene
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PCT/KR2012/007132
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French (fr)
Korean (ko)
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홍형표
이재연
이승용
임대성
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동우화인켐 주식회사
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Priority claimed from KR1020110142671A external-priority patent/KR20120078612A/en
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Publication of WO2013100318A1 publication Critical patent/WO2013100318A1/en

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/02—Details
    • H01L31/0236—Special surface textures
    • H01L31/02363—Special surface textures of the semiconductor body itself, e.g. textured active layers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy

Definitions

  • the present invention relates to a texture etching liquid composition of a crystalline silicon wafer capable of increasing light efficiency by minimizing the texture quality variation of each surface of the crystalline silicon wafer surface and a texture etching method of the crystalline silicon wafer using the same.
  • 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 for supplying oxygen to a texture etching solution in which silicon is dissolved in ethylene glycol, potassium hydroxide and residual water, that is, moistureing the 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 low boiling isopropyl alcohol, so it is not economical in terms of productivity and cost to add them during the texturing process, and the addition of isopropyl alcohol causes a temperature gradient of the etching solution, which causes The texture quality variation of each position may increase, resulting in poor uniformity.
  • Patent Document 1 Korean Registered Patent No. 0180621
  • the present invention is to minimize the quality variation of the texture by location in forming a fine pyramid structure on the surface of the crystalline silicon wafer It is an object to provide a texture etching liquid composition of a crystalline silicon wafer capable of increasing light efficiency.
  • another object of the present invention is to provide a texture etching solution composition of a crystalline silicon wafer that does not require the addition of a separate etching solution component during the texturing process and the application of an air rating step.
  • another object of the present invention is to provide a texture etching liquid composition of a crystalline silicon wafer which can be used in a significantly smaller amount than the conventional texture etching liquid composition, thereby increasing the number of processed sheets.
  • Another object of the present invention is to provide a texture etching method using the texture etching liquid composition of the silicon wafer.
  • alkali compound 1. 0.1-20% by weight of alkali compound; 0.000001 to 1% by weight of at least one surfactant selected from the group consisting of polyoxyethylene-based (POE) compounds, polyoxypropylene-based (POP) compounds, and copolymers thereof; And a residual amount of water.
  • POE polyoxyethylene-based
  • POP polyoxypropylene-based
  • the texture etching liquid composition of the crystalline silicon wafer further comprises 0.1 to 50% by weight of the cyclic compound.
  • alkali compound is at least one selected from the group consisting of potassium hydroxide, sodium hydroxide, ammonium hydroxide, tetrahydroxymethylammonium and tetrahydroxyethylammonium etch silicon texture texture composition.
  • the surfactant is polyoxyethylene glycol, polyoxyethylene glycol methyl ether, polyoxyethylene monoallyl ether, polyoxyethylene neopentyl ether, polyethylene glycol mono (tristyrylphenyl) ether, polyoxyethylene Cetyl ether, polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxyethylene stearyl ether, polyoxyethylene tridecyl ether, polyoxyethylene decyl ether, polyoxyethylene octyl ether, polyoxyethylene bisphenol-A ether , Polyoxyethylene glycerin ether, polyoxyethylene nonylphenyl ether, polyoxyethylene benzyl ether, polyoxyethylene phenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene phenol ether, polyoxyethylene having 6 to 30 carbon atoms Alkylcyclohexyl ether, Polyoxyethylene (beta) -naphthol ether
  • the cyclic compound is piperazine, N-methylpiperazine, N-ethylpiperazine, hydroxyethylpiperazine, N- (2-aminoethyl) piperazine, N, N'-dimethylpipe Razine, morpholine, N-methylmorpholine, N-ethylmorpholine, N-phenylmorpholine, N-cocomorpholine, N- (2-aminoethyl) morpholine, N- (2-cyanoethyl) Pauline, N- (2-hydroxyethyl) morpholine, N- (2-hydroxypropyl) morpholine, N-acetylmorpholine, N-formylmorpholine, N-methylmorpholine-N-oxide, methylpyridine , N-methylpiperidine, 3,5-dimethylpiperidine, N-ethylpiperidine, N- (2-hydroxyethyl) piperidine, N-methyl-4-piperidone,
  • 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-containing compound selected from the group consisting of liquid lithium silicate.
  • Texture etching method of crystalline silicon 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 8.
  • the deposition, spraying or deposition and spraying is a texture etching method of crystalline silicon is carried out for 30 seconds to 60 minutes at a temperature of 50 to 100 °C.
  • the texture etching solution composition of the crystalline silicon wafer according to the present invention can minimize the quality variation of the texture of each position on the surface of the crystalline silicon wafer, that is, improve the uniformity of the texture to maximize the absorption of sunlight and lower the light reflectance to increase the light efficiency. have.
  • the number of treatments can be greatly increased compared to the conventional texture etching solution composition, and it is not necessary to add a separate etching solution component during the texture process, which is advantageous in terms of productivity and cost.
  • the texture etching method according to the present invention does not need to introduce a separate air rating equipment, which is economical in terms of initial production and processing costs, and also enables the formation of a uniform fine pyramid structure.
  • Example 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 1 of the present invention.
  • FIG. 2 is a SEM photograph showing the surface of a single crystal silicon wafer textured etched with the texture etching solution composition of the crystalline silicon wafer of Example 1 of the present invention.
  • FIG. 3 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 12 of the present invention.
  • Example 4 is a SEM photograph showing the surface of a single crystal silicon wafer textured etched with the texture etching solution composition of the crystalline silicon wafer of Example 12 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; At least one surfactant selected from the group consisting of polyoxyethylene-based (POE) compounds, polyoxypropylene-based (POP) compounds, and copolymers thereof; And water.
  • the alkali compound 0.1 to 20% by weight; 0.000001 to 1% by weight of at least one surfactant selected from the group consisting of polyoxyethylene-based (POE) compounds, polyoxypropylene-based (POP) compounds, and copolymers thereof; And a residual amount of water.
  • POE polyoxyethylene-based
  • POP polyoxypropylene-based
  • the texture etching solution composition of the crystalline silicon wafer of the present invention is an alkali compound; At least one surfactant selected from the group consisting of polyoxyethylene-based (POE) compounds, polyoxypropylene-based (POP) compounds, and copolymers thereof; And cyclic compounds in addition to water.
  • POE polyoxyethylene-based
  • POP polyoxypropylene-based
  • cyclic compounds in addition to water.
  • the alkali compound 0.1 to 20% by weight; 0.1-50% by weight of the cyclic compound; 0.000001 to 1% by weight of at least one surfactant selected from the group consisting of polyoxyethylene-based (POE) compounds, polyoxypropylene-based (POP) compounds, and copolymers thereof; And a residual amount of water.
  • POE polyoxyethylene-based
  • POP polyoxypropylene-based
  • 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, 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. When the content falls within the above range, etching of the surface of the silicon wafer can be performed.
  • 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, and improves the wettability of the surface of the crystalline silicon wafer to prevent overetching by alkali compounds. This can minimize the quality variation of the texture and at the same time reduce the amount of hydrogen bubbles generated by etching, thereby preventing the occurrence of bubble stick phenomenon.
  • the boiling point can be used in a small amount compared to isopropyl alcohol is conventionally used as well as increase the number of treatment for the same amount of use.
  • a boiling point of a cyclic compound is high as 100 degreeC or more, More preferably, it is 150-400 degreeC.
  • the type of the cyclic compound is not particularly limited as long as the boiling point is 100 ° C. or more, and the piperazine-based, morpholine-based, pyridine-based, piperidine-based, piperidone-based, pyrrolidine-based, pyrrolidone-based, and imidazolidinone-based compounds are not particularly limited. And furan, aniline, toluidine and lactone compounds.
  • piperazine N-methylpiperazine, N-ethylpiperazine, hydroxyethylpiperazine, N- (2-aminoethyl) piperazine, N, N'-dimethylpiperazine; Morpholine, N-methylmorpholine, N-ethylmorpholine, N-phenylmorpholine, N-cocomorpholine, N- (2-aminoethyl) morpholine, N- (2-cyanoethyl) morpholine, N- (2-hydroxyethyl) morpholine, N- (2-hydroxypropyl) morpholine, N-acetylmorpholine, N-formylmorpholine, N-methylmorpholine-N-oxide; Methylpyridine; N-methylpiperidine, 3,5-dimethylpiperidine, N-ethylpiperidine, N- (2-hydroxyethyl) piperidine; N-methyl-4-piperidone, N-vinyl-2
  • the cyclic compound is preferably included in an amount of 0.1 to 50% by weight, more preferably 2 to 10% by weight based on 100% by weight of the total amount of the texture etching solution composition of the crystalline silicon wafer.
  • the content falls within the above range, the wettability of the surface of the silicon wafer may be effectively improved, thereby minimizing texture quality variation, thereby improving uniformity.
  • a compound having a hydroxy group A polyoxyethylene-based (POE) compound, a polyoxypropylene-based (POP) compound, and a copolymer which is used as a surfactant are selected and used, which is characterized by using it in an optimum content range.
  • the number of treatments for the same amount of use can be increased by minimizing the difference in the etching rates.
  • by improving the wettability of the surface of the crystalline silicon wafer to quickly reduce the amount of hydrogen bubbles generated by etching to prevent the bubble stick phenomenon to occur by reducing the variation of the texture quality by position in the texture to improve uniformity And appearance can be improved.
  • 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 at least one surfactant selected from the group consisting of polyoxyethylene-based (POE) compounds, polyoxypropylene-based (POP) compounds and copolymers thereof is 0.000001 to 1 based on 100% by weight of the total amount of the texture etching solution composition of the crystalline silicon wafer. It is preferably included in the weight%, more preferably 0.00001 to 0.1% by weight, most preferably 0.0001 to 0.1% by weight. When the content falls within the above range, the texture quality of each silicon wafer surface may be reduced, and the appearance of the wafer may be improved, and the number of treatments for the same amount of use may be increased.
  • POE polyoxyethylene-based
  • POP polyoxypropylene-based
  • the texture etching solution composition of the crystalline silicon wafer of the present invention comprises a fluorine-based surfactant with at least one surfactant selected from the group consisting of polyoxyethylene-based (POE) compounds, polyoxypropylene-based (POP) compounds, and copolymers thereof. It may further include.
  • a fluorine-based surfactant selected from the group consisting of polyoxyethylene-based (POE) compounds, polyoxypropylene-based (POP) compounds, and copolymers thereof. It may further include.
  • the fluorine-based surfactant together with the polyoxy compound-based surfactant, lowers the surface tension of the etching solution composition to further improve the wettability of the surface of the crystalline silicon wafer, thereby preventing overetching by the alkali compound.
  • the type of the fluorine-based surfactant is not particularly limited, and examples thereof include anionic surfactants such as perfluoroalkyl carboxylate, perfluoroalkyl sulfonate, perfluoroalkyl sulfate, and perfluoroalkyl phosphate; Cationic surfactants such as perfluoroalkyl amine salts and perfluoroalkyl quaternary ammonium salts; Amphoteric ionic surfactants such as perfluoroalkyl carboxybetaine and perfluoroalkyl sulfobetaine; And nonionic surfactants such as fluorinated alkyl polyoxyethylene and perfluoroalkyl polyoxyethylene. These compounds may be those having 1 to 30 carbon atoms in each alkyl group. These can be used individually or in mixture of 2 or more types.
  • the fluorine-based surfactant may be included in an amount of 0.000001 to 1% by weight, preferably 0.00001 to 0.1% by weight, and more preferably 0.0001 to 0.1% by weight based on 100% by weight of the texture etching solution composition of the crystalline silicon wafer.
  • the content falls within the above range, the wettability of the silicon wafer surface can be effectively improved.
  • texture etching solution composition of the crystalline silicon wafer of the present invention may further comprise a silica-containing compound.
  • Silica-containing compounds physically adsorb onto the crystalline silicon wafer surface and serve as a kind of mask, thereby making the silicon wafer surface into a fine pyramid shape.
  • silica-containing 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-containing compound may be included in an amount of 0.00001 to 10% by weight, and preferably 0.0001 to 1% 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, it is possible to facilitate formation of 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.
  • the texture etching solution composition of the crystalline silicon wafer of the present invention comprising the above components is particularly a polyoxyethylene-based (POE) compound, a polyoxypropylene-based (POP) compound, and a copolymer thereof together with a cyclic compound.
  • POE polyoxyethylene-based
  • POP polyoxypropylene-based
  • the uniformity of the texture may be improved by minimizing the variation of the texture quality for each position of the surface of the crystalline silicon wafer. This maximizes the absorption of sunlight and lowers the light reflectance to increase light efficiency.
  • 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 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.
  • the texture etching solution compositions of the crystalline silicon wafers of Examples 2 to 27 were prepared using the ingredients and contents (wt%) shown in Table 1 below.
  • etching solution compositions of Comparative Examples 1 to 10 were prepared in the same manner as in Example 1, using the ingredients and contents (% by weight) shown in Table 2 below.
  • the single crystal silicon wafer substrate was immersed in the texture etching liquid composition of the prepared single crystal silicon wafer at a temperature of 80 ° C. for 20 minutes.
  • Texture variation ie, uniformity
  • the discoloration means that a change in temporal change occurs when the temperature is raised to the texture process temperature, so that a texture test is not necessary.
  • 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.
  • the alkali compound according to the present invention At least one surfactant selected from the group consisting of polyoxyethylene-based (POE) compounds, polyoxypropylene-based (POP) compounds, and copolymers thereof;
  • POE polyoxyethylene-based
  • POP polyoxypropylene-based
  • copolymers thereof When the texture is etched using the texture etching solution composition of Examples 1 to 11 containing water and the variation of the quality of each position of the fine pyramid formed on the surface of the single crystal silicon wafer is small, the uniformity is excellent and the light reflectance is low to improve the light efficiency could confirm.
  • the surface tension of the etching solution composition is lowered to further promote the improvement of the wettability of the surface of the crystalline silicon wafer, thereby preventing overetching by the alkali compound.
  • 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 1
  • 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.
  • the texture etchant composition of Comparative Example 3 has a poor texture and cost more due to the temperature gradient generated by continuously inputting it during the texture process due to the low boiling point of isopropyl alcohol (IPA) contained in the etchant composition.
  • IPA isopropyl alcohol
  • the texture etching solution composition of Comparative Example 4 exhibited significantly inferior characteristics in comparison with Examples in terms of texture uniformity and light reflectance.
  • Example 13 Using a texture etching solution composition prepared in Example 13 and Comparative Example 7-10 was subjected to texture etching of the single crystal silicon wafer substrate, but the number of sheets that can be treated with the same content was confirmed. At this time, the number of treatments of Comparative Example 7-10 was calculated based on the number of treatments of Example 13, and fairness was evaluated based on this.
  • At least one surfactant and water selected from the group consisting of alkali compounds, polyoxyethylene-based (POE) compounds, polyoxypropylene-based (POP) compounds and copolymers thereof according to the present invention
  • the texture etchant composition of the embodiment was able to significantly increase the number of treatments compared to the conventional texture etchant composition by including a cyclic compound, it is confirmed that it is advantageous in terms of productivity and cost because it does not need to add a separate etchant component during the texture process It was.
  • the texture etching solution composition of Example was further confirmed that by further including a fluorine-based surfactant, the surface tension of the etching solution composition can be further promoted to improve the wettability of the surface of the crystalline silicon wafer, thereby preventing overetching by the alkali compound.
  • FIG. 3 is a 3D optical micrograph showing the surface of the crystalline silicon wafer texture etched with the texture etching solution composition of Example 12,
  • Figure 4 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 Examples 7 and 9 in which the content of the polyoxy compound-based surfactant or the cyclic compound are not within the scope of the present invention show good results in terms of the formation of the fine pyramid structure in the silicon surface, but the number of treatments for the same content The processability was not good compared with the Example.
  • Comparative Examples 8 and 10 the silicon etching rate due to the alkali compound was significantly lowered, so that pyramids could not be formed properly.
  • the texture etchant composition of Comparative Example 3 has a poor texture and cost more due to the temperature gradient generated by continuously inputting it during the texture process due to the low boiling point of isopropyl alcohol (IPA) contained in the etchant composition.
  • IPA isopropyl alcohol

Abstract

The present invention relates to a texture etchant composition for a crystalline silicon wafer, and a texture etching method, and more specifically, to a texture etchant composition for a crystalline silicon wafer, comprising: an alkali compound; a cyclic compound; one or more surfactants selected from the group consisting of a polyoxyethylene (POE)-based compound, polyoxypropylene (POP)-based compound, and a copolymer thereof; and water, wherein the deviation of texture quality on the surface of a crystalline silicon wafer is minimized, thereby improving the uniformity of a texture structure so as to maximize the absorption of solar radiation and decreasing light reflectivity so as to increase light efficiency, the amount used is remarkably reduced, thereby increasing the number of sheets to be treated, and it is unnecessary to inject additional etchant component during a texture process, thereby increasing productivity and being economical in cost, and to a texture etching method.

Description

결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물 및 텍스쳐 에칭방법Texture Etching Compositions and Texture Etching Methods of Crystalline Silicon Wafers
본 발명은 결정성 실리콘 웨이퍼 표면의 위치별 텍스쳐 품질 편차를 최소화하여 광효율을 높일 수 있는 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물 및 이를 이용하는 결정성 실리콘 웨이퍼의 텍스쳐 에칭방법에 관한 것이다.The present invention relates to a texture etching liquid composition of a crystalline silicon wafer capable of increasing light efficiency by minimizing the texture quality variation of each surface of the crystalline silicon wafer surface and a texture etching method of the crystalline silicon wafer using the same.
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 수분하는 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 for supplying oxygen to a texture etching solution in which silicon is dissolved in ethylene glycol, potassium hydroxide and residual water, that is, moistureing the 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 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, these etching solutions contain low boiling isopropyl alcohol, so it is not economical in terms of productivity and cost to add them during the texturing process, and the addition of isopropyl alcohol causes a temperature gradient of the etching solution, which causes The texture quality variation of each position may increase, resulting in poor uniformity.
[선행기술문헌][Preceding technical literature]
[특허문헌][Patent Documents]
(특허문헌 1) 한국등록특허 제0180621호(Patent Document 1) Korean Registered Patent No. 0180621
본 발명은 결정성 실리콘 웨이퍼의 표면에 미세 피라미드 구조를 형성함에 있어서 위치별 텍스쳐의 품질 편차를 최소화함으로써 광 효율을 증가시킬 수 있는 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물을 제공하는 것을 목적으로 한다.The present invention is to minimize the quality variation of the texture by location in forming a fine pyramid structure on the surface of the crystalline silicon wafer It is an object to provide a texture etching liquid composition of a crystalline silicon wafer capable of increasing light efficiency.
또한, 본 발명은 텍스쳐 공정 중 별도의 에칭액 성분의 투입과 에어레이팅 공정의 적용이 필요 없는 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물을 제공하는 것을 다른 목적으로 한다.In addition, another object of the present invention is to provide a texture etching solution composition of a crystalline silicon wafer that does not require the addition of a separate etching solution component during the texturing process and the application of an air rating step.
또한, 본 발명은 종래의 텍스쳐 에칭액 조성물과 비교하여 그 사용량이 현저히 적어 처리 매수를 증가시킬 수 있는 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물을 제공하는 것을 다른 목적으로 한다.In addition, another object of the present invention is to provide a texture etching liquid composition of a crystalline silicon wafer which can be used in a significantly smaller amount than the conventional texture etching liquid composition, thereby increasing the number of processed sheets.
또한, 본 발명은 상기 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 silicon wafer.
1. 알칼리 화합물 0.1 내지 20중량%; 폴리옥시에틸렌계(POE) 화합물, 폴리옥시프로필렌계(POP) 화합물 및 이들의 공중합체로 이루어진 군으로부터 선택된 1종 이상의 계면활성제 0.000001 내지 1중량%; 및 잔량의 물을 포함하는 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물.1. 0.1-20% by weight of alkali compound; 0.000001 to 1% by weight of at least one surfactant selected from the group consisting of polyoxyethylene-based (POE) compounds, polyoxypropylene-based (POP) compounds, and copolymers thereof; And a residual amount of water.
2. 위 1에 있어서, 고리형 화합물 0.1 내지 50중량%를 추가로 포함하는 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물.2. according to the above 1, the texture etching liquid composition of the crystalline silicon wafer further comprises 0.1 to 50% by weight of the cyclic compound.
3. 위 2에 있어서, 고리형 화합물은 비점이 100℃ 이상인 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물.3. In the above 2, wherein the cyclic compound has a boiling point of 100 ℃ or more texture etching liquid composition of the crystalline silicon wafer.
4. 위 1에 있어서, 알칼리 화합물은 수산화칼륨, 수산화나트륨, 수산화암모늄, 테트라히드록시메틸암모늄 및 테트라히드록시에틸암모늄으로 이루어진 군으로부터 선택되는 1종 이상인 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물.4. The method 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 etch silicon texture texture composition.
5. 위 1에 있어서, 계면활성제는 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, 폴리옥시에틸렌 수소화 캐스터 에테르; 폴리옥시에틸렌라우릴에스테르, 폴리옥시에틸렌스테아릴에스테르, 폴리옥시에틸렌올레일에스테르; 폴리옥시에틸렌라우릴아민, 폴리옥시에틸렌스테아릴아민, 폴리옥시에틸렌탈로우아민; 폴리프로필렌글리콜; 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 및 에틸렌디아민 부가형 폴리옥시에틸렌-폴리옥시프로필렌 공중합체로 이루어진 군으로부터 선택된 1종 이상인 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물.5. In the above 1, the surfactant is polyoxyethylene glycol, polyoxyethylene glycol methyl ether, polyoxyethylene monoallyl ether, polyoxyethylene neopentyl ether, polyethylene glycol mono (tristyrylphenyl) ether, polyoxyethylene Cetyl ether, polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxyethylene stearyl ether, polyoxyethylene tridecyl ether, polyoxyethylene decyl ether, polyoxyethylene octyl ether, polyoxyethylene bisphenol-A ether , Polyoxyethylene glycerin ether, polyoxyethylene nonylphenyl ether, polyoxyethylene benzyl ether, polyoxyethylene phenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene phenol ether, polyoxyethylene having 6 to 30 carbon atoms Alkylcyclohexyl ether, Polyoxyethylene (beta) -naphthol ether, Polyoxyethyl Caster ether, polyoxyethylene hydrogenated castor ether; Polyoxyethylene lauryl ester, polyoxyethylene stearyl ester, polyoxyethylene oleyl ester; Polyoxyethylene laurylamine, polyoxyethylene stearylamine, polyoxyethylene tallowamine; Polypropylene glycol; Polyoxyethylene-polyoxypropylene copolymer, polyoxyethylene-polyoxypropylene decanyl ether copolymer, polyoxyethylene-polyoxypropylene undecanyl ether copolymer, polyoxyethylene-polyoxypropylene dodecanyl ether copolymer, poly Oxyethylene-polyoxypropylene tetradecanyl ether copolymer, polyoxyethylene-polyoxypropylene 2-ethylhexyl ether copolymer, polyoxyethylene-polyoxypropylene lauryl ether copolymer, polyoxyethylene-polyoxypropylene stearyl A texture etching solution composition of at least one crystalline silicon wafer selected from the group consisting of an ether copolymer, a glycerin addition polyoxyethylene-polyoxypropylene copolymer and an ethylenediamine addition polyoxyethylene-polyoxypropylene copolymer.
6. 위 2에 있어서, 고리형 화합물은 피페라진, N-메틸피페라진, N-에틸피페라진, 히드록시에틸피페라진, N-(2-아미노에틸)피페라진, N,N'-디메틸피페라진, 모르폴린, N-메틸모르폴린, N-에틸모르폴린, N-페닐모르폴린, 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-메틸-4-피페리돈, N-비닐-2-피페리돈, N-메틸피롤리딘, N-메틸피롤리돈, N-에틸-2-피롤리돈, N-이소프로필-2-피롤리돈, N-부틸-2-피롤리돈, N-tert-부틸-2-피롤리돈, N-헥실-2-피롤리돈, N-옥틸-2-피롤리돈, N-벤질-2-피롤리돈, N-시클로헥실-2-피롤리돈, N-비닐-2-피롤리돈, N-(2-히드록시에틸)-2-피롤리돈, N-(2-메톡시에틸)-2-피롤리돈, N-(2-메톡시프로필)-2-피롤리돈, N-(2-에톡시에틸)-2-피롤리돈, N-메틸 이미다졸리디논, 디메틸이미다졸리디논, N-(2-히드록시에틸)-에틸렌우레아, 테트라히드로퓨란, 테트라히드로퍼푸릴알코올, 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, 톨릴트리아졸, 1,2,3-벤조트리아졸, 1,2,3-트리아졸, 1,2,4-트리아졸, 3-아미노-1,2,4-트리아졸, 4-아미노-4H-1,2,4-트리아졸, 1-히드록시벤조트리아졸, 1-메틸벤조트리아졸, 2-메틸벤조트리아졸, 5-메틸벤조트리아졸, 벤조트리아졸-5-카르본산, 니트로벤조트리아졸 및 2-(2H-벤조트리아졸-2-일)-4,6-디-t-부틸페놀로 이루어진 군으로부터 선택된 1종 이상인 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물.6. In the above 2, the cyclic compound is piperazine, N-methylpiperazine, N-ethylpiperazine, hydroxyethylpiperazine, N- (2-aminoethyl) piperazine, N, N'-dimethylpipe Razine, morpholine, N-methylmorpholine, N-ethylmorpholine, N-phenylmorpholine, N-cocomorpholine, N- (2-aminoethyl) morpholine, N- (2-cyanoethyl) Pauline, N- (2-hydroxyethyl) morpholine, N- (2-hydroxypropyl) morpholine, N-acetylmorpholine, N-formylmorpholine, N-methylmorpholine-N-oxide, methylpyridine , N-methylpiperidine, 3,5-dimethylpiperidine, N-ethylpiperidine, N- (2-hydroxyethyl) piperidine, N-methyl-4-piperidone, N-vinyl- 2-piperidone, N-methylpyrrolidone, N-methylpyrrolidone, N-ethyl-2-pyrrolidone, N-isopropyl-2-pyrrolidone, N-butyl-2-pyrrolidone, N-tert-butyl-2-pyrrolidone, N-hexyl-2-pyrrolidone, N-octyl-2-pyrrolidone, N-benzyl-2-pyrrolidone, N-cyclohexyl-2-py Ralidone, N-vinyl-2-pyrroli , N- (2-hydroxyethyl) -2-pyrrolidone, N- (2-methoxyethyl) -2-pyrrolidone, N- (2-methoxypropyl) -2-pyrrolidone, N -(2-ethoxyethyl) -2-pyrrolidone, N-methyl imidazolidinone, dimethylimidazolidinone, N- (2-hydroxyethyl) -ethyleneurea, tetrahydrofuran, tetrahydroperfuryl Alcohol, 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, tolyl Triazole, 1,2,3-benzotriazole, 1,2,3-triazole, 1,2,4-triazole, 3-amino-1,2,4-triazole, 4-amino-4H- 1,2,4-triazole, 1-hydroxybenzotriazole, 1-methylbenzotriazole, 2-methylbenzotriazole, 5-methylbenzotriazole, benzotriazole-5-carboxylic acid, nitrobenzotria Sol and 2- (2H-benzotri -2-yl) -4,6-di -t- determining at least one member selected from the group consisting of butyl phenol texture etching liquid composition of the silicone wafer.
7. 위 1에 있어서, 각 알킬기의 탄소수가 1 내지 30인 과불소알킬 카르복시산염, 과불소알킬 술폰산염, 과불소알킬 황산염, 과불소알킬 인산염, 과불소알킬 아민염, 과불소알킬 4급암모늄염, 과불소알킬 카르복시베타인, 과불소알킬 술포베타인, 불소화알킬 폴리옥시에틸렌 및 과불소알킬 폴리옥시에틸렌으로 이루어진 군으로부터 선택된 1종 이상의 불소계 계면활성제를 0.000001 내지 1중량%로 더 포함하는 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물.7. In the above 1, the perfluoroalkyl carboxylate, perfluoroalkyl sulfonate, perfluoroalkyl sulfate, perfluoroalkyl phosphate, perfluoroalkyl amine salt, perfluoroalkyl quaternary ammonium salt having 1 to 30 carbon atoms of each alkyl group , 0.000001 to 1% by weight of at least one fluorine-based surfactant selected from the group consisting of perfluoroalkyl carboxybetaine, perfluoroalkyl sulfobetaine, fluorinated alkyl polyoxyethylene and perfluoroalkyl polyoxyethylene Texture etching liquid composition of a silicon wafer.
8. 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 함유 화합물을 더 포함하는 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물.8. 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-containing compound selected from the group consisting of liquid lithium silicate.
9. 위 1 내지 8 중 어느 한 항의 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물로 결정성 실리콘 웨이퍼를 침적, 분무 또는 침적 및 분무하는 단계를 포함하는 결정성 실리콘의 텍스쳐 에칭방법.9. Texture etching method of crystalline silicon 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 8.
10. 위 9에 있어서, 침적, 분무 또는 침적 및 분무는 50 내지 100℃의 온도에서 30초 내지 60분 동안 수행되는 결정성 실리콘의 텍스쳐 에칭방법.10. The method of 9 above, the deposition, spraying or deposition and spraying is a texture etching method of crystalline silicon is carried out for 30 seconds to 60 minutes at a temperature of 50 to 100 ℃.
본 발명에 따른 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물은 결정성 실리콘 웨이퍼 표면의 위치별 텍스쳐의 품질 편차를 최소화, 즉 텍스쳐의 균일성을 향상시켜 태양광의 흡수량을 극대화시키고 광 반사율을 낮춰 광효율을 높일 수 있다.The texture etching solution composition of the crystalline silicon wafer according to the present invention can minimize the quality variation of the texture of each position on the surface of the crystalline silicon wafer, that is, improve the uniformity of the texture to maximize the absorption of sunlight and lower the light reflectance to increase the light efficiency. have.
또한, 텍스쳐 공정 중 별도의 에칭액 성분을 투입할 필요가 없어 생산성을 향상시키고 비용 면에서도 경제적이다.In addition, there is no need to add a separate etchant component during the texture process, which improves productivity and is economical in terms of cost.
또한, 비점이 높은 고리형 화합물을 포함하는 경우에는 기존의 텍스쳐 에칭액 조성물에 비해 처리 매수를 대폭 증가시킬 수 있고 텍스쳐 공정 중 별도의 에칭액 성분을 투입할 필요가 없어 생산성과 비용 면에서 유리하다.In addition, when the high boiling point cyclic compound is included, the number of treatments can be greatly increased compared to the conventional texture etching solution composition, and it is not necessary to add a separate etching solution component during the texture process, which is advantageous in terms of productivity and cost.
또한, 본 발명에 따른 텍스쳐 에칭 방법은 별도의 에어레이팅 장비를 도입할 필요가 없어 초기 생산 및 공정 비용 면에서 경제적일 뿐만 아니라 균일한 미세 피라미드 구조의 형성을 가능하게 한다.In addition, the texture etching method according to the present invention does not need to introduce a separate air rating equipment, which is economical in terms of initial production and processing costs, and also enables the formation of a uniform fine pyramid structure.
도 1은 본 발명의 실시예 1의 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물로 텍스쳐 에칭된 단결정 실리콘 웨이퍼의 표면을 나타낸 3D 광학현미경 사진이다.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 1 of the present invention.
도 2는 본 발명의 실시예 1의 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물로 텍스쳐 에칭된 단결정 실리콘 웨이퍼의 표면을 나타낸 SEM 사진이다.FIG. 2 is a SEM photograph showing the surface of a single crystal silicon wafer textured etched with the texture etching solution composition of the crystalline silicon wafer of Example 1 of the present invention.
도 3은 본 발명의 실시예 12의 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물로 텍스쳐 에칭된 단결정 실리콘 웨이퍼의 표면을 나타낸 3D 광학현미경 사진이다.3 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 12 of the present invention.
도 4는 본 발명의 실시예 12의 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물로 텍스쳐 에칭된 단결정 실리콘 웨이퍼의 표면을 나타낸 SEM 사진이다.4 is a SEM photograph showing the surface of a single crystal silicon wafer textured etched with the texture etching solution composition of the crystalline silicon wafer of Example 12 of the present invention.
본 발명은 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물 및 이를 이용하는 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; 폴리옥시에틸렌계(POE) 화합물, 폴리옥시프로필렌계(POP) 화합물 및 이들의 공중합체로 이루어진 군으로부터 선택된 1종 이상의 계면활성제; 및 물을 포함한다.The texture etching solution composition of the crystalline silicon wafer of the present invention is an alkali compound; At least one surfactant selected from the group consisting of polyoxyethylene-based (POE) compounds, polyoxypropylene-based (POP) compounds, and copolymers thereof; And water.
보다 상세하게, 알칼리 화합물 0.1 내지 20중량%; 폴리옥시에틸렌계(POE) 화합물, 폴리옥시프로필렌계(POP) 화합물 및 이들의 공중합체로 이루어진 군으로부터 선택된 1종 이상의 계면활성제 0.000001 내지 1중량%; 및 잔량의 물을 포함하는 것이 바람직하다.More specifically, the alkali compound 0.1 to 20% by weight; 0.000001 to 1% by weight of at least one surfactant selected from the group consisting of polyoxyethylene-based (POE) compounds, polyoxypropylene-based (POP) compounds, and copolymers thereof; And a residual amount of water.
또한, 본 발명의 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물은 알칼리 화합물; 폴리옥시에틸렌계(POE) 화합물, 폴리옥시프로필렌계(POP) 화합물 및 이들의 공중합체로 이루어진 군으로부터 선택된 1종 이상의 계면활성제; 및 물 이외에 고리형 화합물을 추가로 포함할 수 있다.In addition, the texture etching solution composition of the crystalline silicon wafer of the present invention is an alkali compound; At least one surfactant selected from the group consisting of polyoxyethylene-based (POE) compounds, polyoxypropylene-based (POP) compounds, and copolymers thereof; And cyclic compounds in addition to water.
보다 상세하게, 알칼리 화합물 0.1 내지 20중량%; 고리형 화합물 0.1 내지 50중량%; 폴리옥시에틸렌계(POE) 화합물, 폴리옥시프로필렌계(POP) 화합물 및 이들의 공중합체로 이루어진 군으로부터 선택된 1종 이상의 계면활성제 0.000001 내지 1중량%; 및 잔량의 물을 포함하는 것이 바람직하다.More specifically, the alkali compound 0.1 to 20% by weight; 0.1-50% by weight of the cyclic compound; 0.000001 to 1% by weight of at least one surfactant selected from the group consisting of polyoxyethylene-based (POE) compounds, polyoxypropylene-based (POP) compounds, and copolymers thereof; And a 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, 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, 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 표면의 에칭을 수행할 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, etching of the surface of the silicon wafer can be performed.
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 있다. 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, and improves the wettability of the surface of the crystalline silicon wafer to prevent overetching by alkali compounds. This can minimize the quality variation of the texture and at the same time reduce the amount of hydrogen bubbles generated by etching, thereby preventing the occurrence of bubble stick phenomenon. In addition, the boiling point can be used in a small amount compared to isopropyl alcohol is conventionally used as well as increase the number of treatment for the same amount of use.
고리형 화합물은 비점이 100℃ 이상으로 높은 것이 바람직하고, 보다 바람직하게는 150 내지 400℃인 것이 좋다.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.
고리형 화합물은 비점이 100℃ 이상인 것이라면 그 종류가 특별히 한정되지 않으며, 피페라진계, 모르폴린계, 피리딘계, 피페리딘계, 피페리돈계, 피롤리딘계, 피롤리돈계, 이미다졸리디논계, 퓨란계, 아닐린계, 톨루이딘계 및 락톤계 화합물을 들 수 있다. 구체적인 예로는, 피페라진, N-메틸피페라진, N-에틸피페라진, 히드록시에틸피페라진, N-(2-아미노에틸)피페라진, N,N'-디메틸피페라진; 모르폴린, N-메틸모르폴린, N-에틸모르폴린, N-페닐모르폴린, 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-메틸-4-피페리돈, N-비닐-2-피페리돈; N-메틸피롤리딘, N-메틸피롤리돈, N-에틸-2-피롤리돈, N-이소프로필-2-피롤리돈, N-부틸-2-피롤리돈, N-tert-부틸-2-피롤리돈, N-헥실-2-피롤리돈, N-옥틸-2-피롤리돈, N-벤질-2-피롤리돈, N-시클로헥실-2-피롤리돈, N-비닐-2-피롤리돈, N-(2-히드록시에틸)-2-피롤리돈, N-(2-메톡시에틸)-2-피롤리돈, N-(2-메톡시프로필)-2-피롤리돈, N-(2-에톡시에틸)-2-피롤리돈; N-메틸 이미다졸리디논, 디메틸이미다졸리디논, N-(2-히드록시에틸)-에틸렌우레아; 테트라히드로퓨란, 테트라히드로퍼푸릴알코올; 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, 톨릴트리아졸, 1,2,3-벤조트리아졸, 1,2,3-트리아졸, 1,2,4-트리아졸, 3-아미노-1,2,4-트리아졸, 4-아미노-4H-1,2,4-트리아졸, 1-히드록시벤조트리아졸, 1-메틸벤조트리아졸, 2-메틸벤조트리아졸, 5-메틸벤조트리아졸, 벤조트리아졸-5-카르본산, 니트로벤조트리아졸, 2-(2H-벤조트리아졸-2-일)-4,6-디-t-부틸페놀 등을 들 수 있으며, 이들은 단독 또는 2종 이상 혼합하여 사용할 수 있다.The type of the cyclic compound is not particularly limited as long as the boiling point is 100 ° C. or more, and the piperazine-based, morpholine-based, pyridine-based, piperidine-based, piperidone-based, pyrrolidine-based, pyrrolidone-based, and imidazolidinone-based compounds are not particularly limited. And furan, aniline, toluidine and lactone compounds. Specific examples include piperazine, N-methylpiperazine, N-ethylpiperazine, hydroxyethylpiperazine, N- (2-aminoethyl) piperazine, N, N'-dimethylpiperazine; Morpholine, N-methylmorpholine, N-ethylmorpholine, N-phenylmorpholine, N-cocomorpholine, N- (2-aminoethyl) morpholine, N- (2-cyanoethyl) morpholine, N- (2-hydroxyethyl) morpholine, N- (2-hydroxypropyl) morpholine, N-acetylmorpholine, N-formylmorpholine, N-methylmorpholine-N-oxide; Methylpyridine; N-methylpiperidine, 3,5-dimethylpiperidine, N-ethylpiperidine, N- (2-hydroxyethyl) piperidine; N-methyl-4-piperidone, N-vinyl-2-piperidone; N-methylpyrrolidin, N-methylpyrrolidone, N-ethyl-2-pyrrolidone, N-isopropyl-2-pyrrolidone, N-butyl-2-pyrrolidone, N-tert-butyl -2-pyrrolidone, N-hexyl-2-pyrrolidone, N-octyl-2-pyrrolidone, N-benzyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N- Vinyl-2-pyrrolidone, N- (2-hydroxyethyl) -2-pyrrolidone, N- (2-methoxyethyl) -2-pyrrolidone, N- (2-methoxypropyl)- 2-pyrrolidone, N- (2-ethoxyethyl) -2-pyrrolidone; N-methyl imidazolidinone, dimethylimidazolidinone, N- (2-hydroxyethyl) -ethyleneurea; Tetrahydrofuran, tetrahydroperfuryl alcohol; 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, tolyltriazole, 1,2,3-benzotriazole, 1,2,3-triazole, 1,2,4-triazole, 3-amino-1,2,4-triazole , 4-amino-4H-1,2,4-triazole, 1-hydroxybenzotriazole, 1-methylbenzotriazole, 2-methylbenzotriazole, 5-methylbenzotriazole, benzotriazole-5 -Carboxylic acid, nitrobenzotriazole, 2- (2H-benzotriazol-2-yl) -4,6-di-t-butylphenol, and the like, and these can be used alone or in combination of two or more thereof. .
고리형 화합물은 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물 총 100중량%에 대하여 0.1 내지 50중량%로 포함되는 것이 바람직하고, 보다 바람직하게는 2 내지 10중량%인 것이 좋다. 함량이 상기 범위에 해당되는 경우 실리콘 웨이퍼 표면의 젖음성을 효과적으로 개선시켜 텍스쳐 품질 편차를 최소화시켜 균일성을 향상시킬 수 있다.The cyclic compound is preferably included in an amount of 0.1 to 50% by weight, more preferably 2 to 10% 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 wettability of the surface of the silicon wafer may be effectively improved, thereby minimizing texture quality variation, thereby improving uniformity.
본 발명에서는 계면활성제로 특히, 히드록시기를 갖는 화합물인 폴리옥시에틸렌계(POE) 화합물, 폴리옥시프로필렌계(POP) 화합물 및 이들의 공중합체인 계면활성제를 선택 사용하되, 이를 최적의 함량 범위로 사용하는데 특징이 있다.In the present invention, particularly as a surfactant, a compound having a hydroxy group A polyoxyethylene-based (POE) compound, a polyoxypropylene-based (POP) compound, and a copolymer which is used as a surfactant are selected and used, which is characterized by using it in an optimum content range.
폴리옥시에틸렌계(POE) 화합물, 폴리옥시프로필렌계(POP) 화합물 및 이들의 공중합체인 계면활성제는 텍스쳐 에칭액 조성물 중 히드록시 이온[OH-]의 활동도를 조절하여 Si100 방향과 Si111 방향에 대한 에칭 속도의 차이를 최소화시켜 동일 사용량에 대한 처리 매수를 증가시킬 수 있다. 뿐만 아니라, 결정성 실리콘 웨이퍼 표면의 젖음성을 개선시켜 에칭에 의해 생성된 수소 버블의 양을 빠르게 감소시킴으로써 버블 스틱 현상이 발생하는 것을 방지하여 텍스쳐 시 위치별 텍스쳐 품질의 편차를 감소시켜 균일성을 향상시키고 외관도 개선시킬 수 있다.Polyoxyethylene-based (POE) compounds, polyoxypropylene-based (POP) compounds, and their copolymers, surfactants, regulate the activity of hydroxy ions [OH − ] in the texture etching solution composition in the Si 100 and Si 111 directions. The number of treatments for the same amount of use can be increased by minimizing the difference in the etching rates. In addition, by improving the wettability of the surface of the crystalline silicon wafer to quickly reduce the amount of hydrogen bubbles generated by etching to prevent the bubble stick phenomenon to occur, by reducing the variation of the texture quality by position in the texture to improve uniformity And appearance can be improved.
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 공중합체로 이루어진 군으로부터 선택된 1종 이상의 계면활성제는 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물 총 100중량%에 대하여 0.000001 내지 1중량%로 포함되는 것이 바람직하고, 보다 바람직하게는 0.00001 내지 0.1중량%, 가장 바람직하게는 0.0001 내지 0.1중량%인 것이 좋다. 함량이 상기 범위에 해당되는 경우 실리콘 웨이퍼 표면의 텍스쳐 시 위치별 텍스쳐 품질의 편차를 감소시키고 웨이퍼 외관을 개선시킬뿐만 아니라 동일 사용량에 대한 처리 매수도 증가시킬 수 있다.The at least one surfactant selected from the group consisting of polyoxyethylene-based (POE) compounds, polyoxypropylene-based (POP) compounds and copolymers thereof is 0.000001 to 1 based on 100% by weight of the total amount of the texture etching solution composition of the crystalline silicon wafer. It is preferably included in the weight%, more preferably 0.00001 to 0.1% by weight, most preferably 0.0001 to 0.1% by weight. When the content falls within the above range, the texture quality of each silicon wafer surface may be reduced, and the appearance of the wafer may be improved, and the number of treatments for the same amount of use may be increased.
본 발명의 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물은 폴리옥시에틸렌계(POE) 화합물, 폴리옥시프로필렌계(POP) 화합물 및 이들의 공중합체로 이루어진 군으로부터 선택된 1종 이상의 계면활성제와 함께 불소계 계면활성제를 더 포함할 수 있다.The texture etching solution composition of the crystalline silicon wafer of the present invention comprises a fluorine-based surfactant with at least one surfactant selected from the group consisting of polyoxyethylene-based (POE) compounds, polyoxypropylene-based (POP) compounds, and copolymers thereof. It may further include.
불소계 계면활성제는 상기 폴리옥시 화합물계 계면활성제와 함께 에칭액 조성물의 표면장력을 낮추어 결정성 실리콘 웨이퍼 표면의 젖음성 개선을 더욱 촉진시켜 알칼리 화합물에 의한 과에칭을 방지한다.The fluorine-based surfactant, together with the polyoxy compound-based surfactant, lowers the surface tension of the etching solution composition to further improve the wettability of the surface of the crystalline silicon wafer, thereby preventing overetching by the alkali compound.
*불소계 계면활성제의 종류는 특별히 한정되지 않으나, 예컨대 과불소알킬 카르복시산염, 과불소알킬 술폰산염, 과불소알킬 황산염, 과불소알킬 인산염 등의 음이온계 계면활성제; 과불소알킬 아민염, 과불소알킬 4급암모늄염 등의 양이온계 계면활성제; 과불소알킬 카르복시베타인, 과불소알킬 술포베타인 등의 양쪽성 이온계 계면활성제; 불소화알킬 폴리옥시에틸렌 및 과불소알킬 폴리옥시에틸렌 등의 비이온계 계면활성제 등을 들 수 있다. 이들 화합물은 각 알킬기의 탄소수가 1 내지 30인 것일 수 있다. 이들은 단독 또는 2종 이상 혼합하여 사용할 수 있다.The type of the fluorine-based surfactant is not particularly limited, and examples thereof include anionic surfactants such as perfluoroalkyl carboxylate, perfluoroalkyl sulfonate, perfluoroalkyl sulfate, and perfluoroalkyl phosphate; Cationic surfactants such as perfluoroalkyl amine salts and perfluoroalkyl quaternary ammonium salts; Amphoteric ionic surfactants such as perfluoroalkyl carboxybetaine and perfluoroalkyl sulfobetaine; And nonionic surfactants such as fluorinated alkyl polyoxyethylene and perfluoroalkyl polyoxyethylene. These compounds may be those having 1 to 30 carbon atoms in each alkyl group. These can be used individually or in mixture of 2 or more types.
불소계 계면활성제는 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물 총 100중량%에 대하여 0.000001 내지 1중량%로 포함될 수 있고, 바람직하게는 0.00001 내지 0.1중량%, 보다 바람직하게는 0.0001 내지 0.1중량%인 것이 좋다. 함량이 상기 범위에 해당되는 경우 실리콘 웨이퍼 표면의 젖음성을 효과적으로 개선할 수 있다.The fluorine-based surfactant may be included in an amount of 0.000001 to 1% by weight, preferably 0.00001 to 0.1% by weight, and more preferably 0.0001 to 0.1% 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, the wettability of the silicon wafer surface can be effectively improved.
또한, 본 발명의 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물은 실리카 함유 화합물을 더 포함할 수 있다.In addition, the texture etching solution composition of the crystalline silicon wafer of the present invention may further comprise a silica-containing compound.
실리카 함유 화합물은 결정성 실리콘 웨이퍼 표면에 물리적으로 흡착하여 일종의 마스크 역할을 함으로써 실리콘 웨이퍼 표면을 미세 피라미드 형상으로 만들어 준다.Silica-containing compounds physically adsorb onto the crystalline silicon wafer surface and serve as a kind of mask, thereby making the silicon wafer surface into a fine pyramid shape.
실리카 함유 화합물로는 분말형, 콜로이드 용액형 또는 액상 규산 금속 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-containing 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 함유 화합물은 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물 총 100중량%에 대하여 0.00001 내지 10중량%로 포함될 수 있고, 바람직하게는 0.0001 내지 1중량%인 것이 좋다. 함량이 상기 범위에 해당되는 경우 결정성 실리콘 웨이퍼 표면에 미세 피라미드 형성을 용이하게 할 수 있다.The silica-containing compound may be included in an amount of 0.00001 to 10% by weight, and preferably 0.0001 to 1% 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, it is possible to facilitate formation of 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 폴리옥시에틸렌계(POE) 화합물, 폴리옥시프로필렌계(POP) 화합물 및 이들의 공중합체로 이루어진 군으로부터 선택된 1종 이상의 계면활성제를 최적의 함량 범위로 선택 사용함으로써 결정성 실리콘 웨이퍼 표면의 위치별 텍스쳐 품질의 편차를 최소화시켜 텍스쳐의 균일성을 향상시킬 수 있다. 이를 통하여 태양광의 흡수량을 극대화시키고 광 반사율을 낮춰 광효율을 높일 수 있다. 또한, 사용량을 현저히 낮추어 처리 매수를 증가시킬 수 있을 뿐만 아니라 텍스쳐 공정 중 별도의 에칭액 성분을 추가 투입할 필요가 없어 생산성과 비용 면에서 우수하다.The texture etching solution composition of the crystalline silicon wafer of the present invention comprising the above components is particularly a polyoxyethylene-based (POE) compound, a polyoxypropylene-based (POP) compound, and a copolymer thereof together with a cyclic compound. By selecting and using one or more surfactants selected from the group consisting of an optimal content range, the uniformity of the texture may be improved by minimizing the variation of the texture quality for each position of the surface of the crystalline silicon wafer. This maximizes the absorption of sunlight and lowers the light reflectance to increase light efficiency. In addition, it is possible to increase the number of sheets by significantly lowering the amount of use, and it is excellent in productivity and cost since there is no need to add an additional etching liquid component during the texture process.
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 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 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 1 내지 27Examples 1 to 27
수산화칼륨(KOH) 2중량%, 폴리옥시에틸렌벤질에테르(PBE) 0.016중량%, 과불소알킬 황산염(PFAS) 0.016중량% 및 잔량의 탈이온 증류수를 혼합하여 실시예 1의 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물을 제조하였다.Texture of crystalline silicon wafer of Example 1 by mixing 2% by weight of potassium hydroxide (KOH), 0.016% by weight of polyoxyethylene benzyl ether (PBE), 0.016% by weight of perfluoroalkyl sulfate (PFAS) and the remaining amount of deionized distilled water An etching liquid composition was prepared.
동일한 방법으로 하기 표 1에 기재된 성분 및 함량(중량%)으로 실시예 2 내지 27의 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물을 제조하였다.In the same manner, the texture etching solution compositions of the crystalline silicon wafers of Examples 2 to 27 were prepared using the ingredients and contents (wt%) shown in Table 1 below.
표 1
구분(중량%) 알칼리 화합물 고리형 화합물 POE계 계면활성제 불소계 계면활성제 실리카 함유 화합물 탈이온 증류수
종류 함량 종류 함량 종류 함량 종류 함량 종류 함량 함량
실시예1 KOH 2 - - PBE 0.016 PFAS 0.016 - - 잔량
실시예2 KOH 2 - - POE 0.016 PFAS 0.016 - - 잔량
실시예3 KOH 2 - - PPE 0.016 PFAS 0.016 - - 잔량
실시예4 KOH 2 - - PPE 0.016 PFAP 0.016 - - 잔량
실시예5 NaOH 2 - - PPE 0.016 PFAS 0.016 - - 잔량
실시예6 KOH 3 - - PPE 0.016 PFAS 0.016 - - 잔량
실시예7 KOH 4 - - PPE 0.016 PFAS 0.016 - - 잔량
실시예8 KOH 2 - - PPE 0.048 PFAS 0.016 - - 잔량
실시예9 KOH 2 - - PPE 0.016 PFAS 0.032 - - 잔량
실시예10 KOH 2 - - PPE 0.016 PFAS 0.016 SSS 0.5 잔량
실시예11 KOH 2 - - PPE 0.016 PFAS 0.016 CS 0.5 잔량
실시예12 KOH 2 NMP 1.5 PBE 0.008 PFAS 0.008 - - 잔량
실시예13 KOH 2 NMP 2 PBE 0.008 PFAS 0.008 - - 잔량
실시예14 KOH 2 NMP 2 POE 0.008 PFAS 0.008 - - 잔량
실시예15 KOH 2 NMP 2 PPE 0.008 PFAS 0.008 - - 잔량
실시예16 KOH 2 NMP 2 PPE 0.008 PFAP 0.008 - - 잔량
실시예17 NaOH 1 NMPAEP 1.90.1 PPE 0.008 PFAP 0.008 - - 잔량
실시예18 KOH 2 NMPGBL 1.90.1 PPE 0.008 PFAP 0.008 - - 잔량
실시예19 KOH 2 NMM AEP 1.90.1 PPE 0.008 PFAP 0.008 - - 잔량
실시예20 KOH 2 NMMGBL 1.90.1 PPE 0.008 PFAP 0.008 - - 잔량
실시예21 NaOH 1 NMP 2 PPE 0.008 PFAS 0.008 - - 잔량
실시예22 KOH 3 NMP 2 PPE 0.008 PFAS 0.008 - - 잔량
실시예23 KOH 4 NMP 2 PPE 0.008 PFAS 0.008 - - 잔량
실시예24 KOH 2 NMP 2 PPE 0.024 PFAS 0.008 - - 잔량
실시예25 KOH 2 NMP 2 PPE 0.008 PFAS 0.016 - - 잔량
실시예26 KOH 2 NMP 1.9 PPE 0.008 PFAS 0.008 SSS 0.5 잔량
실시예27 KOH 2 NMP 1.9 PPE 0.008 PFAS 0.008 CS 0.5 잔량
KOH: 수산화칼륨NaOH: 수산화나트륨NMP: N-메틸피롤리돈NMM: N-메틸모르폴린AEP: N-(2-아미노에틸)피페라진GBL: γ-부티로락톤PBE: 폴리옥시에틸렌벤질에테르POE: 폴리옥시에틸렌옥틸페닐에테르PPE: 폴리옥시에틸렌페닐에테르PFAS: 과불소화알킬 황산염PFAP: 과불소화알킬 인산염SSS: 액상 규산 나트륨CS: Na2O로 안정화시킨 콜로이드 실리카 용액
Table 1
Division (weight%) Alkali compounds Cyclic compound POE surfactant Fluorinated Surfactant Silica containing compounds Deionized distilled water
Kinds content Kinds content Kinds content Kinds content Kinds content content
Example 1 KOH 2 - - PBE 0.016 PFAS 0.016 - - Remaining amount
Example 2 KOH 2 - - POE 0.016 PFAS 0.016 - - Remaining amount
Example 3 KOH 2 - - PPE 0.016 PFAS 0.016 - - Remaining amount
Example 4 KOH 2 - - PPE 0.016 PFAP 0.016 - - Remaining amount
Example 5 NaOH 2 - - PPE 0.016 PFAS 0.016 - - Remaining amount
Example 6 KOH 3 - - PPE 0.016 PFAS 0.016 - - Remaining amount
Example 7 KOH 4 - - PPE 0.016 PFAS 0.016 - - Remaining amount
Example 8 KOH 2 - - PPE 0.048 PFAS 0.016 - - Remaining amount
Example 9 KOH 2 - - PPE 0.016 PFAS 0.032 - - Remaining amount
Example 10 KOH 2 - - PPE 0.016 PFAS 0.016 SSS 0.5 Remaining amount
Example 11 KOH 2 - - PPE 0.016 PFAS 0.016 CS 0.5 Remaining amount
Example 12 KOH 2 NMP 1.5 PBE 0.008 PFAS 0.008 - - Remaining amount
Example 13 KOH 2 NMP 2 PBE 0.008 PFAS 0.008 - - Remaining amount
Example 14 KOH 2 NMP 2 POE 0.008 PFAS 0.008 - - Remaining amount
Example 15 KOH 2 NMP 2 PPE 0.008 PFAS 0.008 - - Remaining amount
Example 16 KOH 2 NMP 2 PPE 0.008 PFAP 0.008 - - Remaining amount
Example 17 NaOH One NMPAEP 1.90.1 PPE 0.008 PFAP 0.008 - - Remaining amount
Example 18 KOH 2 NMPGBL 1.90.1 PPE 0.008 PFAP 0.008 - - Remaining amount
Example 19 KOH 2 NMM AEP 1.90.1 PPE 0.008 PFAP 0.008 - - Remaining amount
Example 20 KOH 2 NMMGBL 1.90.1 PPE 0.008 PFAP 0.008 - - Remaining amount
Example 21 NaOH One NMP 2 PPE 0.008 PFAS 0.008 - - Remaining amount
Example 22 KOH 3 NMP 2 PPE 0.008 PFAS 0.008 - - Remaining amount
Example 23 KOH 4 NMP 2 PPE 0.008 PFAS 0.008 - - Remaining amount
Example 24 KOH 2 NMP 2 PPE 0.024 PFAS 0.008 - - Remaining amount
Example 25 KOH 2 NMP 2 PPE 0.008 PFAS 0.016 - - Remaining amount
Example 26 KOH 2 NMP 1.9 PPE 0.008 PFAS 0.008 SSS 0.5 Remaining amount
Example 27 KOH 2 NMP 1.9 PPE 0.008 PFAS 0.008 CS 0.5 Remaining amount
KOH: potassium hydroxide NaOH: sodium hydroxide NMP: N-methylpyrrolidone NMM: N-methylmorpholine AEP: N- (2-aminoethyl) piperazine GBL: γ-butyrolactone PBE: polyoxyethylene benzyl ether POE polyoxyethylene octylphenyl ether PPE: polyoxyethylene phenyl ether PFAS: perfluorinated alkyl sulfate PFAP: perfluorinated alkyl phosphate SSS: a colloidal silica solution was stabilized with Na 2 O: liquid sodium silicate CS
비교예 1 내지 10Comparative Examples 1 to 10
실시예 1과 동일한 방법으로 하기 표 2에 기재된 성분 및 함량(중량%)으로 비교예 1 내지 10의 에칭액 조성물을 제조하였다.The etching solution compositions of Comparative Examples 1 to 10 were prepared in the same manner as in Example 1, using the ingredients and contents (% by weight) shown in Table 2 below.
표 2
구분 알칼리 화합물 고리형 화합물 POE계 계면활성제 불소계 계면활성제 실리카 함유 화합물 탈이온 증류수
종류 함량 종류 함량 종류 함량 종류 함량 종류 함량 함량
비교예1 KOH 2 - - PPE - PFAS 0.016 - - 잔량
비교예2 KOH 2 - - PPE 1.2 PFAS 0.016 - - 잔량
비교예 3 수산화칼륨(KOH) 1.5중량%, 이소프로필알코올(IPA) 5중량% 및 잔량의 탈이온 증류수
비교예 4 수산화칼륨(KOH) 1.5중량%, 에틸렌글리콜(EG) 5중량% 및 잔량의 탈이온 증류수
비교예 5 수산화칼륨(KOH) 1.5중량%, 디에틸렌 글리콜 모노메틸 에테르 5중량% 및 잔량의 탈이온 증류수
비교예 6 수산화칼륨(KOH) 1.5중량%, 모노에탄올아민 5중량% 및 잔량의 탈이온 증류수
비교예7 KOH 2 NMP 2 PPE - PFAS 0.008 - - 잔량
비교예8 KOH 2 NMP 2 PPE 1.2 PFAS 0.008 - - 잔량
비교예9 KOH 2 NMP - PPE 0.008 PFAS 0.008 - - 잔량
비교예10 KOH 2 NMP 51 PPE 0.008 PFAS 0.008 - - 잔량
KOH: 수산화칼륨NMP: N-메틸피롤리돈PPE: 폴리옥시에틸렌페닐에테르PFAS: 과불소화알킬 황산염
TABLE 2
division Alkali compounds Cyclic compound POE surfactant Fluorinated Surfactant Silica containing compounds Deionized distilled water
Kinds content Kinds content Kinds content Kinds content Kinds content content
Comparative Example 1 KOH 2 - - PPE - PFAS 0.016 - - Remaining amount
Comparative Example 2 KOH 2 - - PPE 1.2 PFAS 0.016 - - Remaining amount
Comparative Example 3 1.5% by weight potassium hydroxide (KOH), 5% by weight isopropyl alcohol (IPA) and residual deionized distilled water
Comparative Example 4 1.5% by weight potassium hydroxide (KOH), 5% by weight ethylene glycol (EG) and residual deionized distilled water
Comparative Example 5 1.5% by weight potassium hydroxide (KOH), 5% by weight diethylene glycol monomethyl ether and residual deionized distilled water
Comparative Example 6 1.5% by weight potassium hydroxide (KOH), 5% by weight monoethanolamine and residual deionized distilled water
Comparative Example 7 KOH 2 NMP 2 PPE - PFAS 0.008 - - Remaining amount
Comparative Example 8 KOH 2 NMP 2 PPE 1.2 PFAS 0.008 - - Remaining amount
Comparative Example 9 KOH 2 NMP - PPE 0.008 PFAS 0.008 - - Remaining amount
Comparative Example 10 KOH 2 NMP 51 PPE 0.008 PFAS 0.008 - - Remaining amount
KOH: Potassium hydroxide NMP: N-methylpyrrolidone PPE: Polyoxyethylene phenyl ether PFAS: Perfluoroalkyl sulfate
시험예 1Test Example 1
상기 실시예 1-11 및 비교예 1-6에서 제조된 단결정 실리콘 웨이퍼의 텍스쳐 에칭액 조성물의 텍스쳐 에칭 효과를 하기 방법으로 평가하고, 그 결과를 하기 표 3에 나타내었다.The texture etching effect of the texture etching solution composition of the single crystal silicon wafers prepared in Examples 1-11 and Comparative Examples 1-6 was evaluated by the following method, and the results are shown in Table 3 below.
- 단결정 실리콘 웨이퍼 기판을 제조된 단결정 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 single crystal 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 카메라와 3D 광학현미경을 이용하여 육안으로 관찰하고, 하기 기준에 의거하여 평가하였다. 이때, 변색은 텍스쳐 공정 온도로의 승온 시 자체 경시 변화가 발생하여 텍스쳐 시험이 필요 없는 것을 의미한다.Texture variation, ie, uniformity, of the texture formed on the surface of the etched single crystal silicon wafer substrate was visually observed using a digital camera and a 3D optical microscope, and evaluated based on the following criteria. At this time, the discoloration means that a change in temporal change occurs when the temperature is raised to the texture process temperature, so that a texture test is not necessary.
<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 3
구분 텍스쳐 균일성 피라미드 평균 크기(㎛) 평균 반사율(%)
실시예1 ◎ 6 12.02
실시예2 ◎ 6 12.12
실시예3 ◎ 6 11.82
실시예4 ◎ 6 12.15
실시예5 ◎ 7 12.04
실시예6 ◎ 8 12.29
실시예7 ◎ 10 12.24
실시예8 ◎ 6 12.32
실시예9 ◎ 6 12.17
실시예10 ◎ 5 12.19
실시예11 ◎ 4 12.08
비교예1 × 12 20.11
비교예2 × 6 23.21
비교예3 ○ 5 13.22
비교예4 × 10 21.13
비교예5 에칭액 변색
비교예6 에칭액 변색
TABLE 3
division Texture Uniformity Pyramid Average Size (μm) Average reflectance (%)
Example 1 ◎ 6 12.02
Example 2 ◎ 6 12.12
Example 3 ◎ 6 11.82
Example 4 ◎ 6 12.15
Example 5 ◎ 7 12.04
Example 6 ◎ 8 12.29
Example 7 ◎ 10 12.24
Example 8 ◎ 6 12.32
Example 9 ◎ 6 12.17
Example 10 ◎ 5 12.19
Example 11 ◎ 4 12.08
Comparative Example 1 × 12 20.11
Comparative Example 2 × 6 23.21
Comparative Example 3 ○ 5 13.22
Comparative Example 4 × 10 21.13
Comparative Example 5 Etching Discoloration
Comparative Example 6 Etching Discoloration
위 표 3과 같이, 본 발명에 따라 알칼리 화합물; 폴리옥시에틸렌계(POE) 화합물, 폴리옥시프로필렌계(POP) 화합물 및 이들의 공중합체로 이루어진 군으로부터 선택된 1종 이상의 계면활성제; 및 물을 포함하는 실시예 1 내지 11의 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 있음을 확인할 수 있었다. 또한, 불소계 계면활성제를 추가로 포함함으로써 에칭액 조성물의 표면 장력이 낮아져 결정성 실리콘 웨이퍼 표면의 젖음성 개선을 더욱 촉진시킬 수 있어서 알칼리 화합물에 의한 과에칭이 방지됨을 확인할 수 있었다.As shown in Table 3, the alkali compound according to the present invention; At least one surfactant selected from the group consisting of polyoxyethylene-based (POE) compounds, polyoxypropylene-based (POP) compounds, and copolymers thereof; When the texture is etched using the texture etching solution composition of Examples 1 to 11 containing water and the variation of the quality of each position of the fine pyramid formed on the surface of the single crystal silicon wafer is small, the uniformity is excellent and the light reflectance is low to improve the light efficiency Could confirm. In addition, it was confirmed that by further including a fluorine-based surfactant, the surface tension of the etching solution composition is lowered to further promote the improvement of the wettability of the surface of the crystalline silicon wafer, thereby preventing overetching by the alkali compound.
도 1은 실시예 1의 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 1, 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, 폴리옥시화합물계 계면활성제를 포함하지 않는 비교예 1의 텍스쳐 에칭액 조성물을 이용하는 경우 수산화칼륨에 의한 실리콘의 과에칭 현상이 발생하여 웨이퍼 전면에 피라미드가 랜덤하게 형성되었으며, 폴리옥시화합물계 계면활성제를 과량으로 포함하는 비교예 2의 텍스쳐 에칭액 조성물을 이용하는 경우 에칭 속도가 늦어져 피라미드가 형성되지 않았다.On the other hand, in the case of using the texture etching solution composition of Comparative Example 1 that does not contain a polyoxy compound-based surfactant, an over-etching phenomenon of silicon caused by potassium hydroxide occurred, so that pyramids were randomly formed on the entire surface of the wafer. In the case of using the texture etching solution composition of Comparative Example 2 containing an excessive amount, the etching rate was slowed to form a pyramid.
비교예 3의 텍스쳐 에칭액 조성물은 에칭액 조성물에 포함된 이소프로필알코올(IPA)의 낮은 비점으로 인해 텍스쳐 공정 중 이를 지속적으로 투입함으로써 발생되는 온도 구배에 기인하여 텍스쳐 불량이 일어나고 비용도 더 발생하였다.The texture etchant composition of Comparative Example 3 has a poor texture and cost more due to the temperature gradient generated by continuously inputting it during the texture process due to the low boiling point of isopropyl alcohol (IPA) contained in the etchant composition.
비교예 4의 텍스쳐 에칭액 조성물은 텍스쳐 균일성과 광 반사율 면에서 실시예에 비해 크게 뒤떨어진 특성을 나타내었다.The texture etching solution composition of Comparative Example 4 exhibited significantly inferior characteristics in comparison with Examples in terms of texture uniformity and light reflectance.
또한, 비교예 5 및 6의 텍스쳐 에칭액 조성물은 텍스쳐 공정 온도로의 승온 시 에칭액 조성물 자체에 경시 변화가 발생하였다.In addition, in the texture etching solution compositions of Comparative Examples 5 and 6, a change with time occurred in the etching solution composition itself when the temperature was raised to the texture process temperature.
시험예 2Test Example 2
상기 실시예 12-27 및 비교예 3-10에서 제조된 단결정 실리콘 웨이퍼의 텍스쳐 에칭액 조성물의 텍스쳐 에칭 효과를 시험예 1과 같은 방법으로 평가하고, 추가로 실시예 13 및 비교예 7-10의 텍스쳐 에칭액 조성물을 이용하여 공정성을 다음과 같이 평가하였다. 그 결과를 하기 표 4 및 5에 나타내었다.The texture etching effect of the texture etching solution composition of the single crystal silicon wafers prepared in Examples 12-27 and Comparative Examples 3-10 was evaluated in the same manner as in Test Example 1, and further, the textures of Example 13 and Comparative Examples 7-10 were The processability was evaluated as follows using the etching liquid composition. The results are shown in Tables 4 and 5 below.
(4) 공정성(처리 매수)(4) Fairness (the number of processing)
실시예 13 및 비교예 7-10에서 제조된 텍스쳐 에칭액 조성물을 이용하여 단결정 실리콘 웨이퍼 기판을 텍스쳐 에칭하되, 동일 함량으로 처리할 수 있는 매수를 확인하였다. 이때, 실시예 13의 처리 매수를 기준으로 하여 비교예 7-10의 처리 매수를 계산하고, 이를 토대로 하여 공정성을 평가하였다.Using a texture etching solution composition prepared in Example 13 and Comparative Example 7-10 was subjected to texture etching of the single crystal silicon wafer substrate, but the number of sheets that can be treated with the same content was confirmed. At this time, the number of treatments of Comparative Example 7-10 was calculated based on the number of treatments of Example 13, and fairness was evaluated based on this.
<평가기준><Evaluation Criteria>
○: 실시예 13의 처리 매수와 동일.(Circle): It is the same as the process number of Example 13.
△: 실시예 13의 처리 매수보다 5-10% 적음.Δ: 5-10% less than the number of sheets in Example 13.
×: 실시예 13의 처리 매수보다 10% 초과로 적음.X: It is less than 10% more than the number of sheets of Example 13.
표 4
구분 텍스쳐 균일성 피라미드 평균 크기(㎛) 평균 반사율(%)
실시예12 ◎ 6 12.04
실시예13 ◎ 4 11.99
실시예14 ◎ 4 12.05
실시예15 ◎ 4 12.07
실시예16 ◎ 5 12.30
실시예17 ◎ 4 12.01
실시예18 ◎ 3 11.98
실시예19 ◎ 5 12.01
실시예20 ◎ 4 12.10
실시예21 ◎ 5 12.05
실시예22 ◎ 5 12.10
실시예23 ◎ 7 12.15
실시예24 ◎ 4 12.50
실시예25 ◎ 4 12.10
실시예26 ◎ 4 11.99
실시예27 ◎ 3 12.05
비교예3 ○ 5 13.22
비교예4 × 10 21.13
비교예5 에칭액 변색
비교예6 에칭액 변색
비교예7 ◎ 4 12.62
비교예8 × 6 24.38
비교예9 ○ 6 12.52
비교예10 × 0.5 21.19
Table 4
division Texture Uniformity Pyramid Average Size (μm) Average reflectance (%)
Example 12 ◎ 6 12.04
Example 13 ◎ 4 11.99
Example 14 ◎ 4 12.05
Example 15 ◎ 4 12.07
Example 16 ◎ 5 12.30
Example 17 ◎ 4 12.01
Example 18 ◎ 3 11.98
Example 19 ◎ 5 12.01
Example 20 ◎ 4 12.10
Example 21 ◎ 5 12.05
Example 22 ◎ 5 12.10
Example 23 ◎ 7 12.15
Example 24 ◎ 4 12.50
Example 25 ◎ 4 12.10
Example 26 ◎ 4 11.99
Example 27 ◎ 3 12.05
Comparative Example 3 ○ 5 13.22
Comparative Example 4 × 10 21.13
Comparative Example 5 Etching Discoloration
Comparative Example 6 Etching Discoloration
Comparative Example 7 ◎ 4 12.62
Comparative Example 8 × 6 24.38
Comparative Example 9 ○ 6 12.52
Comparative Example 10 × 0.5 21.19
표 5
구분 실시예13 비교예7 비교예8 비교예9 비교예10
공정성 기준 △ × △ ×
Table 5
division Example 13 Comparative Example 7 Comparative Example 8 Comparative Example 9 Comparative Example 10
Fairness standard △ × △ ×
위 표 4 및 5와 같이, 본 발명에 따라 알칼리 화합물, 폴리옥시에틸렌계(POE) 화합물, 폴리옥시프로필렌계(POP) 화합물 및 이들의 공중합체로 이루어진 군으로부터 선택된 1종 이상의 계면활성제 및 물을 최적의 함량으로 포함하는 실시예 12 내지 27의 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 있을 뿐만 아니라 동일 함량에 대한 처리 매수를 증가시킬 수 있어 공정성도 우수하였다.As shown in Tables 4 and 5, at least one surfactant and water selected from the group consisting of alkali compounds, polyoxyethylene-based (POE) compounds, polyoxypropylene-based (POP) compounds and copolymers thereof according to the present invention When the texture was etched using the texture etching solution compositions of Examples 12 to 27 containing the optimum content, the uniformity of the fine pyramids formed on the surface of the single crystal silicon wafer was small, resulting in excellent uniformity and low light reflectance. In addition to increasing the number of treatments for the same content was also excellent in fairness.
또한, 실시예의 텍스쳐 에칭액 조성물은 고리형 화합물을 포함함으로써 기존의 텍스쳐 에칭액 조성물에 비해 처리 매수를 대폭 증가시킬 수 있었고 텍스쳐 공정 중 별도의 에칭액 성분을 투입할 필요가 없어 생산성과 비용 면에서 유리함을 확인하였다.In addition, the texture etchant composition of the embodiment was able to significantly increase the number of treatments compared to the conventional texture etchant composition by including a cyclic compound, it is confirmed that it is advantageous in terms of productivity and cost because it does not need to add a separate etchant component during the texture process It was.
또한, 실시예의 텍스쳐 에칭액 조성물은 불소계 계면활성제를 추가로 포함함으로써 에칭액 조성물의 표면 장력이 낮아져 결정성 실리콘 웨이퍼 표면의 젖음성 개선을 더욱 촉진시킬 수 있어서 알칼리 화합물에 의한 과에칭이 방지됨을 확인할 수 있었다.In addition, the texture etching solution composition of Example was further confirmed that by further including a fluorine-based surfactant, the surface tension of the etching solution composition can be further promoted to improve the wettability of the surface of the crystalline silicon wafer, thereby preventing overetching by the alkali compound.
도 3은 실시예 12의 텍스쳐 에칭액 조성물로 텍스쳐 에칭된 결정성 실리콘 웨이퍼의 표면을 나타낸 3D 광학현미경 사진이고, 도 4는 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.3 is a 3D optical micrograph showing the surface of the crystalline silicon wafer texture etched with the texture etching solution composition of Example 12, Figure 4 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, 폴리옥시화합물계 계면활성제 또는 고리형 화합물의 함량이 본 발명의 범위에 해당되지 않는 비교예 7 및 9는 실리콘 표면 내 미세 피라미드 구조의 형성 면에서는 양호한 결과를 보이지만 동일 함량에 대한 처리 매수가 적어 실시예에 비해 공정성이 좋지 못하였다. 또한, 비교예 8 및 10은 알칼리 화합물에 의한 실리콘 에칭 속도가 현저하게 저하되어 피라미드가 제대로 형성되지 못하였다.On the other hand, Comparative Examples 7 and 9 in which the content of the polyoxy compound-based surfactant or the cyclic compound are not within the scope of the present invention show good results in terms of the formation of the fine pyramid structure in the silicon surface, but the number of treatments for the same content The processability was not good compared with the Example. In addition, in Comparative Examples 8 and 10, the silicon etching rate due to the alkali compound was significantly lowered, so that pyramids could not be formed properly.
비교예 3의 텍스쳐 에칭액 조성물은 에칭액 조성물에 포함된 이소프로필알코올(IPA)의 낮은 비점으로 인해 텍스쳐 공정 중 이를 지속적으로 투입함으로써 발생되는 온도 구배에 기인하여 텍스쳐 불량이 일어나고 비용도 더 발생하였다.The texture etchant composition of Comparative Example 3 has a poor texture and cost more due to the temperature gradient generated by continuously inputting it during the texture process due to the low boiling point of isopropyl alcohol (IPA) contained in the etchant composition.
비교예 4는 텍스쳐 에칭액 조성물은 텍스쳐 균일성과 광 반사율 면에서 실시예에 비해 크게 뒤떨어진 특성을 나타내었다.In Comparative Example 4, the texture etching solution composition exhibited significantly inferior characteristics in comparison with Examples in terms of texture uniformity and light reflectance.
또한, 비교예 5 및 6의 텍스쳐 에칭액 조성물은 텍스쳐 공정 온도로의 승온 시 에칭액 조성물 자체에 경시 변화가 발생하였다.In addition, in the texture etching solution compositions of Comparative Examples 5 and 6, a change with time occurred in the etching solution composition itself when the temperature was raised to the texture process temperature.

Claims (10)

  1. 알칼리 화합물 0.1 내지 20중량%; 폴리옥시에틸렌계(POE) 화합물, 폴리옥시프로필렌계(POP) 화합물 및 이들의 공중합체로 이루어진 군으로부터 선택된 1종 이상의 계면활성제 0.000001 내지 1중량%; 및 잔량의 물을 포함하는 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물.0.1-20% by weight of alkaline compound; 0.000001 to 1% by weight of at least one surfactant selected from the group consisting of polyoxyethylene-based (POE) compounds, polyoxypropylene-based (POP) compounds, and copolymers thereof; And a residual amount of water.
  2. 청구항 1에 있어서, 고리형 화합물 0.1 내지 50중량%를 추가로 포함하는 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물.The texture etchant composition of claim 1, further comprising 0.1 to 50 wt% of the cyclic compound.
  3. 청구항 2에 있어서, 고리형 화합물은 비점이 100℃ 이상인 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물.The texture etching solution composition of claim 2, wherein the cyclic compound has a boiling point of 100 ° C. or higher.
  4. 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.
  5. 청구항 1에 있어서, 계면활성제는 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, 폴리옥시에틸렌 수소화 캐스터 에테르; 폴리옥시에틸렌라우릴에스테르, 폴리옥시에틸렌스테아릴에스테르, 폴리옥시에틸렌올레일에스테르; 폴리옥시에틸렌라우릴아민, 폴리옥시에틸렌스테아릴아민, 폴리옥시에틸렌탈로우아민; 폴리프로필렌글리콜; 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 및 에틸렌디아민 부가형 폴리옥시에틸렌-폴리옥시프로필렌 공중합체로 이루어진 군으로부터 선택된 1종 이상인 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물.The surfactant according to claim 1, wherein the surfactant is polyoxyethylene glycol, polyoxyethylene glycol methyl ether, polyoxyethylene monoallyl ether, polyoxyethylene neopentyl ether, polyethylene glycol mono (tristyrylphenyl) ether, polyoxyethylene cetyl ether , Polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxyethylene stearyl ether, polyoxyethylene tridecyl ether, polyoxyethylene decyl ether, polyoxyethylene octyl ether, polyoxyethylene bisphenol-A ether, poly Oxyethylene glycerin ether, polyoxyethylene nonylphenyl ether, polyoxyethylene benzyl ether, polyoxyethylene phenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene phenol ether, polyoxyethylene alkylcyclo having 6 to 30 carbon atoms Hexyl ether, polyoxyethyleneβ-naphthol ether, polyoxye Alkylene caster ether, polyoxyethylene hydrogenated castor ether; Polyoxyethylene lauryl ester, polyoxyethylene stearyl ester, polyoxyethylene oleyl ester; Polyoxyethylene laurylamine, polyoxyethylene stearylamine, polyoxyethylene tallowamine; Polypropylene glycol; Polyoxyethylene-polyoxypropylene copolymer, polyoxyethylene-polyoxypropylene decanyl ether copolymer, polyoxyethylene-polyoxypropylene undecanyl ether copolymer, polyoxyethylene-polyoxypropylene dodecanyl ether copolymer, poly Oxyethylene-polyoxypropylene tetradecanyl ether copolymer, polyoxyethylene-polyoxypropylene 2-ethylhexyl ether copolymer, polyoxyethylene-polyoxypropylene lauryl ether copolymer, polyoxyethylene-polyoxypropylene stearyl A texture etching solution composition of at least one crystalline silicon wafer selected from the group consisting of an ether copolymer, a glycerin-added polyoxyethylene-polyoxypropylene copolymer, and an ethylenediamine-added polyoxyethylene-polyoxypropylene copolymer.
  6. 청구항 2에 있어서, 고리형 화합물은 피페라진, N-메틸피페라진, N-에틸피페라진, 히드록시에틸피페라진, N-(2-아미노에틸)피페라진, N,N'-디메틸피페라진, 모르폴린, N-메틸모르폴린, N-에틸모르폴린, N-페닐모르폴린, 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-메틸-4-피페리돈, N-비닐-2-피페리돈, N-메틸피롤리딘, N-메틸피롤리돈, N-에틸-2-피롤리돈, N-이소프로필-2-피롤리돈, N-부틸-2-피롤리돈, N-tert-부틸-2-피롤리돈, N-헥실-2-피롤리돈, N-옥틸-2-피롤리돈, N-벤질-2-피롤리돈, N-시클로헥실-2-피롤리돈, N-비닐-2-피롤리돈, N-(2-히드록시에틸)-2-피롤리돈, N-(2-메톡시에틸)-2-피롤리돈, N-(2-메톡시프로필)-2-피롤리돈, N-(2-에톡시에틸)-2-피롤리돈, N-메틸 이미다졸리디논, 디메틸이미다졸리디논, N-(2-히드록시에틸)-에틸렌우레아, 테트라히드로퓨란, 테트라히드로퍼푸릴알코올, 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, 톨릴트리아졸, 1,2,3-벤조트리아졸, 1,2,3-트리아졸, 1,2,4-트리아졸, 3-아미노-1,2,4-트리아졸, 4-아미노-4H-1,2,4-트리아졸, 1-히드록시벤조트리아졸, 1-메틸벤조트리아졸, 2-메틸벤조트리아졸, 5-메틸벤조트리아졸, 벤조트리아졸-5-카르본산, 니트로벤조트리아졸 및 2-(2H-벤조트리아졸-2-일)-4,6-디-t-부틸페놀로 이루어진 군으로부터 선택된 1종 이상인 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물.The compound according to claim 2, wherein the cyclic compound is piperazine, N-methylpiperazine, N-ethylpiperazine, hydroxyethylpiperazine, N- (2-aminoethyl) piperazine, N, N'-dimethylpiperazine, Morpholine, N-methylmorpholine, N-ethylmorpholine, N-phenylmorpholine, N-cocomorpholine, N- (2-aminoethyl) morpholine, N- (2-cyanoethyl) morpholine, N- (2-hydroxyethyl) morpholine, N- (2-hydroxypropyl) morpholine, N-acetylmorpholine, N-formylmorpholine, N-methylmorpholine-N-oxide, methylpyridine, N -Methylpiperidine, 3,5-dimethylpiperidine, N-ethylpiperidine, N- (2-hydroxyethyl) piperidine, N-methyl-4-piperidone, N-vinyl-2- Piperidone, N-methylpyrrolidin, N-methylpyrrolidone, N-ethyl-2-pyrrolidone, N-isopropyl-2-pyrrolidone, N-butyl-2-pyrrolidone, N- tert-butyl-2-pyrrolidone, N-hexyl-2-pyrrolidone, N-octyl-2-pyrrolidone, N-benzyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone , N-vinyl-2-pyrrole Money, N- (2-hydroxyethyl) -2-pyrrolidone, N- (2-methoxyethyl) -2-pyrrolidone, N- (2-methoxypropyl) -2-pyrrolidone, N- (2-ethoxyethyl) -2-pyrrolidone, N-methyl imidazolidinone, dimethylimidazolidinone, N- (2-hydroxyethyl) -ethyleneurea, tetrahydrofuran, tetrahydroper Furyl alcohol, 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, Tolyltriazole, 1,2,3-benzotriazole, 1,2,3-triazole, 1,2,4-triazole, 3-amino-1,2,4-triazole, 4-amino-4H -1,2,4-triazole, 1-hydroxybenzotriazole, 1-methylbenzotriazole, 2-methylbenzotriazole, 5-methylbenzotriazole, benzotriazole-5-carboxylic acid, nitrobenzo Triazoles and 2- (2H-benzot 2-yl) -4,6-di -t- determining at least one member selected from the group consisting of butyl phenol texture etching liquid composition of the silicone wafer.
  7. 청구항 1에 있어서, 각 알킬기의 탄소수가 1 내지 30인 과불소알킬 카르복시산염, 과불소알킬 술폰산염, 과불소알킬 황산염, 과불소알킬 인산염, 과불소알킬 아민염, 과불소알킬 4급암모늄염, 과불소알킬 카르복시베타인, 과불소알킬 술포베타인, 불소화알킬 폴리옥시에틸렌 및 과불소알킬 폴리옥시에틸렌으로 이루어진 군으로부터 선택된 1종 이상의 불소계 계면활성제를 0.000001 내지 1중량%로 더 포함하는 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물.The perfluoroalkyl carboxylate, the perfluoroalkyl sulfonate, the perfluoroalkyl sulfate, the perfluoroalkyl phosphate, the perfluoroalkyl amine salt, the perfluoroalkyl quaternary ammonium salt, and perfluorine according to claim 1, wherein each alkyl group has 1 to 30 carbon atoms. A crystalline silicon wafer further comprising 0.000001 to 1% by weight of one or more fluorine-based surfactants selected from the group consisting of small alkyl carboxybetaine, perfluoroalkyl sulfobetaine, fluorinated alkyl polyoxyethylene and perfluoroalkyl polyoxyethylene Texture etching solution composition.
  8. 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 함유 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-containing compound selected from the group consisting of liquid lithium silicate.
  9. 청구항 1 내지 8 중 어느 한 항의 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물로 결정성 실리콘 웨이퍼를 침적, 분무 또는 침적 및 분무하는 단계를 포함하는 결정성 실리콘의 텍스쳐 에칭방법.A method of etching a texture of crystalline silicon comprising depositing, spraying or depositing and spraying the crystalline silicon wafer with the texture etching liquid composition of any one of claims 1 to 8.
  10. 청구항 9에 있어서, 침적, 분무 또는 침적 및 분무는 50 내지 100℃의 온도에서 30초 내지 60분 동안 수행되는 결정성 실리콘의 텍스쳐 에칭방법.The method of claim 9, 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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