WO2012169721A1 - Texture etching solution composition and texture etching method for crystalline silicon wafer - Google Patents

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

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WO2012169721A1
WO2012169721A1 PCT/KR2012/001741 KR2012001741W WO2012169721A1 WO 2012169721 A1 WO2012169721 A1 WO 2012169721A1 KR 2012001741 W KR2012001741 W KR 2012001741W WO 2012169721 A1 WO2012169721 A1 WO 2012169721A1
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acid
cellulose
silicon wafer
texture
crystalline silicon
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PCT/KR2012/001741
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French (fr)
Korean (ko)
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홍형표
이재연
임대성
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동우화인켐 주식회사
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Priority to CN201280024311.0A priority Critical patent/CN103547654B/en
Publication of WO2012169721A1 publication Critical patent/WO2012169721A1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K13/00—Etching, surface-brightening or pickling compositions
    • C09K13/02—Etching, surface-brightening or pickling compositions containing an alkali metal hydroxide
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K13/00—Etching, surface-brightening or pickling compositions
    • C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
    • C09K13/06—Etching, surface-brightening or pickling compositions containing an inorganic acid with organic material
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/10—Etching compositions
    • C23F1/14—Aqueous compositions
    • C23F1/16—Acidic compositions
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
    • 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 and a texture etching method of a crystalline silicon wafer capable of uniformly forming a crystalline silicon wafer surface in a fine pyramid structure to increase light efficiency.
  • Solar cells which are rapidly spreading in recent years, are electronic devices that directly convert solar energy, which is clean energy, into electricity as a next-generation energy source, and diffuse phosphorus on its surface based on P-type silicon semiconductors containing boron in silicon. It consists of the PN junction semiconductor substrate in which the N type silicon semiconductor layer was formed.
  • the surface of the solar cell silicon wafer constituting the PN junction semiconductor substrate is formed into a fine pyramid structure and the antireflection film is treated.
  • the surface of the silicon wafer textured with the fine pyramid structure increases the intensity of the light absorbed by lowering the reflectance of incident light having a wide wavelength band, thereby improving the performance of the solar cell.
  • U.S. Patent No. 4,137,123 discloses 0.5-10 weight in an anisotropic etching solution containing 0-75% by volume of ethylene glycol, 0.05-50% by weight of potassium hydroxide and the remaining amount of water.
  • a silicon texture etching solution in which% silicon is dissolved is disclosed.
  • this etchant can cause pyramid formation defects to increase the light reflectance and cause a decrease in efficiency.
  • European Patent No. 0477424 discloses a texture etching method of supplying oxygen to a texture etching solution in which silicon is dissolved in ethylene glycol, potassium hydroxide and residual water, that is, performing an air rating process.
  • this etching method has a disadvantage in that it causes poor pyramid formation, which leads to an increase in light reflectivity and a decrease in efficiency, and requires the installation of a separate air rating equipment.
  • Korean Patent No. 0180621 discloses a texture etching solution mixed at a ratio of 0.5-5% potassium hydroxide solution, 3-20% by volume of isopropyl alcohol, and 75-96.5% by volume of deionized water
  • US Patent No. 6,451,218 No. discloses a texture etching solution comprising an alkali compound, isopropyl alcohol, a water soluble alkaline ethylene glycol and water.
  • these etching solutions contain isopropyl alcohol having a low boiling point and need to be added during the texturing process, it is not economical in terms of productivity and cost, and the addition of isopropyl alcohol causes a temperature gradient of the etching solution, resulting in the surface of the silicon wafer.
  • the texture quality variation of each position may increase, resulting in poor uniformity.
  • An object of the present invention is to provide a texture etching liquid composition of a crystalline silicon wafer that can improve the light efficiency by improving the uniformity of the texture by position in forming a texture of the fine pyramid structure on the surface of the crystalline silicon wafer.
  • an object of the present invention is to provide a texture etching liquid composition of a crystalline silicon wafer that does not require the addition of an additional etching liquid component and the application of an air rating process during the etching process.
  • Another object of the present invention is to provide a texture etching method using the texture etching liquid composition of the crystalline silicon wafer.
  • alkali compound 1. 0.1-20% by weight of alkali compound; Polysaccharides 10 -9 to 10% by weight; 10 -9 to 10 weight percent of fatty acids, metal salts thereof, or mixtures thereof; And a residual amount of water.
  • composition according to the above 1, wherein the alkali compound is at least one selected from the group consisting of potassium hydroxide, sodium hydroxide, ammonium hydroxide, tetrahydroxymethylammonium and tetrahydroxyethylammonium.
  • polysaccharide is at least one selected from the group consisting of glucan-based compounds, fructan-based compounds, mannan-based compounds, galactan-based compounds and metal salts of the texture etching liquid composition of the crystalline silicon wafer.
  • the polysaccharide is cellulose, dimethylaminoethyl cellulose, diethylaminoethyl cellulose, ethyl hydroxyethyl cellulose, methyl hydroxyethyl cellulose, 4-aminobenzyl cellulose, triethylaminoethyl cellulose, cyanoethyl cellulose , Ethyl cellulose, methyl cellulose, carboxymethyl cellulose, carboxyethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, alginic acid, amylose, amylopectin, pectin, starch, dextrin, ⁇ -cyclodextrin, ⁇ -cyclodextrin, ⁇ - 1 type selected from the group consisting of cyclodextrin, hydroxypropyl- ⁇ -cyclodextrin, methyl- ⁇ -cyclodextrin, dextran, dextransulfate sodium, sapon
  • the polysaccharide has an average molecular weight of 5,000 to 1,000,000 texture etching liquid composition of a crystalline silicon wafer.
  • the fatty acid is acetic acid, propionic acid, butyric acid, valeric acid, enantiic acid, caprylic acid, pelagonic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachid Acid, behenic acid, lignocerinic acid, sertoic acid, eicosapentaenoic acid, docosahexaenoic acid, linoleic acid, ⁇ -linolenic acid, ⁇ -linolenic acid, dihomo- ⁇ -linolenic acid, arachidonic acid, oleic acid, elideic acid
  • fine powder silica Colloidal silica solution stabilized with Na 2 O; Colloidal silica solution stabilized with K 2 O; Colloidal silica solution stabilized with acid solution; Colloidal silica solution stabilized with NH 3 ; Colloidal silica solution stabilized with at least one organic solvent selected from the group consisting of ethyl alcohol, propyl alcohol, ethylene glycol, methyl ethyl ketone and methyl isobutyl ketone; Liquid sodium silicate; Liquid potassium silicate; And at least one silica compound selected from the group consisting of liquid lithium silicate.
  • Texture etching method of the crystalline silicon wafer comprising the step of depositing, spraying or depositing and spraying the crystalline silicon wafer with the texture etching liquid composition of any one of the above 1 to 8.
  • the deposition, spraying or deposition and spraying is a texture etching method of a crystalline silicon wafer is carried out for 30 seconds to 60 minutes at a temperature of 50 to 100 °C.
  • the texture of the fine pyramid structure is uniformly formed on the surface of the crystalline silicon wafer to maximize the absorption of solar light and lower the light reflectance to increase the light efficiency.
  • the present invention does not need to add a separate etching liquid component during the texturing process and does not need to introduce an air rating equipment, thereby improving the quality and productivity, and also has an advantage in terms of process cost.
  • Example 1 is a 3D optical micrograph showing the surface of a single crystal silicon wafer texture-etched with the texture etching liquid composition of the crystalline silicon wafer of Example 10 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 10 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; Polysaccharides; Fatty acids, metal salts thereof or mixtures thereof; And a residual amount of water.
  • the alkali compound 0.1 to 20% by weight; Polysaccharides 10 -9 to 10% by weight; 10 -9 to 10 weight percent of fatty acids, metal salts thereof, or mixtures thereof; And residual amount of water.
  • An alkali compound is a component which etches the surface of a crystalline silicon wafer,
  • the kind is not specifically limited.
  • potassium hydroxide, sodium hydroxide, ammonium hydroxide, tetrahydroxymethylammonium, tetrahydroxyethylammonium, etc. are mentioned, Among these, potassium hydroxide and sodium hydroxide are preferable. These can be used individually or in mixture of 2 or more types.
  • the alkali compound is preferably included in an amount of 0.1 to 20% by weight, and more preferably 1 to 5% by weight, based on 100% by weight of the total amount of the texture etching solution composition of the crystalline silicon wafer.
  • the silicon wafer surface can be etched.
  • the present invention is characterized by including the polysaccharide in an optimum content.
  • Polysaccharides are saccharides in which two or more monosaccharides are glycosidic bonds to form large molecules, and are formed by etching while forming a uniform fine pyramid and improving appearance by preventing overetching and accelerated etching by alkaline compounds. It is a component that prevents the bubble stick phenomenon by quickly dropping the hydrogen bubbles from the silicon wafer surface.
  • polysaccharides examples include glucan compounds, fructan compounds, mannan compounds, galactan compounds, or metal salts thereof, among which glucan compounds and metal salts thereof (e.g., Alkali metal salts) are preferred. These can be used individually or in mixture of 2 or more types.
  • glucan compound examples include cellulose, dimethylaminoethyl cellulose, diethylaminoethyl cellulose, ethyl hydroxyethyl cellulose, methyl hydroxyethyl cellulose, 4-aminobenzyl cellulose, triethylaminoethyl cellulose, cyanoethyl cellulose, ethyl cellulose, Methyl cellulose, carboxymethyl cellulose, carboxyethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, alginic acid, amylose, amylopectin, pectin, starch, dextrin, ⁇ -cyclodextrin, ⁇ -cyclodextrin, ⁇ -cyclodextrin, hydrate Oxypropyl- ⁇ -cyclodextrin, methyl- ⁇ -cyclodextrin, dextran, dextransulfate sodium, saponin, glycogen, zymoic acid
  • the polysaccharide may have an average molecular weight of 5,000 to 1,000,000, preferably 50,000 to 200,000.
  • the polysaccharide may be included in an amount of 10 -9 to 10% by weight, preferably 10 -6 to 1% by weight, based on 100% by weight of the texture etching solution composition of the crystalline silicon wafer. If the content falls within the above range, it is possible to effectively prevent over-etching and etching acceleration. If the content is more than 10% by weight, it is difficult to form the desired fine pyramid by drastically lowering the etching rate by the alkali compound.
  • the present invention is characterized in that it contains an optimal amount of a fatty acid, a metal salt thereof, or a mixture thereof together with a polysaccharide.
  • Fatty acids and their metal salts are used together with polysaccharides to further prevent over-etching by alkaline compounds to form uniform fine pyramids and at the same time drop hydrogen bubbles generated by etching more quickly from the surface of the silicon wafer, resulting in a bubble stick phenomenon. It is also a component that prevents.
  • Fatty acids are carboxylic acids of hydrocarbon chains containing carboxyl groups, specifically acetic acid, propionic acid, butyric acid, valeric acid, enantiic acid, caprylic acid, pelagonic acid, capric acid, lauric acid, myristic acid, palmitic acid, Stearic acid, arachidic acid, behenic acid, lignocerinic acid, serotic acid, eicosapentaenoic acid, docosahexaenoic acid, linoleic acid, ⁇ -linolenic acid, ⁇ -linolenic acid, dihomo- ⁇ -linolenic acid, arachidonic acid, Oleic acid, elideic acid, erucic acid, nerbonic acid, and the like.
  • the metal salt of a fatty acid may include an ester reactant of the above fatty acid with a metal salt such as NaOH or KOH. These can be used individually or in mixture of 2 or more types.
  • Fatty acids, metal salts thereof, and mixtures thereof may be included in amounts of 10 -9 to 10% by weight, preferably 10 -6 to 1% by weight, based on 100% by weight of the total amount of the texture etching solution composition of the crystalline silicon wafer. When the content falls within the above range, over-etching can be effectively prevented.
  • the texture etching solution composition of the crystalline silicon wafer of the present invention may further include a fluorine-based surfactant.
  • the fluorine-based surfactant lowers the surface tension of the etching solution composition to further promote the wettability improvement of the surface of the crystalline silicon wafer, thereby preventing overetching by the alkali compound.
  • fluorine-type surfactant such as a perfluoroalkyl carboxylate, a perfluoroalkyl sulfonate, a perfluoroalkyl sulfate, a 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 10 -9 to 10% by weight, preferably 10 -6 to 1% by weight, based on 100% by weight of the texture etching solution composition of the crystalline silicon wafer. When the content falls within the above range, 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 compound.
  • the silica compound is a component that makes the surface of the crystalline silicon wafer easy to form a fine pyramid by physically adsorbing the surface of the crystalline silicon wafer and acting as a kind of mask.
  • silica compound examples include powder, colloidal solution, or liquid metal silicate compounds. Specifically, fine powder silica; Colloidal silica solution stabilized with Na 2 O; Colloidal silica solution stabilized with K 2 O; Colloidal silica solution stabilized with acid solution; Colloidal silica solution stabilized with NH 3 ; Colloidal silica solution stabilized with at least one organic solvent selected from the group consisting of ethyl alcohol, propyl alcohol, ethylene glycol, methyl ethyl ketone and methyl isobutyl ketone; Liquid sodium silicate; Liquid potassium silicate; Liquid lithium silicate etc. can be mentioned, These can be used individually or in mixture of 2 or more types.
  • the silica compound may be included in an amount of 10 -9 to 10% by weight, preferably 10 -6 to 1% by weight, based on 100% by weight of the total amount of the texture etching solution composition of the crystalline silicon wafer. If the content falls within the above range, it is possible to easily form a fine pyramid on the surface of the crystalline silicon wafer.
  • Water may be included in the remaining amount in the total 100% by weight of the texture etching solution composition of the crystalline silicon wafer.
  • the kind of water is not specifically limited, It is preferable that it is deionized distilled water, More preferably, it is preferable that the specific resistance value is 18 kW / cm or more as deionized distilled water for a semiconductor process.
  • the texture etching liquid composition of the crystalline silicon wafer of the present invention comprising the above components comprises a micropyramidal structure on the surface of the crystalline silicon wafer, in particular by containing an optimal amount of fatty acids, metal salts thereof or mixtures thereof with polysaccharides. Formed uniformly with the texture of maximizing the absorption of sunlight and lowering the light reflectance can increase the light efficiency. In addition, there is no need to add a separate etchant component during the texture etching process, and there is no need to introduce an air rating equipment, which is advantageous in terms of productivity and cost.
  • the texture etching liquid composition of the crystalline silicon wafer of the present invention can be applied to all conventional etching processes, such as dip, spray and single wafer etching processes.
  • the present invention provides a texture etching method of a crystalline silicon wafer using the texture etching liquid composition of the crystalline silicon wafer.
  • the texture etching method of the crystalline silicon wafer includes depositing, spraying or depositing and spraying the crystalline silicon wafer using the texture etching liquid composition of the crystalline silicon wafer of the present invention.
  • the number of depositions and sprays is not particularly limited, and the order of both deposition and spraying is not limited.
  • Deposition, spraying or depositing and spraying may be performed for 30 seconds to 60 minutes at a temperature of 50 to 100 ° C.
  • the texture etching method of the crystalline silicon wafer of the present invention does not need to introduce a separate air-rating apparatus for supplying oxygen, so it is economical in terms of initial production and processing costs, and is uniform even in a simple process. It allows the formation of a structure.
  • the texture etching solution composition of the crystalline silicon wafer was prepared by mixing 4% by weight of potassium hydroxide (KOH), 0.005% by weight of dimethylaminoethyl cellulose (DMAEC), 0.005% by weight of caprylic acid (OA), and residual deionized distilled water.
  • KOH potassium hydroxide
  • DMAEC dimethylaminoethyl cellulose
  • OA caprylic acid
  • Example 2 The same procedure as in Example 1, except that the same ingredients and contents as in Table 1 were used. Here, the content represents weight percent.
  • a 1.5% by weight potassium hydroxide (KOH), 5% by weight isopropyl alcohol (IPA) and the remaining amount of deionized distilled water was mixed to prepare a texture etching solution composition of the crystalline silicon wafer.
  • the single crystal silicon wafer substrate was immersed in the texture etching liquid composition of the prepared silicon wafer for 20 minutes at a temperature of 80 ° C.
  • Texture variation that is, uniformity, formed on the surface of the etched single crystal silicon wafer substrate was visually observed using a digital camera, a 3D optical microscope, and a scanning electron microscope (SEM), and evaluated based on the following criteria. .
  • the size of the fine pyramid formed on the surface of the textured etched single crystal silicon wafer substrate was measured using a scanning electron microscope (SEM). At this time, the size of the fine pyramid formed in the unit area was measured and expressed as their average value.
  • the average reflectance when the surface of the texture-etched single crystal silicon wafer substrate was irradiated with light having a wavelength band of 400-800 nm using a UV spectrophotometer was measured.
  • the alkali compound according to the present invention Polysaccharides; Fatty acids, metal salts thereof or mixtures thereof; And when the texture was etched using the texture etching solution composition of Examples 1 to 17 containing the optimum amount of water was excellent in the uniformity of the fine pyramid formed on the surface of the single crystal silicon wafer and the light reflectance was able to increase the light efficiency .
  • 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 10,
  • Figure 2 is a SEM photograph showing the surface of the texture etched crystalline silicon wafer. Through this, it can be seen that the fine pyramid is formed over the entire surface of the wafer so that the quality variation is small and the texture uniformity is improved.
  • Comparative Example 1 which does not include polysaccharides, the etching proceeds rapidly, so that the size of the pyramid is not only large, but also a large number of portions where the pyramid is not formed. Some parts were not present.
  • Comparative Example 3 containing an excessive amount of polysaccharide and Comparative Example 4 containing an excess of fatty acid or metal salt thereof, the etching rate was too slow to increase the reflectance.
  • the texture etching solution composition of Comparative Example 5 due to the low temperature of the isopropyl alcohol (IPA) due to the temperature gradient generated by the continuous input of the texture during the texture failure and cost more,
  • the texture etchant composition showed significantly inferior characteristics in comparison with Examples in terms of texture uniformity and light reflectance.
  • the texture etching solution compositions of Comparative Examples 7 and 8 exhibited a change with time in the etching solution composition itself when heated to the texture process temperature.

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Abstract

The present invention relates to a texture etching solution composition and a texture etching method for a crystalline silicon wafer, and more specifically, to a texture etching method and a composition for a texture etching solution for a crystalline silicon wafer, comprising an optimum content of: an alkali compound; a polysaccharide; a fatty acid, and a metal salt thereof or a mixture of same; and the remainder, water, thereby enhancing the uniformity of a texture having a fine pyramid structure on the surface of the crystalline silicon wafer which maximizes solar light absorption, and reduces light reflectivity for increasing luminous efficiency.

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 표면을 미세 피라미드 구조로 균일하게 형성하여 광효율을 높일 수 있는 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물 및 텍스쳐 에칭방법에 관한 것이다.The present invention relates to a texture etching liquid composition and a texture etching method of a crystalline silicon wafer capable of uniformly forming a crystalline silicon wafer surface in a fine pyramid structure to increase light efficiency.
최근 들어 급속하게 보급되고 있는 태양전지는 차세대 에너지원으로서 클린 에너지인 태양 에너지를 직접 전기로 변환하는 전자 소자로서, 실리콘에 붕소를 첨가한 P형 실리콘 반도체를 기본으로 하여 그 표면에 인을 확산시켜 N형 실리콘 반도체층을 형성시킨 PN 접합 반도체 기판으로 구성되어 있다.Solar cells, which are rapidly spreading in recent years, are electronic devices that directly convert solar energy, which is clean energy, into electricity as a next-generation energy source, and diffuse phosphorus on its surface based on P-type silicon semiconductors containing boron in silicon. It consists of the PN junction semiconductor substrate in which the N type silicon semiconductor layer was formed.
PN 접합에 의해 전계가 형성된 기판에 태양광과 같은 빛을 조사할 경우 반도체 내의 전자(-)와 정공(+)이 여기되어 반도체 내부를 자유로이 이동하는 상태가 되며, 이러한 PN 접합에 의해 생긴 전계에 들어오게 되면 전자(-)는 N형 반도체에, 정공(+)은 P형 반도체에 이르게 된다. P형 반도체와 N형 반도체 표면에 전극을 형성하여 전자를 외부회로로 흐르게 하면 전류가 발생하게 되는데, 이와 같은 원리로 태양 에너지가 전기 에너지로 변환된다. 따라서 태양 에너지의 변환 효율을 높이기 위해서 PN 접합 반도체 기판의 단위 면적당 전기적 출력을 극대화시켜야 하며, 이를 위해서 반사율은 낮게 하고 광 흡수량은 최대화시켜야 한다. 이러한 점을 고려하여 PN 접합 반도체 기판을 구성하는 태양전지용 실리콘 웨이퍼의 표면을 미세 피라미드 구조로 형성시키고 반사 방지막을 처리하고 있다. 미세 피라미드 구조로 텍스쳐링된 실리콘 웨이퍼의 표면은 넓은 파장대를 갖는 입사광의 반사율을 낮춰 기 흡수된 광의 강도를 증가시킴으로써 태양전지의 성능, 즉 효율을 높일 수 있게 된다.When light such as sunlight is irradiated onto a substrate on which an electric field is formed by a PN junction, electrons (-) and holes (+) in the semiconductor are excited to move freely inside the semiconductor, and the electric field generated by the PN junction Upon entering, electrons (-) reach the N-type semiconductor and holes (+) reach the P-type semiconductor. When electrodes are formed on the surfaces of the P-type semiconductor and the N-type semiconductor to flow electrons to an external circuit, current is generated. Solar energy is converted into electrical energy based on the same principle. Therefore, in order to increase the conversion efficiency of solar energy, the electrical output per unit area of the PN junction semiconductor substrate should be maximized. For this purpose, the reflectance should be low and the light absorption amount should be maximized. In view of this point, the surface of the solar cell silicon wafer constituting the PN junction semiconductor substrate is formed into a fine pyramid structure and the antireflection film is treated. The surface of the silicon wafer textured with the fine pyramid structure increases the intensity of the light absorbed by lowering the reflectance of incident light having a wide wavelength band, thereby improving the performance of the solar cell.
실리콘 웨이퍼 표면을 미세 피라미드 구조로 텍스쳐하는 방법으로, 미국특허 제4,137,123호에는 0-75부피%의 에틸렌글리콜, 0.05-50중량%의 수산화칼륨 및 잔량의 물을 포함하는 이방성 에칭액에 0.5-10중량%의 실리콘이 용해된 실리콘 텍스쳐 에칭액이 개시되어 있다. 그러나, 이 에칭액은 피라미드 형성 불량을 일으켜 광 반사율을 증가시키고 효율의 저하를 초래할 수 있다.As a method of texturing a silicon wafer surface with a fine pyramid structure, U.S. Patent No. 4,137,123 discloses 0.5-10 weight in an anisotropic etching solution containing 0-75% by volume of ethylene glycol, 0.05-50% by weight of potassium hydroxide and the remaining amount of water. A silicon texture etching solution in which% silicon is dissolved is disclosed. However, this etchant can cause pyramid formation defects to increase the light reflectance and cause a decrease in efficiency.
또한, 유럽특허 제0477424호에는 에틸렌글리콜, 수산화칼륨 및 잔량의 물에 실리콘을 용해시킨 텍스쳐 에칭액에 산소를 공급시키는, 즉 에어레이팅 공정을 수행하는 텍스쳐 에칭 방법이 개시되어 있다. 그러나, 이 에칭 방법은 피라미드 형성 불량을 일으켜 광 반사율 증가와 효율의 저하를 초래할 뿐만 아니라 별도의 에어레이팅 장비의 설치를 필요로 한다는 단점이 있다.In addition, European Patent No. 0477424 discloses a texture etching method of supplying oxygen to a texture etching solution in which silicon is dissolved in ethylene glycol, potassium hydroxide and residual water, that is, performing an air rating process. However, this etching method has a disadvantage in that it causes poor pyramid formation, which leads to an increase in light reflectivity and a decrease in efficiency, and requires the installation of a separate air rating equipment.
또한, 한국등록특허 제0180621호에는 수산화칼륨 용액 0.5-5%, 이소프로필알코올 3-20부피%, 탈이온수 75-96.5부피%의 비율로 혼합된 텍스쳐 에칭 용액이 개시되어 있고, 미국특허 제6,451,218호에는 알칼리 화합물, 이소프로필알코올, 수용성 알카리성 에틸렌글리콜 및 물을 포함하는 텍스쳐 에칭 용액이 개시되어 있다. 그러나, 이들 에칭 용액은 비점이 낮은 이소프로필알코올을 포함하고 있어 텍스쳐 공정 중 이를 추가 투입해야 하므로 생산성 및 비용 면에서 경제적이지 못하며, 추가 투입된 이소프로필알코올로 인해 에칭액의 온도 구배가 발생하여 실리콘 웨이퍼 표면의 위치별 텍스쳐 품질 편차가 커져 균일성이 떨어질 수 있다.In addition, Korean Patent No. 0180621 discloses a texture etching solution mixed at a ratio of 0.5-5% potassium hydroxide solution, 3-20% by volume of isopropyl alcohol, and 75-96.5% by volume of deionized water, US Patent No. 6,451,218 No. discloses a texture etching solution comprising an alkali compound, isopropyl alcohol, a water soluble alkaline ethylene glycol and water. However, since these etching solutions contain isopropyl alcohol having a low boiling point and need to be added during the texturing process, it is not economical in terms of productivity and cost, and the addition of isopropyl alcohol causes a temperature gradient of the etching solution, resulting in the surface of the silicon wafer. The texture quality variation of each position may increase, resulting in poor uniformity.
본 발명은 결정성 실리콘 웨이퍼의 표면에 미세 피라미드 구조의 텍스쳐를 형성함에 있어서 위치별 텍스쳐의 균일성을 향상시켜 광 효율을 높일 수 있는 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물을 제공하는 것을 목적으로 한다.An object of the present invention is to provide a texture etching liquid composition of a crystalline silicon wafer that can improve the light efficiency by improving the uniformity of the texture by position in forming a texture of the fine pyramid structure on the surface of the crystalline silicon wafer.
또한, 본 발명은 에칭 공정 중 별도의 에칭액 성분의 투입과 에어레이팅 공정의 적용이 필요 없는 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물을 제공하는 것을 목적으로 한다.In addition, an object of the present invention is to provide a texture etching liquid composition of a crystalline silicon wafer that does not require the addition of an additional etching liquid component and the application of an air rating process during the etching process.
또한, 본 발명은 상기 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물을 이용한 텍스쳐 에칭방법을 제공하는 것을 다른 목적으로 한다.Another object of the present invention is to provide a texture etching method using the texture etching liquid composition of the crystalline silicon wafer.
1. 알칼리 화합물 0.1 내지 20중량%; 다당류 10-9 내지 10중량%; 지방산, 이의 금속염 또는 이들의 혼합물 10-9 내지 10중량%; 및 잔량의 물을 포함하는 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물.1. 0.1-20% by weight of alkali compound; Polysaccharides 10 -9 to 10% by weight; 10 -9 to 10 weight percent of fatty acids, metal salts thereof, or mixtures thereof; And a residual amount of water.
2. 위 1에 있어서, 알칼리 화합물은 수산화칼륨, 수산화나트륨, 수산화암모늄, 테트라히드록시메틸암모늄 및 테트라히드록시에틸암모늄으로 이루어진 군으로부터 선택되는 1종 이상인 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물.2. The composition according to the above 1, wherein the alkali compound is at least one selected from the group consisting of potassium hydroxide, sodium hydroxide, ammonium hydroxide, tetrahydroxymethylammonium and tetrahydroxyethylammonium.
3. 위 1에 있어서, 다당류는 글루칸계 화합물, 프룩탄계 화합물, 만난계 화합물, 갈락탄계 화합물 및 이들의 금속염으로 이루어진 군으로부터 선택된 1종 이상인 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물.3. The method according to the above 1, wherein the polysaccharide is at least one selected from the group consisting of glucan-based compounds, fructan-based compounds, mannan-based compounds, galactan-based compounds and metal salts of the texture etching liquid composition of the crystalline silicon wafer.
4. 위 3에 있어서, 다당류는 셀룰로오스, 디메틸아미노에틸셀룰로오스, 디에틸아미노에틸셀룰로오스, 에틸히드록시에틸셀룰로오스, 메틸히드록시에틸셀룰로오스, 4-아미노벤질셀룰로오스, 트리에틸아미노에틸셀룰로오스, 시아노에틸셀룰로오스, 에틸셀룰로오스, 메틸셀룰로오스, 카르복시메틸셀룰로오스, 카르복시에틸셀룰로오스, 히드록시에틸셀룰로오스, 히드록시프로필셀룰로오스, 알긴산, 아밀로오스, 아밀로펙틴, 펙틴, 스타치, 덱스트린, α-시클로덱스트린, β-시클로덱스트린, γ-시클로덱스트린, 히드록시프로필-β-시클로덱스트린, 메틸-β-시클로덱스트린, 덱스트란, 덱스트란설페이트나트륨, 사포닌, 글리코겐, 자이모산, 렌티난, 시조피난 및 이들의 금속염으로 이루어진 군으로부터 선택된 1종 이상의 글루칸계 화합물인 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물.4. In the above 3, the polysaccharide is cellulose, dimethylaminoethyl cellulose, diethylaminoethyl cellulose, ethyl hydroxyethyl cellulose, methyl hydroxyethyl cellulose, 4-aminobenzyl cellulose, triethylaminoethyl cellulose, cyanoethyl cellulose , Ethyl cellulose, methyl cellulose, carboxymethyl cellulose, carboxyethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, alginic acid, amylose, amylopectin, pectin, starch, dextrin, α-cyclodextrin, β-cyclodextrin, γ- 1 type selected from the group consisting of cyclodextrin, hydroxypropyl-β-cyclodextrin, methyl-β-cyclodextrin, dextran, dextransulfate sodium, saponin, glycogen, zymoic acid, lentinan, sizopinean and metal salts thereof Crystalline silicone web which is the above glucan type compound Texture etching liquid composition of the buffer.
5. 위 3에 있어서, 다당류는 평균 분자량이 5,000 내지 1,000,000인 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물.5. In the above 3, the polysaccharide has an average molecular weight of 5,000 to 1,000,000 texture etching liquid composition of a crystalline silicon wafer.
6. 위 1에 있어서, 지방산은 아세트산, 프로피온산, 부틸산, 발레르산, 에난틱산, 카프릴산, 펠라곤산, 카프릭산, 라우르산, 미리스트산, 팔미트산, 스테아르산, 아라키드산, 베헨산, 리그노세린산, 세로트산, 에이코사펜타엔산, 도코사헥사엔산, 리놀레산, α-리놀렌산, γ-리놀렌산, 디호모-γ-리놀렌산, 아라키돈산, 올레산, 엘라이드산, 에루스산 및 네르본산으로 이루어진 군으로부터 선택된 1종 이상인 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물.6. In the above 1, the fatty acid is acetic acid, propionic acid, butyric acid, valeric acid, enantiic acid, caprylic acid, pelagonic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachid Acid, behenic acid, lignocerinic acid, sertoic acid, eicosapentaenoic acid, docosahexaenoic acid, linoleic acid, α-linolenic acid, γ-linolenic acid, dihomo-γ-linolenic acid, arachidonic acid, oleic acid, elideic acid The texture etching solution composition of at least one crystalline silicon wafer selected from the group consisting of, erucic acid and nerbonic acid.
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 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 , Texture etching liquid composition of crystalline silicon wafer further comprising at least one fluorine-based surfactant selected from the group consisting of perfluoroalkyl carboxybetaine, perfluoroalkyl sulfobetaine, fluorinated alkyl polyoxyethylene and perfluoroalkyl polyoxyethylene .
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 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 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 실리콘 웨이퍼의 텍스쳐 에칭방법.9. Texture etching method of the crystalline silicon wafer comprising the step of depositing, spraying or depositing and spraying the crystalline silicon wafer with the texture etching liquid composition of any one of the above 1 to 8.
10. 위 9에 있어서, 침적, 분무 또는 침적 및 분무는 50 내지 100℃의 온도에서 30초 내지 60분 동안 수행되는 결정성 실리콘 웨이퍼의 텍스쳐 에칭방법.10. The method of 9 above, the deposition, spraying or deposition and spraying is a texture etching method of a crystalline silicon wafer is carried out for 30 seconds to 60 minutes at a temperature of 50 to 100 ℃.
본 발명의 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물 및 텍스쳐 에칭방법에 따르면 결정성 실리콘 웨이퍼 표면에 미세 피라미드 구조의 텍스쳐를 균일하게 형성하여 태양광의 흡수량을 극대화시키고 광 반사율을 낮춰 광효율을 높일 수 있다.According to the texture etching liquid composition and the texture etching method of the crystalline silicon wafer of the present invention, the texture of the fine pyramid structure is uniformly formed on the surface of the crystalline silicon wafer to maximize the absorption of solar light and lower the light reflectance to increase the light efficiency.
또한, 본 발명은 텍스쳐 공정 중 별도의 에칭액 성분을 투입할 필요가 없고 에어레이팅 장비도 도입할 필요가 없어 품질과 생산성을 향상시키는 동시에 공정 비용 면에서도 이점이 있다.In addition, the present invention does not need to add a separate etching liquid component during the texturing process and does not need to introduce an air rating equipment, thereby improving the quality and productivity, and also has an advantage in terms of process cost.
도 1은 본 발명의 실시예 10의 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물로 텍스쳐 에칭된 단결정 실리콘 웨이퍼의 표면을 나타낸 3D 광학현미경 사진이며,1 is a 3D optical micrograph showing the surface of a single crystal silicon wafer texture-etched with the texture etching liquid composition of the crystalline silicon wafer of Example 10 of the present invention,
도 2는 본 발명의 실시예 10의 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 10 of the present invention.
본 발명은 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물 및 이를 이용한 결정성 실리콘 웨이퍼의 텍스쳐 에칭방법에 관한 것이다.The present invention relates to a texture etching liquid composition of a crystalline silicon wafer and a method of etching the texture of a crystalline silicon wafer using the same.
이하 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.
본 발명의 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물은 알칼리 화합물; 다당류; 지방산, 이의 금속염 또는 이들의 혼합물; 및 잔량의 물을 포함하는 것을 특징으로 한다.The texture etching solution composition of the crystalline silicon wafer of the present invention is an alkali compound; Polysaccharides; Fatty acids, metal salts thereof or mixtures thereof; And a residual amount of water.
보다 상세하게, 알칼리 화합물 0.1 내지 20중량%; 다당류 10-9 내지 10중량%; 지방산, 이의 금속염 또는 이들의 혼합물 10-9 내지 10중량%; 및 잔량의 물을 포함한다.More specifically, the alkali compound 0.1 to 20% by weight; Polysaccharides 10 -9 to 10% by weight; 10 -9 to 10 weight percent of fatty acids, metal salts thereof, or mixtures thereof; And residual amount of water.
알칼리 화합물은 결정성 실리콘 웨이퍼의 표면을 에칭하는 성분으로서 그 종류는 특별히 한정되지 않는다. 예컨대, 수산화칼륨, 수산화나트륨, 수산화암모늄, 테트라히드록시메틸암모늄, 테트라히드록시에틸암모늄 등을 들 수 있으며, 이 중에서 수산화칼륨, 수산화나트륨이 바람직하다. 이들은 단독 또는 2종 이상 혼합하여 사용할 수 있다.An alkali compound is a component which etches the surface of a crystalline silicon wafer, The kind is not specifically limited. For example, potassium hydroxide, sodium hydroxide, ammonium hydroxide, tetrahydroxymethylammonium, tetrahydroxyethylammonium, etc. are mentioned, Among these, potassium hydroxide and sodium hydroxide are preferable. These can be used individually or in mixture of 2 or more types.
알칼리 화합물은 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물 총 100중량%에 대하여 0.1 내지 20중량%로 포함되는 것이 바람직하고, 보다 바람직하게는 1 내지 5중량%인 것이 좋다. 함량이 상기 범위에 해당되는 경우 실리콘 웨이퍼 표면을 에칭할 수 있게 된다.The alkali compound is preferably included in an amount of 0.1 to 20% by weight, and more preferably 1 to 5% by weight, based on 100% by weight of the total amount of the texture etching solution composition of the crystalline silicon wafer. When the content falls within the above range, the silicon wafer surface can be etched.
본 발명에서는 특히, 다당류를 최적의 함량으로 포함하는데 특징이 있다.In particular, the present invention is characterized by including the polysaccharide in an optimum content.
다당류(polysaccharide)는 단당류 2개 이상이 글리코시드 결합하여 큰 분자를 만들고 있는 당류로서, 알칼리 화합물에 의한 과에칭과 에칭 가속화를 방지함으로써 균일한 미세 피라미드를 형성하고 외관을 개선하는 동시에 에칭에 의해 생성된 수소 버블을 실리콘 웨이퍼 표면으로부터 빨리 떨어뜨려 버블 스틱 현상을 방지하는 성분이다.Polysaccharides are saccharides in which two or more monosaccharides are glycosidic bonds to form large molecules, and are formed by etching while forming a uniform fine pyramid and improving appearance by preventing overetching and accelerated etching by alkaline compounds. It is a component that prevents the bubble stick phenomenon by quickly dropping the hydrogen bubbles from the silicon wafer surface.
다당류로는 글루칸계(glucan) 화합물, 프룩탄계(fructan) 화합물, 만난계(mannan) 화합물, 갈락탄계(galactan) 화합물 또는 이들의 금속염 등을 들 수 있으며, 이 중에서 글루칸계 화합물과 이의 금속염(예컨대, 알칼리 금속염)이 바람직하다. 이들은 단독 또는 2종 이상 혼합하여 사용할 수 있다.Examples of the polysaccharides include glucan compounds, fructan compounds, mannan compounds, galactan compounds, or metal salts thereof, among which glucan compounds and metal salts thereof (e.g., Alkali metal salts) are preferred. These can be used individually or in mixture of 2 or more types.
글루칸계 화합물로는 셀룰로오스, 디메틸아미노에틸셀룰로오스, 디에틸아미노에틸셀룰로오스, 에틸히드록시에틸셀룰로오스, 메틸히드록시에틸셀룰로오스, 4-아미노벤질셀룰로오스, 트리에틸아미노에틸셀룰로오스, 시아노에틸셀룰로오스, 에틸셀룰로오스, 메틸셀룰로오스, 카르복시메틸셀룰로오스, 카르복시에틸셀룰로오스, 히드록시에틸셀룰로오스, 히드록시프로필셀룰로오스, 알긴산, 아밀로오스, 아밀로펙틴, 펙틴, 스타치, 덱스트린, α-시클로덱스트린, β-시클로덱스트린, γ-시클로덱스트린, 히드록시프로필-β-시클로덱스트린, 메틸-β-시클로덱스트린, 덱스트란, 덱스트란설페이트나트륨, 사포닌, 글리코겐, 자이모산, 렌티난, 시조피난 또는 이들의 금속염 등을 들 수 있다.Examples of the glucan compound include cellulose, dimethylaminoethyl cellulose, diethylaminoethyl cellulose, ethyl hydroxyethyl cellulose, methyl hydroxyethyl cellulose, 4-aminobenzyl cellulose, triethylaminoethyl cellulose, cyanoethyl cellulose, ethyl cellulose, Methyl cellulose, carboxymethyl cellulose, carboxyethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, alginic acid, amylose, amylopectin, pectin, starch, dextrin, α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin, hydrate Oxypropyl-β-cyclodextrin, methyl-β-cyclodextrin, dextran, dextransulfate sodium, saponin, glycogen, zymoic acid, lentinan, sizopinean or metal salts thereof.
다당류는 평균 분자량이 5,000 내지 1,000,000인 것일 수 있으며, 바람직하게 50,000 내지 200,000인 것이 좋다.The polysaccharide may have an average molecular weight of 5,000 to 1,000,000, preferably 50,000 to 200,000.
다당류는 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물 총 100중량%에 대하여 10-9 내지 10중량%로 포함될 수 있으며, 바람직하게는 10-6 내지 1중량%인 것이 좋다. 함량이 상기 범위에 해당되는 경우 과에칭과 에칭 가속화를 효과적으로 방지할 수 있다. 함량이 10중량% 초과인 경우 알칼리 화합물에 의한 에칭 속도를 급격하게 저하시켜 원하는 미세 피라미드를 형성하기 어렵다.The polysaccharide may be included in an amount of 10 -9 to 10% by weight, preferably 10 -6 to 1% by weight, based on 100% by weight of the texture etching solution composition of the crystalline silicon wafer. If the content falls within the above range, it is possible to effectively prevent over-etching and etching acceleration. If the content is more than 10% by weight, it is difficult to form the desired fine pyramid by drastically lowering the etching rate by the alkali compound.
본 발명은 다당류와 함께 지방산, 이의 금속염 또는 이들의 혼합물을 최적의 함량으로 포함하는데 특징이 있다.The present invention is characterized in that it contains an optimal amount of a fatty acid, a metal salt thereof, or a mixture thereof together with a polysaccharide.
지방산 및 이의 금속염은 다당류와 함께 사용되어 알칼리 화합물에 의한 과에칭을 더욱 방지함으로써 균일한 미세 피라미드를 형성하고 동시에 에칭에 의해 생성된 수소 버블을 실리콘 웨이퍼 표면으로부터 더욱 빨리 떨어뜨려 버블 스틱 현상이 발생하는 것도 방지하는 성분이다.Fatty acids and their metal salts are used together with polysaccharides to further prevent over-etching by alkaline compounds to form uniform fine pyramids and at the same time drop hydrogen bubbles generated by etching more quickly from the surface of the silicon wafer, resulting in a bubble stick phenomenon. It is also a component that prevents.
지방산은 카르복시기를 함유하는 탄화수소 사슬의 카르복시산으로서, 구체적으로 아세트산, 프로피온산, 부틸산, 발레르산, 에난틱산, 카프릴산, 펠라곤산, 카프릭산, 라우르산, 미리스트산, 팔미트산, 스테아르산, 아라키드산, 베헨산, 리그노세린산, 세로트산, 에이코사펜타엔산, 도코사헥사엔산, 리놀레산, α-리놀렌산, γ-리놀렌산, 디호모-γ-리놀렌산, 아라키돈산, 올레산, 엘라이드산, 에루스산, 네르본산 등을 들 수 있다. 또한, 지방산의 금속염은 위 지방산과 NaOH 또는 KOH와 같은 금속염의 에스테르 반응물을 들 수 있다. 이들은 단독 또는 2종 이상 혼합하여 사용할 수 있다.Fatty acids are carboxylic acids of hydrocarbon chains containing carboxyl groups, specifically acetic acid, propionic acid, butyric acid, valeric acid, enantiic acid, caprylic acid, pelagonic acid, capric acid, lauric acid, myristic acid, palmitic acid, Stearic acid, arachidic acid, behenic acid, lignocerinic acid, serotic acid, eicosapentaenoic acid, docosahexaenoic acid, linoleic acid, α-linolenic acid, γ-linolenic acid, dihomo-γ-linolenic acid, arachidonic acid, Oleic acid, elideic acid, erucic acid, nerbonic acid, and the like. In addition, the metal salt of a fatty acid may include an ester reactant of the above fatty acid with a metal salt such as NaOH or KOH. These can be used individually or in mixture of 2 or more types.
지방산, 이의 금속염 및 이들의 혼합물은 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물 총 100중량%에 대하여 10-9 내지 10중량%로 포함될 수 있으며, 바람직하게는 10-6 내지 1중량%인 것이 좋다. 함량이 상기 범위에 해당되는 경우 과에칭을 효과적으로 방지할 수 있다.Fatty acids, metal salts thereof, and mixtures thereof may be included in amounts of 10 -9 to 10% by weight, preferably 10 -6 to 1% by weight, based on 100% by weight of the total amount of the texture etching solution composition of the crystalline silicon wafer. When the content falls within the above range, over-etching can be effectively prevented.
본 발명의 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물은 불소계 계면활성제를 더 포함할 수 있다.The texture etching solution composition of the crystalline silicon wafer of the present invention may further include a fluorine-based surfactant.
불소계 계면활성제는 에칭액 조성물의 표면장력을 낮추어 결정성 실리콘 웨이퍼 표면의 젖음성 개선을 더욱 촉진시켜 알칼리 화합물에 의한 과에칭을 방지한다.The fluorine-based surfactant lowers the surface tension of the etching solution composition to further promote the wettability improvement 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.Although the kind of fluorine-type surfactant is not specifically limited, For example, Anionic surfactant, such as a perfluoroalkyl carboxylate, a perfluoroalkyl sulfonate, a perfluoroalkyl sulfate, a 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 10-9 내지 10중량%로 포함될 수 있으며, 바람직하게는 10-6 내지 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 10 -9 to 10% by weight, preferably 10 -6 to 1% by weight, based on 100% by weight of the texture etching solution composition of the crystalline silicon wafer. When the content falls within the above range, the wettability of the silicon wafer surface can be effectively improved.
또한, 본 발명의 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물은 실리카 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 compound.
실리카 화합물은 결정성 실리콘 웨이퍼 표면에 물리적으로 흡착하여 일종의 마스크 역할을 함으로써 결정성 실리콘 웨이퍼 표면을 미세 피라미드 형상으로 용이하게 만들어 주는 성분이다.The silica compound is a component that makes the surface of the crystalline silicon wafer easy to form a fine pyramid by physically adsorbing the surface of the crystalline silicon wafer and acting as a kind of mask.
실리카 화합물로는 분말형, 콜로이드 용액형 또는 액상 규산금속 화합물 등을 들 수 있다. 구체적으로, 미분말 실리카; Na2O로 안정화시킨 콜로이드 실리카 용액; K2O로 안정화시킨 콜로이드 실리카 용액; 산성액으로 안정화시킨 콜로이드 실리카 용액; NH3로 안정화시킨 콜로이드 실리카 용액; 에틸알코올, 프로필알코올, 에틸렌글리콜, 메틸에틸케톤 및 메틸이소부틸케톤으로 이루어진 군으로부터 선택된 1종 이상의 유기용매로 안정화시킨 콜로이드 실리카 용액; 액상 규산나트륨; 액상 규산칼륨; 액상 규산리튬 등을 들 수 있으며, 이들은 단독 또는 2종 이상 혼합하여 사용할 수 있다.Examples of the silica compound include powder, colloidal solution, or liquid metal silicate compounds. Specifically, fine powder silica; Colloidal silica solution stabilized with Na 2 O; Colloidal silica solution stabilized with K 2 O; Colloidal silica solution stabilized with acid solution; Colloidal silica solution stabilized with NH 3 ; Colloidal silica solution stabilized with at least one organic solvent selected from the group consisting of ethyl alcohol, propyl alcohol, ethylene glycol, methyl ethyl ketone and methyl isobutyl ketone; Liquid sodium silicate; Liquid potassium silicate; Liquid lithium silicate etc. can be mentioned, These can be used individually or in mixture of 2 or more types.
실리카 화합물은 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물 총 100중량%에 대하여 10-9 내지 10중량%로 포함될 수 있고, 바람직하게는 10-6 내지 1중량%인 것이 좋다. 함량이 상기 범위에 해당되는 경우 결정성 실리콘 웨이퍼 표면에 미세 피라미드를 용이하게 형성할 수 있다.The silica compound may be included in an amount of 10 -9 to 10% by weight, preferably 10 -6 to 1% by weight, based on 100% by weight of the total amount of the texture etching solution composition of the crystalline silicon wafer. If the content falls within the above range, it is possible to easily form a fine pyramid on the surface of the crystalline silicon wafer.
물은 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물 총 100중량%에 잔량으로 포함될 수 있다.Water may be included in the remaining amount in the total 100% by weight of the texture etching solution composition of the crystalline silicon wafer.
물의 종류는 특별히 한정되지 않으나, 탈이온 증류수인 것이 바람직하고, 보다 바람직하게는 반도체 공정용 탈이온 증류수로서 비저항값이 18㏁/㎝ 이상인 것이 좋다.Although the kind of water is not specifically limited, It is preferable that it is deionized distilled water, More preferably, it is preferable that the specific resistance value is 18 kW / cm or more as deionized distilled water for a semiconductor process.
상기와 같은 성분을 포함하여 구성되는 본 발명의 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물은, 특히 다당류와 함께 지방산, 이의 금속염 또는 이들의 혼합물을 최적의 함량으로 포함함으로써 결정성 실리콘 웨이퍼 표면을 미세 피라미드 구조의 텍스쳐로 균일하게 형성하여 태양광의 흡수량을 극대화시키고 광 반사율을 낮춰 광효율을 높일 수 있다. 또한, 텍스쳐 에칭 공정 중 별도의 에칭액 성분을 투입할 필요가 없고 에어레이팅 장비도 도입할 필요가 없어 생산성과 비용 면에서 이점이 있다.The texture etching liquid composition of the crystalline silicon wafer of the present invention comprising the above components comprises a micropyramidal structure on the surface of the crystalline silicon wafer, in particular by containing an optimal amount of fatty acids, metal salts thereof or mixtures thereof with polysaccharides. Formed uniformly with the texture of maximizing the absorption of sunlight and lowering the light reflectance can increase the light efficiency. In addition, there is no need to add a separate etchant component during the texture etching process, and there is no need to introduce an air rating equipment, which is advantageous in terms of productivity and cost.
본 발명의 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물은 통상의 에칭 공정, 예컨대 딥방식, 분무방식 및 매엽방식의 에칭 공정에 모두 적용 가능하다.The texture etching liquid composition of the crystalline silicon wafer of the present invention can be applied to all conventional etching processes, such as dip, spray and single wafer etching processes.
본 발명은 상기 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물을 이용한 결정성 실리콘 웨이퍼의 텍스쳐 에칭방법을 제공한다.The present invention provides a texture etching method of a crystalline silicon wafer using the texture etching liquid composition of the crystalline silicon wafer.
결정성 실리콘 웨이퍼의 텍스쳐 에칭방법은 본 발명의 결정성 실리콘웨이퍼의 텍스쳐 에칭액 조성물을 이용하여 결정성 실리콘 웨이퍼를 침적, 분무 또는 침적 및 분무하는 단계를 포함한다.The texture etching method of the crystalline silicon wafer includes depositing, spraying or depositing and spraying the crystalline silicon wafer using the texture etching liquid composition of the crystalline silicon wafer of the present invention.
침적과 분무의 횟수는 특별히 한정되지 않으며, 침적과 분무를 모두 수행하는 경우 그 순서도 한정되지 않는다.The number of depositions and sprays is not particularly limited, and the order of both deposition and spraying is not limited.
침적, 분무 또는 침적 및 분무하는 단계는 50 내지 100℃의 온도에서 30초 내지 60분 동안 수행될 수 있다.Deposition, spraying or depositing and spraying may be performed for 30 seconds to 60 minutes at a temperature of 50 to 100 ° C.
상기한 바와 같은 본 발명의 결정성 실리콘 웨이퍼의 텍스쳐 에칭방법은 산소를 공급시키는 별도의 에어레이팅 장비를 도입할 필요가 없어 초기 생산 및 공정 비용 면에서 경제적일 뿐만 아니라 간단한 공정으로도 균일한 미세 피라미드 구조의 형성을 가능하게 한다.As described above, the texture etching method of the crystalline silicon wafer of the present invention does not need to introduce a separate air-rating apparatus for supplying oxygen, so it is economical in terms of initial production and processing costs, and is uniform even in a simple process. It allows the formation of a structure.
이하, 본 발명의 이해를 돕기 위하여 바람직한 실시예를 제시하나, 이들 실시예는 본 발명을 예시하는 것일 뿐 첨부된 특허청구범위를 제한하는 것이 아니며, 본 발명의 범주 및 기술사상 범위 내에서 실시예에 대한 다양한 변경 및 수정이 가능함은 당업자에게 있어서 명백한 것이며, 이러한 변형 및 수정이 첨부된 특허청구범위에 속하는 것도 당연한 것이다.Hereinafter, preferred examples are provided to aid the understanding of the present invention, but these examples are merely illustrative of the present invention and are not intended to limit the scope of the appended claims, which are within the scope and spirit of the present invention. It is apparent to those skilled in the art that various changes and modifications can be made to the present invention, and such modifications and changes belong to the appended claims.
실시예Example
실시예 1Example 1
수산화칼륨(KOH) 4중량%, 디메틸아미노에틸셀룰로오스(DMAEC) 0.005중량%, 카프릴산(OA) 0.005중량% 및 잔량의 탈이온 증류수를 혼합하여 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물을 제조하였다.The texture etching solution composition of the crystalline silicon wafer was prepared by mixing 4% by weight of potassium hydroxide (KOH), 0.005% by weight of dimethylaminoethyl cellulose (DMAEC), 0.005% by weight of caprylic acid (OA), and residual deionized distilled water.
실시예 2-17, 비교예 1-4Example 2-17, Comparative Example 1-4
상기 실시예 1과 동일하게 실시하되, 하기 표 1에서와 같은 성분 및 함량을 사용하였다. 여기서, 함량은 중량%를 나타낸다.The same procedure as in Example 1, except that the same ingredients and contents as in Table 1 were used. Here, the content represents weight percent.
표 1
구분 알칼리 화합물 다당류 지방산/염 계면활성제 실리카 화합물
종류 함량 종류 함량 종류 함량 종류 함량 종류 함량
실시예1 KOH 4 DMAEC 0.005 OA 0.005 - - - -
실시예2 KOH 4 EHEC 0.005 DA 0.005 - - - -
실시예3 KOH 4 MC 0.005 LA 0.005 - - - -
실시예4 KOH 4 HEC 0.005 LA 0.005 - - - -
실시예5 KOH 2.5 CMC 0.02 LA 0.02 - - - -
실시예6 KOH 2 AA 0.02 LA 0.02 - - - -
실시예7 KOH 2 DSNa 0.01 LA 0.01 - - - -
실시예8 KOH 2 AP 0.005 LA 0.005 - - - -
실시예9 KOH 3 St 0.005 LA 0.005 - - - -
실시예10 KOH 2 CMCNa 0.02 LANa 0.02 - - - -
실시예11 KOH 2 AANa 0.02 DANa 0.02 - - - -
실시예12 KOH 2 CMCNa 0.02 LANa 0.02 PFAS 0.001
실시예13 KOH 2 AANa 0.02 DANa 0.02 PFAP 0.001 - -
실시예14 KOH 2 CMCNa 0.02 DANa 0.02 - - SCS 0.2
실시예15 KOH 2 AANa 0.02 LANa 0.02 - - SSS 0.1
실시예16 KOH 2 AANa 0.02 LANa 0.02 PFAS 0.001 SCS 0.2
실시예17 KOH 2 AANa 0.02 DANa 0.02 PFAP 0.001 SSS 0.1
비교예1 KOH 2 - - LANa 0.02 - - - -
비교예2 KOH 2 AANa 0.02 - - - - - -
비교예3 KOH 2 AANa 0.02 LANa 11 - - - -
비교예4 KOH 2 AANa 11 LANa 0.02 - - - -
KOH: 수산화칼륨DMAEC: 디메틸아미노에틸셀룰로오스EHEC: 에틸히드록시에틸셀룰로오스MC: 메틸셀룰로오스HEC: 히드록시에틸셀룰로오스CMC: 카르복시메틸셀룰로오스AA: 알긴산DSNa: 덱스트란설페이트나트륨AP: 아밀로펙틴St: 스타치CMCNa: 카르복시메틸셀룰로오스나트륨AANa: 알긴산나트륨OA: 카프릴산(옥탄산)DA: 카프릭산(데칸산)LA: 라우르산LANa: 라우르산나트륨 DANa: 카프릭산나트륨(데칸산나트륨) PFAS: 과불소화알킬 황산염PFAP: 과불소화알킬 인산염SCS: Na2O로 안정화시킨 콜로이드 실리카 용액SSS: 액상 규산나트륨
Table 1
division Alkali compounds Polysaccharides Fatty acid / salt Surfactants Silica compounds
Kinds content Kinds content Kinds content Kinds content Kinds content
Example 1 KOH 4 DMAEC 0.005 OA 0.005 - - - -
Example 2 KOH 4 EHEC 0.005 DA 0.005 - - - -
Example 3 KOH 4 MC 0.005 LA 0.005 - - - -
Example 4 KOH 4 HEC 0.005 LA 0.005 - - - -
Example 5 KOH 2.5 CMC 0.02 LA 0.02 - - - -
Example 6 KOH 2 AA 0.02 LA 0.02 - - - -
Example 7 KOH 2 DSNa 0.01 LA 0.01 - - - -
Example 8 KOH 2 AP 0.005 LA 0.005 - - - -
Example 9 KOH 3 St 0.005 LA 0.005 - - - -
Example 10 KOH 2 CMCNa 0.02 LANa 0.02 - - - -
Example 11 KOH 2 AANa 0.02 DANa 0.02 - - - -
Example 12 KOH 2 CMCNa 0.02 LANa 0.02 PFAS 0.001
Example 13 KOH 2 AANa 0.02 DANa 0.02 PFAP 0.001 - -
Example 14 KOH 2 CMCNa 0.02 DANa 0.02 - - SCS 0.2
Example 15 KOH 2 AANa 0.02 LANa 0.02 - - SSS 0.1
Example 16 KOH 2 AANa 0.02 LANa 0.02 PFAS 0.001 SCS 0.2
Example 17 KOH 2 AANa 0.02 DANa 0.02 PFAP 0.001 SSS 0.1
Comparative Example 1 KOH 2 - - LANa 0.02 - - - -
Comparative Example 2 KOH 2 AANa 0.02 - - - - - -
Comparative Example 3 KOH 2 AANa 0.02 LANa 11 - - - -
Comparative Example 4 KOH 2 AANa 11 LANa 0.02 - - - -
KOH: potassium hydroxide DMAEC: dimethylaminoethyl cellulose EHEC: ethyl hydroxyethyl cellulose MC: methyl cellulose HEC: hydroxyethyl cellulose CMC: carboxymethyl cellulose AA: alginic acid DSNa: dextran sulfate sodium AP: amylopectin St: starch CMCNa: Carboxymethylcellulose sodium AANa: sodium alginate OA: caprylic acid (octanoic acid) DA: capric acid (decanoic acid) LA: lauric acid LANa: sodium laurate DANa: sodium capric acid (sodium decanoate) PFAS: Alkyl perfluoride sulfate PFAP: Alkyl perfluoride phosphate SCS: Colloidal silica solution stabilized with Na 2 O SSS: Liquid sodium silicate
비교예 5Comparative Example 5
수산화칼륨(KOH) 1.5중량%, 이소프로필알코올(IPA) 5중량% 및 잔량의 탈이온 증류수를 혼합하여 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물을 제조하였다.A 1.5% by weight potassium hydroxide (KOH), 5% by weight isopropyl alcohol (IPA) and the remaining amount of deionized distilled water was mixed to prepare a texture etching solution composition of the crystalline silicon wafer.
비교예 6Comparative Example 6
상기 비교예 5와 동일하게 실시하되, 이소프로필알코올(IPA) 대신에 에틸렌글리콜(EG)을 사용하였다.In the same manner as in Comparative Example 5, ethylene glycol (EG) was used instead of isopropyl alcohol (IPA).
비교예 7Comparative Example 7
상기 비교예 5와 동일하게 실시하되, 이소프로필알코올(IPA) 대신에 메틸디글리콜(MDG)을 사용하였다.In the same manner as in Comparative Example 5, but instead of isopropyl alcohol (IPA) was used methyl diglycol (MDG).
비교예 8Comparative Example 8
상기 비교예 5와 동일하게 실시하되, 이소프로필알코올(IPA) 대신에 모노에틸아민(MEA)을 사용하였다.The same procedure as in Comparative Example 5 except that monoethylamine (MEA) was used instead of isopropyl alcohol (IPA).
시험예Test Example
상기 실시예 및 비교예에서 제조된 실리콘 웨이퍼의 텍스쳐 에칭액 조성물의 텍스쳐 에칭 효과를 하기 방법으로 평가하고, 그 결과를 하기 표 2에 나타내었다.The texture etching effect of the texture etching solution composition of the silicon wafers prepared in Examples and Comparative Examples was evaluated by the following method, and the results are shown in Table 2 below.
- 단결정 실리콘 웨이퍼 기판을 제조된 실리콘 웨이퍼의 텍스쳐 에칭액 조성물에 80℃의 온도로 20분 동안 침적시켰다.The single crystal silicon wafer substrate was immersed in the texture etching liquid composition of the prepared silicon wafer for 20 minutes at a temperature of 80 ° C.
(1) 텍스쳐 균일성(1) texture uniformity
텍스쳐 에칭된 단결정 실리콘 웨이퍼 기판 표면에 형성된 텍스쳐의 편차, 즉 균일성을 디지털 카메라, 3D 광학현미경 및 주사전자현미경(Scanning electron microscope, SEM)을 이용하여 육안으로 관찰하고, 하기 기준에 의거하여 평가하였다.Texture variation, that is, uniformity, formed on the surface of the etched single crystal silicon wafer substrate was visually observed using a digital camera, a 3D optical microscope, and a scanning electron microscope (SEM), and evaluated based on the following criteria. .
<평가기준><Evaluation Criteria>
◎: 웨이퍼 기판 전부에 피라미드 형성.(Double-circle): Pyramid formation in all the wafer substrates.
○: 웨이퍼 기판 일부에 피라미드 미형성(미형성 부분 5% 미만).(Circle): Pyramidal non-formation (less than 5% of unformed part) in a part of wafer substrate.
△: 웨이퍼 기판 일부에 피라미드 미형성(미형성 부분 5-50%).(Triangle | delta): Pyramid non-formation in 5 part of wafer substrates (5-50% of unformed part).
×: 웨이퍼 기판 대부분에 피라미드 미형성(미형성 부분 90% 이상).X: Pyramid unformed in most wafer substrates (90% or more of unformed parts).
(2) 피라미드 평균 크기(㎛)(2) Pyramid average size (㎛)
텍스쳐 에칭된 단결정 실리콘 웨이퍼 기판 표면에 형성된 미세 피라미드의 크기를 주사전자현미경(Scanning electron microscope, SEM)을 이용하여 측정하였다. 이때, 단위 면적에 형성된 미세 피라미드의 크기를 측정한 후 이들의 평균값으로 나타내었다.The size of the fine pyramid formed on the surface of the textured etched single crystal silicon wafer substrate was measured using a scanning electron microscope (SEM). At this time, the size of the fine pyramid formed in the unit area was measured and expressed as their average value.
(3) 평균 반사율(%)(3) Average reflectance (%)
텍스쳐 에칭된 단결정 실리콘 웨이퍼 기판 표면에 UV 분광광도계를 이용하여 400-800㎚의 파장대를 갖는 광을 조사하였을 때의 평균 반사율을 측정하였다.The average reflectance when the surface of the texture-etched single crystal silicon wafer substrate was irradiated with light having a wavelength band of 400-800 nm using a UV spectrophotometer was measured.
표 2
구분 텍스쳐 균일성 피라미드 평균 크기(㎛) 평균 반사율(%)
실시예1 ◎ 3 12.49
실시예2 ◎ 3 12.31
실시예3 ◎ 3 12.41
실시예4 ◎ 3 12.50
실시예5 ◎ 4 11.68
실시예6 ◎ 4 11.75
실시예7 ◎ 4 11.95
실시예8 ◎ 3 12.45
실시예9 ◎ 3 12.54
실시예10 ◎ 4 11.77
실시예11 ◎ 4 11.89
실시예12 ◎ 4 11.89
실시예13 ◎ 4 11.83
실시예14 ◎ 4 11.78
실시예15 ◎ 4 11.69
실시예16 ◎ 4 11.80
실시예17 ◎ 4 11.90
비교예1 △ 10 18.41
비교예2 ○ 5 12.98
비교예3 △ 5 16.21
비교예4 △ 5 22.56
비교예5 ○ 5 13.22
비교예6 × 10 21.13
비교예7 에칭액 변색
비교예8 에칭액 변색
TABLE 2
division Texture Uniformity Pyramid Average Size (μm) Average reflectance (%)
Example 1 ◎ 3 12.49
Example 2 ◎ 3 12.31
Example 3 ◎ 3 12.41
Example 4 ◎ 3 12.50
Example 5 ◎ 4 11.68
Example 6 ◎ 4 11.75
Example 7 ◎ 4 11.95
Example 8 ◎ 3 12.45
Example 9 ◎ 3 12.54
Example 10 ◎ 4 11.77
Example 11 ◎ 4 11.89
Example 12 ◎ 4 11.89
Example 13 ◎ 4 11.83
Example 14 ◎ 4 11.78
Example 15 ◎ 4 11.69
Example 16 ◎ 4 11.80
Example 17 ◎ 4 11.90
Comparative Example 1 △ 10 18.41
Comparative Example 2 ○ 5 12.98
Comparative Example 3 △ 5 16.21
Comparative Example 4 △ 5 22.56
Comparative Example 5 ○ 5 13.22
Comparative Example 6 × 10 21.13
Comparative Example 7 Etching Discoloration
Comparative Example 8 Etching Discoloration
위 표 2와 같이, 본 발명에 따라 알칼리 화합물; 다당류; 지방산, 이의 금속염 또는 이들의 혼합물; 및 물을 최적의 함량으로 포함하는 실시예 1 내지 17의 텍스쳐 에칭액 조성물을 이용하여 텍스쳐 에칭한 경우 단결정 실리콘 웨이퍼의 표면에 형성된 미세 피라미드의 균일성이 우수하고 광 반사율이 낮아 광 효율도 높일 수 있었다.As shown in Table 2, the alkali compound according to the present invention; Polysaccharides; Fatty acids, metal salts thereof or mixtures thereof; And when the texture was etched using the texture etching solution composition of Examples 1 to 17 containing the optimum amount of water was excellent in the uniformity of the fine pyramid formed on the surface of the single crystal silicon wafer and the light reflectance was able to increase the light efficiency .
도 1은 실시예 10의 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 10, Figure 2 is a SEM photograph showing the surface of the texture etched crystalline silicon wafer. Through this, it can be seen that the fine pyramid is formed over the entire surface of the wafer so that the quality variation is small and the texture uniformity is improved.
반면, 다당류를 포함하지 않는 비교예 1은 에칭이 빠르게 진행되어 피라미드의 크기가 클 뿐만 아니라 피라미드가 형성되지 않은 부분이 많이 존재하였고, 지방산 또는 이의 금속염을 포함하지 않는 비교예 2는 피라미드가 형성되지 않은 부분이 일부 존재하였다. 또한, 다당류를 과량 포함하는 비교예 3과 지방산 또는 이의 금속염을 과량 포함하는 비교예 4는 에칭 속도가 너무 느려져 반사율이 높아졌다. 또한, 비교예 5의 텍스쳐 에칭액 조성물은 이소프로필알코올(IPA)의 낮은 비점으로 인해 텍스쳐 공정 중 이를 지속적으로 투입함으로써 발생되는 온도 구배에 기인하여 텍스쳐 불량이 일어나고 비용도 더 발생하였고, 비교예 6의 텍스쳐 에칭액 조성물은 텍스쳐 균일성과 광 반사율 면에서 실시예에 비해 크게 뒤떨어진 특성을 나타내었다. 비교예 7 및 8의 텍스쳐 에칭액 조성물은 텍스쳐 공정 온도로의 승온 시 에칭액 조성물 자체에 경시 변화가 발생하였다.On the other hand, in Comparative Example 1, which does not include polysaccharides, the etching proceeds rapidly, so that the size of the pyramid is not only large, but also a large number of portions where the pyramid is not formed. Some parts were not present. In addition, in Comparative Example 3 containing an excessive amount of polysaccharide and Comparative Example 4 containing an excess of fatty acid or metal salt thereof, the etching rate was too slow to increase the reflectance. In addition, the texture etching solution composition of Comparative Example 5 due to the low temperature of the isopropyl alcohol (IPA) due to the temperature gradient generated by the continuous input of the texture during the texture failure and cost more, The texture etchant composition showed significantly inferior characteristics in comparison with Examples in terms of texture uniformity and light reflectance. The texture etching solution compositions of Comparative Examples 7 and 8 exhibited a change with time in the etching solution composition itself when heated to the texture process temperature.

Claims (10)

  1. 알칼리 화합물 0.1 내지 20중량%; 다당류 10-9 내지 10중량%; 지방산, 이의 금속염 또는 이들의 혼합물 10-9 내지 10중량%; 및 잔량의 물을 포함하는 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물.0.1-20% by weight of alkaline compound; Polysaccharides 10 -9 to 10% by weight; 10 -9 to 10 weight percent of fatty acids, metal salts thereof, or mixtures thereof; And a residual amount of water.
  2. 청구항 1에 있어서, 알칼리 화합물은 수산화칼륨, 수산화나트륨, 수산화암모늄, 테트라히드록시메틸암모늄 및 테트라히드록시에틸암모늄으로 이루어진 군으로부터 선택되는 1종 이상인 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물.The texture etching solution composition of claim 1, wherein the alkali compound is at least one selected from the group consisting of potassium hydroxide, sodium hydroxide, ammonium hydroxide, tetrahydroxymethylammonium, and tetrahydroxyethylammonium.
  3. 청구항 1에 있어서, 다당류는 글루칸계 화합물, 프룩탄계 화합물, 만난계 화합물, 갈락탄계 화합물 및 이들의 금속염으로 이루어진 군으로부터 선택된 1종 이상인 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물.The texture etching solution composition of claim 1, wherein the polysaccharide is at least one selected from the group consisting of a glucan compound, a fructan compound, a mannan compound, a galactan compound, and a metal salt thereof.
  4. 청구항 3에 있어서, 다당류는 셀룰로오스, 디메틸아미노에틸셀룰로오스, 디에틸아미노에틸셀룰로오스, 에틸히드록시에틸셀룰로오스, 메틸히드록시에틸셀룰로오스, 4-아미노벤질셀룰로오스, 트리에틸아미노에틸셀룰로오스, 시아노에틸셀룰로오스, 에틸셀룰로오스, 메틸셀룰로오스, 카르복시메틸셀룰로오스, 카르복시에틸셀룰로오스, 히드록시에틸셀룰로오스, 히드록시프로필셀룰로오스, 알긴산, 아밀로오스, 아밀로펙틴, 펙틴, 스타치, 덱스트린, α-시클로덱스트린, β-시클로덱스트린, γ-시클로덱스트린, 히드록시프로필-β-시클로덱스트린, 메틸-β-시클로덱스트린, 덱스트란, 덱스트란설페이트나트륨, 사포닌, 글리코겐, 자이모산, 렌티난, 시조피난 및 이들의 금속염으로 이루어진 군으로부터 선택된 1종 이상의 글루칸계 화합물인 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물.The method of claim 3, wherein the polysaccharide is cellulose, dimethylaminoethyl cellulose, diethylaminoethyl cellulose, ethyl hydroxyethyl cellulose, methyl hydroxyethyl cellulose, 4-aminobenzyl cellulose, triethylaminoethyl cellulose, cyanoethyl cellulose, ethyl Cellulose, methyl cellulose, carboxymethyl cellulose, carboxyethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, alginic acid, amylose, amylopectin, pectin, starch, dextrin, α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin At least one glucan selected from the group consisting of hydroxypropyl-β-cyclodextrin, methyl-β-cyclodextrin, dextran, dextransulfate sodium, saponin, glycogen, zymoic acid, lentinan, sizopinean and metal salts thereof Crystalline Silicone As A Compound Texture etching liquid composition of the wipers.
  5. 청구항 3에 있어서, 다당류는 평균 분자량이 5,000 내지 1,000,000인 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물.The texture etchant composition of claim 3, wherein the polysaccharide has an average molecular weight of 5,000 to 1,000,000.
  6. 청구항 1에 있어서, 지방산은 아세트산, 프로피온산, 부틸산, 발레르산, 에난틱산, 카프릴산, 펠라곤산, 카프릭산, 라우르산, 미리스트산, 팔미트산, 스테아르산, 아라키드산, 베헨산, 리그노세린산, 세로트산, 에이코사펜타엔산, 도코사헥사엔산, 리놀레산, α-리놀렌산, γ-리놀렌산, 디호모-γ-리놀렌산, 아라키돈산, 올레산, 엘라이드산, 에루스산 및 네르본산으로 이루어진 군으로부터 선택된 1종 이상인 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물.The fatty acid according to claim 1, wherein the fatty acid is acetic acid, propionic acid, butyric acid, valeric acid, enantiic acid, caprylic acid, pelagonic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, Behenic acid, lignoseric acid, sertoic acid, eicosapentaenoic acid, docosahexaenoic acid, linoleic acid, α-linolenic acid, γ-linolenic acid, dihomo-γ-linolenic acid, arachidonic acid, oleic acid, elideic acid, e A texture etching solution composition of at least one crystalline silicon wafer selected from the group consisting of loose acid and nerbonic acid.
  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 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 texture etching solution composition for a crystalline silicon wafer further comprising at least one fluorine-based surfactant selected from the group consisting of a small alkyl carboxybetaine, a perfluoroalkyl sulfobetaine, a fluorinated alkyl polyoxyethylene and a perfluoroalkyl polyoxyethylene.
  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 화합물을 더 포함하는 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물.The method of claim 1, further comprising: fine powder silica; Colloidal silica solution stabilized with Na 2 O; Colloidal silica solution stabilized with K 2 O; Colloidal silica solution stabilized with acid solution; Colloidal silica solution stabilized with NH 3 ; Colloidal silica solution stabilized with at least one organic solvent selected from the group consisting of ethyl alcohol, propyl alcohol, ethylene glycol, methyl ethyl ketone and methyl isobutyl ketone; Liquid sodium silicate; Liquid potassium silicate; And at least one silica compound selected from the group consisting of liquid lithium silicate.
  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 실리콘 웨이퍼의 텍스쳐 에칭방법.A method for etching a texture of a crystalline silicon wafer comprising depositing, spraying or depositing and spraying the crystalline silicon wafer with the texture etching liquid composition of any one of claims 1 to 8.
  10. 청구항 9에 있어서, 침적, 분무 또는 침적 및 분무는 50 내지 100℃의 온도에서 30초 내지 60분 동안 수행되는 결정성 실리콘 웨이퍼의 텍스쳐 에칭방법.The method of claim 9, wherein the deposition, spraying or deposition and spraying are performed for 30 seconds to 60 minutes at a temperature of 50 to 100 ° C. 11.
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CN114032035B (en) * 2021-10-28 2022-06-07 常州时创能源股份有限公司 Additive for alkali polishing of silicon wafer and application thereof

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